Institute for Polymer Materials, POLYMAT and Grupo de Ingeniería Química, Departamento de Química Aplicada, Facultad de Ciencias Químicas, University of Basque Country, Joxe Mari Korta zentroa, Tolosa etorbidea 72, Donostia-San Sebastián 20018, Spain.
Macromol Rapid Commun. 2011 Jan 3;32(1):63-7. doi: 10.1002/marc.201000375. Epub 2010 Sep 20.
Acrylic monomers undergo chain transfer to polymer during polymerization leading to branched and even gelled polymers. It has been experimentally demonstrated that the extent of branching is higher for conventional free radical polymerization than for controlled radical polymerization (ATRP, RAFT, NMP) and this has been qualitatively explained in terms of the differences in the concentrations of highly reactive short-chain radicals between controlled and conventional radical polymerizations. Contrary to this explanation, in this work, it is quantitatively demonstrated that the short transient lifetime of the radicals, i.e., the time between activation and deactivation of the radical in controlled radical polymerization, is the cause for the low level of branching in these polymerizations.
亚克力单体在聚合过程中会向聚合物链转移，导致支化甚至凝胶化聚合物的形成。实验已经证明，传统自由基聚合的支化程度高于可控自由基聚合（ATRP、RAFT、NMP），这可以从可控和传统自由基聚合中高活性短链自由基浓度的差异来定性解释。与这种解释相反，在这项工作中，定量证明了自由基的短暂暂态寿命，即在受控自由基聚合中自由基的活化和失活之间的时间，是这些聚合中支化程度低的原因。
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