Laboratoire de Physico-Chimie, Pharmacotechnie et Biopharmacie, Univ Paris-Sud, UMR CNRS 8612, Faculté de Pharmacie, 5 rue Jean-Baptiste Clément, F-92296 Châtenay-Malabry cedex, France.
Macromol Rapid Commun. 2012 May 14;33(9):805-10. doi: 10.1002/marc.201100866. Epub 2012 Feb 21.
The use of 1,4-dioxane or pyridine as solvents for the polymerization of isoprene mediated by the acid-functional SG1-based alkoxyamines N-(2-methylpropyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxylprop-2-yl)hydroxylamine (BlocBuilder MA) and N-(2-methylpropyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyleth-2-yl)hydroxylamine results in an increase in the rate of consumption of the initiator and narrower molecular weight distributions of the resulting polymer. In pyridine, an improved control of the polymerization was also obtained for a non-acid-functional initiator, and the overall rate of polymerization increased. These effects are likely to be the result of the disruption of intramolecular hydrogen bonding and, in the case of pyridine, stabilization of the polar SG1 free radical.
使用 1,4-二恶烷或吡啶作为溶剂，通过酸功能的基于 SG1 的烷氧基胺 N-(2-甲基丙基)-N-(1-二乙基膦酸-2,2-二甲基丙基)-O-(2-羧基丙-2-基)羟胺（BlocBuilder MA）和 N-(2-甲基丙基）-N-(1-二乙基膦酸-2,2-二甲基丙基）-O-(2-羧乙基-2-基)羟胺引发异戊二烯聚合，会导致引发剂消耗速率增加，所得聚合物的分子量分布变窄。在吡啶中，对于非酸功能引发剂，也可以更好地控制聚合，并且聚合速率整体提高。这些影响可能是由于分子内氢键的破坏，以及在吡啶的情况下，SG1 自由基的稳定化所致。
