Living Anionic Polymerization of Styrene Derivatives Containing Triphenylamine Moieties through Introduction of Protecting Group

Abstract

We carried out the anionic polymerization of styrene derivatives containing the triphenylamine moieties, 4,4′-vinylphenyltriphenylamine (A) and 4,4′-vinylphenyl- N,N -bis(4-tert-butylphenyl)benzenamine (B), with a variety of initiators in tetrahydrofuran (THF) at −78 °C. The anionic polymerization of A was performed with sec-butyllithium, sec-butyllithium with additives, and (diphenylmethyl)potassium in THF at −78 °C. In all cases, an intermolecular side reaction took place between the polymer chains during polymerization. In contrast, the anionic polymerization of B was carried out successfully with sec-butyllithium and potassium naphthalenide in THF at −78 °C for 0.5 h without any observed intermolecular side reaction. Well-defined poly(B)s with predictable molecular weights and narrow molecular weight distributions (M w/M n = 1.05−1.11) were obtained. The sequential block copolymerization of B with styrene and 2-vinylpyridine was attempted subsequently, and the well-defined block copolymers, polystyrene-b-poly(B) and poly(B)-b-poly(2-vinylpyridine), were synthesized quantitatively. The solubilities as well as the thermal and optical properties of the resulting poly(B) were investigated.

Precise synthesis of thermoreversible block copolymers containing reactive furfuryl groups via living anionic polymerization: the countercation effect on block copolymerization behavior

“…38,44 Furfuryl isocyanate (B, Aldrich, 97%) was dried overnight over CaH 2 , distilled under reduced pressure, and finally distilled from CaH 2 on a vacuum line into ampules equipped with break-seals. 38,44 Furfuryl isocyanate (B, Aldrich, 97%) was dried overnight over CaH 2 , distilled under reduced pressure, and finally distilled from CaH 2 on a vacuum line into ampules equipped with break-seals.…”

“…The colorless solution was maintained at −98°C for 0.5 h. After terminating the polymerization, it was verified by SEC that no block copolymerization occurred. 20,21,38,42 Accordingly, it appears that an undesirable side reaction took place when B was added to the living poly(A) solution. As shown in Fig.…”

“…In particular, this [4 + 2] cycloaddition reaction between a diene and a dienophile is a thermally reversible process, and therefore cross-linked polymeric products prepared via the DA reaction can be used for self-healing applications. [38][39][40][41][42][43] Thermally cross-linkable block copolymers, poly(4-ethynylstyrene)-b-poly(A)-b-poly(4-ethynylstyrene) and poly(A)-b-poly(4-ethynylstyrene), have been synthesized as an alternative hole-transporting layer to PEDOT: PSS in polymer light-emitting diodes and an active layer of the memory device. From the synthetic point of view, successful living anionic polymerization of functional monomers allows preparation of welldefined block copolymers with various functionalities.…”

Facile anionic synthesis of a well-controlled thermally cross-linkable block copolymer for polymer-based resistive memory device applications

“…[1][2][3][4][5][6] From the synthetic viewpoint, successful living anionic polymerization of certain monomers allows functional block copolymers with precise macromolecular structures to be prepared by sequential addition of monomers. [10][11][12][13] In general, the block copolymerization has to be performed by sequential addition of a less reactive monomer as the first monomer and a more reactive monomer as the second monomer to obtain the well-defined block copolymers. [10][11][12][13] In general, the block copolymerization has to be performed by sequential addition of a less reactive monomer as the first monomer and a more reactive monomer as the second monomer to obtain the well-defined block copolymers.…”

“…[11][12][13] For instance, from the living nature of 4,4′-vinylphenyl-N,N-bis(4-tert-butylphenyl)benzenamine (B), the reactivity of B could be determined by block copolymerization with functional monomers such as St and 2-vinylpyridine (2VP). [11][12][13] For instance, from the living nature of 4,4′-vinylphenyl-N,N-bis(4-tert-butylphenyl)benzenamine (B), the reactivity of B could be determined by block copolymerization with functional monomers such as St and 2-vinylpyridine (2VP).…”