화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.19, No.10, 1041-1047, October, 2011
DOI10.1007/s13233-011-1007-5  Export Citation
The Effect of the Spacer Length on Binitroxide Mediated Radical Polymerization of Styrene
Andrzej Kaim†, Jadwiga Szydłowska1, and Krzysztof Pietrasik
  • Laboratory of Physicochemical Fundamentals of Chemical Technology, Chemical Department, University of Warsaw, Pasteura 1, 02-093, Warsaw, Poland
  • 1Laboratory of Dielectrics and Magnetics, Chemical Department, University of Warsaw, Al. Zwirki i Wigury 101, 02-089, Warsaw, Poland, Korea
E-mail:
Series of binitroxides, (N,N’-bis(4-(2,2,6,6-tetramethylpiperidin-1-yloxyl)diaminoalkane), ㆍCnㆍ (n=0, 2, 3, 4 methylene groups), was used as mediators in the radical polymerization of styrene initiated with benzoyl peroxide(BPO). The length of the methylene spacer linking two 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) radicals affected the polymerization process. For the mediators, ㆍC0ㆍ, ㆍC2ㆍ and ㆍC3ㆍ, elongation of the spacer decreases the conversion rate as well as the number average molecular weight (Mn), molecular weight distribution (MWD) and polydispersity index (PDI). For all these mediators, a bimodal MWD was confirmed. The use of N,N’-bis(4-(2,2,6,6-tetramethylpiperidin-1-yloxyl))diaminobutane, ㆍC4ㆍ, results in trimodal MWD with an additional polymer fraction with a high molecular weight originating from an uncontrolled process. In the initial stages of polymerization, electron spin resonance spectroscopy (ESR) showed that the combination reaction between ㆍC4ㆍ and growing polymer chain (Pㆍ) is much slower than that for the ㆍC0ㆍ controlling agent, thereby promoting the synthesis of long polymer chains. With the exception of the ㆍC0ㆍ mediator, the remaining biradicals did not exhibit spin-spin interactions between the TEMPO groups in the propagation of polymerization. Therefore, the spin-spin coupling between binitroxide ends does not appear to have a remarkable influence on the polymerization process.
Keywords:controlled/living polymerization binitroxide;styrene;electron spin resonance.
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