Valente Andreia, Zinck Philippe, Mortreux André, Visseaux Marc
Synthèses Organométalliques et Catalyse, Unité de Catalyse et Chimie du Solide, UMR CNRS 8181, USTL - ENSCL, Cité Scientifique, 59652 Villeneuve d'Ascq, France.
Macromol Rapid Commun. 2009 Apr 1;30(7):528-31. doi: 10.1002/marc.200800734. Epub 2009 Jan 21.
Borohydrido-halflanthanidocene/dialkylmagnesium combinations are found to be powerful catalytic systems for the chain transfer polymerization of isoprene and its copolymerization with styrene. A behavior close to a lanthanide catalyzed polyisoprene chain growth on magnesium is reported. Transmetalation is further shown to occur in the course of the statistical copolymerization of isoprene and styrene. For the same monomer feed, the amount of styrene inserted in the copolymer can be increased by a factor 3 using 10 equiv. dialkylmagnesium versus 1 in the range of our experimental conditions. Chain transfer in the course of a metal catalyzed statistical copolymerization may thus be viewed as a new and original way for the control of the composition of a copolymer.
发现硼氢化物-半茂镧系元素/二烷基镁组合是异戊二烯链转移聚合及其与苯乙烯共聚的强大催化体系。报道了一种类似于镧系元素催化的聚异戊二烯在镁上链增长的行为。进一步表明，在异戊二烯和苯乙烯的统计共聚过程中发生了金属转移反应。在我们的实验条件范围内，对于相同的单体进料，使用10当量的二烷基镁相对于1当量时，共聚物中插入的苯乙烯量可增加3倍。因此，金属催化的统计共聚过程中的链转移可被视为控制共聚物组成的一种新的原创方法。
