Anionic polymerization of 4-phenyl-1-buten-3-yne derivatives bearing electron-withdrawing groups

Abstract

The anionic polymerization of derivatives of 4‐phenyl‐1‐buten‐3‐yne was carried out to investigate the effect of substituents on the polymerization behavior. The polymerization of 4‐(4‐fluorophenyl)‐1‐buten‐3‐yne and 4‐(2‐fluorophenyl)‐1‐buten‐3‐yne in tetrahydrofuran at −78 °C with n‐BuLi/sparteine as an initiator gave polymers consisting of 1,2‐ and 1,4‐polymerized units in quantitative yields with ratios of 80/20 and 88/12, respectively. The molecular weights of the polymers were controlled by the ratio of the monomers to n‐BuLi, and the distribution was relatively narrow (weight‐average molecular weight/number‐average molecular weight < 1.2), supporting the living nature of the polymerization. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1016–1023, 2001

Radical Polymerization Behavior of 4-Monosubstituted and 2,4-Disubstituted Enynes

“…In this respect, the polymerization of conjugated enyne monomers has been studied but most of them gave insufficient information on the polymerization behavior and the polymer structure. [9 -13] In our recent works, polymers with well-defined structures were obtained by the radical [14,15] and the living anionic polymerization [16,17] of 4-phenyl-1-buten-3-yne (1 a) derivatives. The radical polymerization of the 4-aromatic enynes proceeds through the specific 1,2-polymerization to give polymers with acetylene moieties in the side chain.…”

Living Anionic Polymerization of 2-Methyl-4- phenyl-1-buten-3-yne

“…5% of the 1,4-polymerization, see ref. [5] Thus, the 1,2-specific nature of the polymerization of 2 may originate from the character of the monomer 2. As is often reported for propargyl anion, the course o the reaction is very much dependent upon the substituens on the propargyl anions and the character of the electrophiles attacked by the anions.…”

“…[4,5] The polymers consist of both the 1,2-and the 1,4-polymerized units whose ratio was affected slightly by the character of the substituent at the 4-position. Besides, the substituents at the 2-position may also affect the anionic polymerization behavior of enynes.…”

Coordination Polymerization of a Conjugated Enyne: Synthesis of a Novel Polyacetylene Derivative Bearing Conjugated Double Bond Moieties

“…[1,2] Radical copolymerization and living anionic polymerizations provided polymers with both acetylene and allene moieties via 1,2-and 1,4-polymerization. [3,4] Alternatively, on realizing polymerization through their triple bond moieties (i. e. 3,4-polymerization), it might be possible to obtain polyacetylene derivatives having conjugated double bond moieties in the side chain, which might serve as novel functional materials. A polymer of analogous structure has been prepared by the coordination polymerization of 4-hydroxy-4-phenyl-1-butyne followed by dehydration.…”