Lithium based anionic polymerization of butadiene in apolar media allows the obtention of polybutadiene with a high vinyl content by using polar modifier or alkali metal alkoxide. For instance, butadiene polymerization with alkyllithium and potassium tert-pentoxide produces polybutadiene with 50% of vinyl content. The aim of this paper is to develop an approach without any alkyllithium moieties in order to synthesize polybutadiene with a high vinyl content (50%–70%) in a controlled way. To do so bi-metallic systems based on di-n-butylmagnesium in association with potassium or sodium tert-pentoxide were studied in apolar medium. The influence of parameters such as the initiator preformation time and the [Mt]/[Mg] ratio were assessed (Mt = K, Na). The potassium tert-pentoxide-based system was found to produce polybutadienes in a controlled way with 50% of vinyl content, while polybutadienes with up to 70% of vinyl content were obtained in a controlled way with Na based systems.

在非极性介质中丁二烯的锂基阴离子聚合可通过使用极性改性剂或碱金属醇盐获得高乙烯基含量的聚丁二烯。例如，丁二烯与烷基锂和叔五氧化钾的聚合反应可产生乙烯基含量为50％的聚丁二烯。本文的目的是开发一种不包含烷基锂部分的方法，以便以可控制的方式合成具有高乙烯基含量（50％–70％）的聚丁二烯。为此，基于二正丁基镁与钾或钠叔的双金属系统在非极性介质中研究了五氧化二戊。评估了诸如引发剂预成型时间和[Mt] / [Mg]比之类的参数的影响（Mt = K，Na）。钾叔戊醇为基础的系统被发现在与乙烯基含量50％的控制的方式产生的聚丁二烯，而在与基于钠系统以受控的方式获得具有的乙烯基含量高达70％的聚丁二烯。