Living tert‐butyllithium initiated anionic polymerization of 2‐vinylnaphthalene in toluene‐tetrahydrofuran mixtures

Abstract

The tert-butyllithium (t-BuLi) initiated polymerization of carefully purified 2-vinylnaphthalene in toluene containing small amounts of tetrahydrofuran with respect to t-BuLi proceeds on a timescale of several hours without significant deactivation and allows the synthesis of very narrow molecular weight distribution poly-(2-vinylnaphthalene) (P2VN) (polydispersities as low as 1.04) and molecular weights between 1000 and 20,000. The absence of P2VN-Li deactivation at these conditions is also indicated by high degrees of trimethylsilyl end functionalization (Ͼ95%) and coupling with dibromoxylene. The respective polymerizations of conventionally purified monomer reveal a complex polymerization profile consistent with deactivation by 2-acetylnaphthalene during the early stages of the reaction.

Tailoring mechanical response through coronal layer overlap in tethered micelle hydrogel networks

“…21 This design criterion was enforced such that PS spherical domains assembled in the melt-state would have a chance to vitrify prior to the onset of PEO crystallization during sample cooling. 26 The crude coupling reaction product contained both SOS triblock copolymer and partially reacted or unreacted SO diblock copolymer. This lower limit, in turn, dictates the formation of very large SO block copolymer molecules.…”

The rapid, living, anionic polymerization of 2‐vinylnaphthalene at ambient temperature: Characterization of an n‐butyllithium/tetrahydrofuran system in 1,2,3,4‐tetrahydronaphthalene

“…Among the St derivatives, 2‐vinylnaphthalene (2‐VNP) is favored for the synthesis of naphthalene‐containing polymers, since it tends to produce chain structures with excellent optical and electrical properties. Numerous studies have thus been devoted to the synthesis of poly(2‐VNP) (PVNP) with well‐defined chain structures via the anionic polymerization of 2‐VNP …”

“…reported that the alkyllithium (RLi) and alkylpotassium (RK) initiated anionic polymerization of 2‐VNP in tetrahydrofuran (THF) (or in a toluene/THF mixture) at −78°C appears to proceed via a living reaction process. This same study found that a key factor related to this phenomenon is the application of an unconventional method when purifying commercially available 2‐VNP to remove 2‐acetylnaphthalene, a reagent used during the synthesis of 2‐VNP and an important impurity . Even when using specially purified 2‐VNP, however, the well‐controlled anionic polymerization of this monomer at room temperature remains challenging due to a variety of factors, including side reactions, a low rate of initiation reaction and low initiator efficiency, such that the initiator efficiency at room temperature is actually considerably lower than that at −78°C .…”

Living cationic polymerization of vinylnaphthalene derivatives

“…In addition, the naphthalene ring is a preferable structure for the fine patterning of photoresists because of the light absorption characteristics and the resistance to etching . However, few block copolymers with functional segments have been synthesized, even though anionic and radical mechanisms allow the living polymerization of 2‐vinylnaphthalene (2VN) by taking advantages of the lack of influence due to electron‐rich aromatic rings . Quite recently, the living cationic polymerization of a vinyl ether with a naphthyl group was achieved using base‐assisting initiating systems with a Lewis acid, to give polymers with a narrow MWD and various copolymers .…”

“…28,29 However, few block copolymers with functional segments have been synthesized, even though anionic and radical mechanisms allow the living polymerization of 2-vinylnaphthalene (2VN) by taking advantages of the lack of influence due to electron-rich aromatic rings. [30][31][32][33] Quite recently, the living cationic polymerization of a vinyl ether with a naphthyl group was achieved using baseassisting initiating systems with a Lewis acid, to give polymers with a narrow MWD and various copolymers. 34,35 Interestingly, the T g of the polymers are higher by 40 C than that of poly(vinyl ether) with a phenyl group.…”