Study of the Termination of Two Acrylonitrile Radicals and Infrared Spectrum
LI Xin1, YANG Meng-shi1, XU Can3, SONG Ping-an1, CHEN Liang2*, DU Hong-chen2, WANG Yu2
1. School of Engineering，Zhejiang Agriculture and Forestry University，Lin’an 311300，China 2. School of Science，Zhejiang Agriculture and Forestry University，Lin’an 311300，China 3. Key Lab for Magnetism and Magnetic Materials of Ministry of Education，School of Physical Science and Technology，Lanzhou University, Lanzhou 730000，China
Abstract：By using the density functional theory, the study of reaction termination mechanism of two (CH3)2(CN)C—CH2—(CN)CH was carried out at the B3LYP/6-31G(d) level. The initiator AIBN was used. Reactants, coupled intermediates, transition states and disproportionation products were optimized at the B3LYP/6-31G(d) level. Then the total energies corrected by zero-point energy, vibrational frequencies and electronic structures were calculated, the transition states structure was also verified. The results show that it forms the energy-rich adducts a through the coupling termination. Then, the disproportionation product P[p1(CH3)2(CN)CCHCHCN+p2(CH3)2(CN)C—CH2—CH2CN]formed via hydrogen shift and dissociation. The reactions of coupling termination and disproportionation termination are all exothermic reactions, and the coupled product has lower energy. The rate constant of step a→TS→P is k(298.15 K)=2.71×10-59 at the normal atmospheric temperature. Disproportionation termination occurs more easily with the reaction temperature rising, so the proportion of disproportionation products is increasing. Also, the analysis of infrared spectrogram of each species in reaction process shows chemical change of free radicals in the whole termination reaction. The authors give the HOMO-LUMO in this paper to verify the accuracy of biradical coupling termination and structures. It has important guiding significance to controlling the free radicals termination methods of acrylonitrile monomer.
李 鑫1，羊梦诗1，徐 灿3，宋平安1，陈 亮2*，杜洪臣2，王 禹2 . 丙烯腈单体自由基反应及光谱分析的研究 [J]. 光谱学与光谱分析, 2014, 34(09): 2331-2336.
LI Xin1, YANG Meng-shi1, XU Can3, SONG Ping-an1, CHEN Liang2*, DU Hong-chen2, WANG Yu2 . Study of the Termination of Two Acrylonitrile Radicals and Infrared Spectrum . SPECTROSCOPY AND SPECTRAL ANALYSIS, 2014, 34(09): 2331-2336.
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