The synthesis of a hydrocarbon-soluble organolithium anionic initiator. A gas-liquid chromatography study of the efficiency of the reaction of s- butyllithium with p-divinylbenzene

Sanderson R.D. ; Costa G. ; Summers G.J. ; Summers C.A. (1999)

Article

The extent of conversion of the reaction between sec-butyllithium and p- divinylbenzene was evaluated by quantitative gas-liquid chromatography. The reaction of stoichiometric amounts of ultra-high purity sec-butyllithium with pure p-divinylbenzene at 0°C produces an anionic initiator, 1,4-bis(1- lithio-3-methylpentyl)benzene, 2, in essentially quantitative yields, with low concentrations of monofunctional impurities. Upon the addition of 10 mol% excess of triethylamine to sec-butyllithium, the reaction of sec-butyllithium with p-divinylbenzene at 0°C yielded a homogeneous product with composition of 96% difunctionality and 4% monofunctionality, with the total disappearance of p-divinylbenzene as observed by GLC. The high purity 1,4-bis(1-lithio-3- methylpentyl)benzene initiator, 2, is an effective initiator for 1,3- butadiene polymerizations in hydrocarbon solvents and allows the synthesis of polybutadienes with microstructures ranging from 13% to 16% 1,2-vinyl content, as observed by 1H NMR analysis.The extent of conversion of the reaction between sec-butyllithium and p-divinylbenzene was evaluated by quantitative gas-liquid chromatography. The reaction of stoichiometric amounts of ultra-high purity sec-butyllithium with pure p-divinylbenzene at 0 °C produces an anionic initiator, 1,4-bis(1-lithio-3-methylpentyl)benzene, 2, in essentially quantitative yields, with low concentrations of monofunctional impurities. Upon the addition of 10 mol% excess of triethylamine to sec-butyllithium, the reaction of sec-butyllithium with p-divinylbenzene at 0 °C yielded a homogeneous product with composition of 96% difunctionality and 4% monofunctionality, with the total disappearance of p-divinylbenzene as observed by GLC. The high purity 1,4-bis(1-lithio-3-methylpentyl)benzene initiator, 2, is an effective initiator for 1,3-butadiene polymerizations in hydrocarbon solvents and allows the synthesis of polybutadienes with microstructures ranging from 13% to 16% 1,2-vinyl content, as observed by 1H NMR analysis.

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