KINETIC AND ELECTRON-SPIN-RESONANCE STUDIES ON THE RADICAL POLYMERIZATION OF DI-NORMAL-BUTYL ITACONATE IN BENZENE
KINETIC AND ELECTRON-SPIN-RESONANCE STUDIES ON THE RADICAL POLYMERIZATION OF DI-NORMAL-BUTYL ITACONATE IN BENZENE
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DOI：
10.1002/pola.1987.080250216
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发表时间：
1987-02-01
影响因子：
--
通讯作者：
TANAKA, K
中科院分区：
文献类型：
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作者：
SATO, T;INUI, S;TANAKA, K
The polymerization of di‐n‐butyl itaconate (DBI) intiated with AIBN was kinetically investigated in benezene. The polymerization rate (Rp) was expressed by:Rp=k[AIBN]0.5[DBI]1.7. The polymerization showed a considerably low overall activation energy of 15.3 kcal/mol. The initiator efficiency of AIBN in this system decreased with increasing DBI concentration, ranging from 0.34 to 0.55°C, which is ascribable to viscosity effect due to the monomer. From an ESR study, the polymerization system was found to involve two kinds of persistent radicals, namely, primary propagating (III) and propagating (I) radicals. The relative concentration ofIIItoIincreased with decreasing monomer concentration. Azo‐nitrile initiators such as AVN and ACN similarly produced two persistent radicals, while MAIB, DBPO, and PBO yielded only propagating radicalIas persistent. The MAIB‐initiated polymerization of DBI was also performed in benzene. Similar kinetic features were observed, that is, a higher dependence ofRpon the DBI concentration and a low overall activation energy (14.4 kcal/mol). The following rate equation was obtained at 50°C:Rp=k[MAIB]0.5[DBI]1.6. The initiator efficiency of MAIB decreased with increasing DBI concentration, ranging from 0.32 to 0.53 at 50°C. The concentration of propagating radicalIwas determined by ESR at 50 and 61°C, from whichkpandktwere estimated. Thekpvalue increased with increasing monomer concentration, while thektone decreased with the DBI concentration. These values are much lower compared with those of MMA.
