Anionic block copolymerization of vinyl functionalized triphenylphosphines with styrene

The anionic polymerization of vinyl monomers with electron donating substituents was investigated. The 4- and 3-styryldiphenylphosphines were synthesized and homopolymerized at –85°C in tetrahydrofuran using sec-butyllithium as initiator. Block copolymerization studies were carried out using styrene as a comonomer. 4-Styryldiphenylphosphine (I) forms a much more stabilized anionic chain end than styrene (III). Thus only the sequence III/I is effective in block copolymerization. In contrast, 3-styryldiphenylphosphine (II) can be combined in both ways to block copolymers.