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
Date
1999
Authors
Sanderson R.D.
Costa G.
Summers G.J.
Summers C.A.
Journal Title
Journal ISSN
Volume Title
Publisher
Abstract
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.
Description
Keywords
Amines, Anionic polymerization, Benzene, Gas chromatography, Lithium compounds, Microstructure, Nuclear magnetic resonance spectroscopy, Organic solvents, Organometallics, Polybutadienes, Stoichiometry, Synthesis (chemical), Butyllithium, Divinylbenzene, Gas-liquid chromatography, Initiators (chemical), 1,3 butadiene, benzene derivative, hydrocarbon, organolithium compound, triethylamine, article, chemical reaction, gas liquid chromatography, polymerization, proton nuclear magnetic resonance, purification, reaction analysis, synthesis
Citation
Polymer
40
19
40
19