Living Anionic Polymerization of 1,4-Divinylbenzene and Its Isomers

Tanaka, Shunsuke; Matsumoto, Masayoshi; Goseki, Raita; Ishizone, Takashi; Hirao, Akira

doi:10.1021/ma302246u

Cited by 28 publications

(58 citation statements)

References 36 publications

(41 reference statements)

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“…m. (m-DVB). 37 ) and/or shorter distance between the two vinyl groups. The 1 H NMR analysis of the star-shaped polymer and the residual arm, which were separated via reprecipitation in n-hexane, indicated that the unreacted vinyl groups remained in the star-shaped polymer and that the ω-end functionality of the arm polymer was low (Supplementary Figure S5).…”

Section: Cationic Polymerization Of St and Its Derivativesmentioning

confidence: 99%

Cationic polymerization of p-methylstyrene using various metal chlorides: design rationale of initiating systems for controlled polymerization of styrenes

Saitoh

Kanazawa

Kanaoka

et al. 2016

Polym J

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Cationic polymerization of p-methylstyrene (pMeSt) was examined using various metal chlorides as Lewis acid catalysts in dichloromethane. All of the catalysts used produced poly(pMeSt)s in the presence of 2,6-di-tert-butylpyridine (DTBP). However, the polymerization behavior differed depending on the type of metal chloride. The polymerization reactions conducted using SnCl 4 and ZnCl 2 proceeded in a controlled manner and yielded well-defined polymers, whereas metal trichlorides (for example, AlCl 3 , FeCl 3 and GaCl 3 ) induced uncontrolled polymerization. In addition, the combination of SnCl 4 and DTBP allowed the controlled polymerization of styrene (St) and p-chlorostyrene (pClSt). Moreover, this initiating system was efficient for the synthesis of star-shaped poly(pMeSt)s via the arm-first method through the addition of an alkylstyrene-type divinyl compound used as a cross-linking agent.

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Section: Cationic Polymerization Of St and Its Derivativesmentioning

confidence: 99%

Cationic polymerization of p-methylstyrene using various metal chlorides: design rationale of initiating systems for controlled polymerization of styrenes

Saitoh

Kanazawa

Kanaoka

et al. 2016

Polym J

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“…SEC profiles of polymers in THF; a) poly( 2 ) obtained with K‐Naph after 1 min (run 9), b) poly( 2 ) with αMSLi/ t BuOK after 1 h (run 13), and c) poly( o ‐DVB) prepared by the anionic polymerization of o ‐DVB under the same condition as run 13 …”

Section: Resultsmentioning

confidence: 93%

“…The anionic polymerizations of DVB isomers, o ‐DVB and m ‐DVB, were also attempted with αMSLi/ t BuOK . The polymerization of o ‐DVB was highly controlled under the identical condition for p ‐DVB described above, giving a soluble polymer with well‐controlled chain structures.…”

Section: Introductionmentioning

confidence: 99%

Anionic Polymerization of Divinylbenzenes Possessing Methoxy Group

OTAKE

Matsumoto

Tanaka

et al. 2017

Macro Chemistry & Physics

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The anionic polymerizations of novel methoxy-substituted divinylbenzenes possessing nonequivalent vinyl groups, such as 2-methoxy-1,4-divinylbenzene (1), 4-methoxy-1,2-divinylbenzene (2), and 4-methoxy-1,3-divinylbenzene (3), are carried out with oligo(α-methylstyryl) lithium (αMSLi) in the presence of potassium tert-butoxide (tBuOK) in tetrahydrofuran at −78 °C. The poly(1)-poly(3) obtained with αMSLi/tBuOK are completely soluble and possess predicted molecular weights and narrow molecular weight distributions (MWD) (M w /M n < 1.1). On the other hand, the corresponding symmetrical divinylbenzenes, 2-methoxy-1,3-divinylbenzene (4) and 5-methoxy-1,3-divinylbenzene (5), undergo anionic polymerization to afford polymers with broad MWDs, indicating the occurrence of a serious intermolecular side reaction. The stability of the propagating carbanion derived from 1-3 is demonstrated by the quantitative efficiency of the sequential copolymerization with tert-butyl methacrylate. The chemical structure of the repeating unit of poly (1)-poly(3) is characterized by the 1 H and 13 C nuclear magnetic resonance measurements, suggesting that the polymerization of asymmetrical divinylbenzenes, 1-3, proceeds mainly on one of the nonequivalent vinyl groups. The electronic and steric effects of the electrondonating methoxy group play important roles in realizing the living anionic polymerization of these divinylbenzenes. The resulting poly(1)-poly(3) show a thermal cross-linking property over 300 °C, indicating the reactivity of the residual pendant vinyl group in each repeating unit.

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“…Although several other potassium alkoxides were found to be also effective in the polymerization of p-DVB, KOBu t was always used throughout this study because it was one of the best additives. 11 The polymerization of p-DIPB readily proceeded in THF at −78°C to afford a soluble polymer in 95% yield after 48 h. The dark red color, characteristic of the living styryl anion derived from p-DIPB, remained unchanged during the polymerization. The resulting polymer shows a sharp SEC peak (M w /M n = 1.03) without any higher-molecular-weight portion ( Figure 1).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Thus, the less stabilized and more reactive chain-end anion may facilitate the addition reaction leading to the chainbranching, like m-DVB previously reported. 11 The polymerization of o-DIPB was also carried out under the identical conditions. In this case, only a small amount of oligomer (average molecular weight = ca.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Living Anionic Polymerization of 1,4-Diisopropenylbenzene

et al. 2015

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The anionic polymerization of diisopropenylbenzene (DIPB) derivatives was conducted in THF at −78°C with a specially designed initiator system prepared from oligo(α-methylstyryl)lithium and an excess potassium tert-butoxide (KOBu t ) (2.7−5.0 equiv to the Li salt). Among the ortho-, meta-, and para-isomers of DIPB derivatives, it was found that the para-isomer (p-DIPB) successfully underwent the living polymerization in a selective manner through one of the two isopropenyl groups under the above stated conditions. With this living polymerization system, soluble polymers with controllable M n values ranging from 7620 to 31 500 g/mol and near monodisperse distributions (M w /M n ≤ 1.03) were obtained for the first time. The obtained living polymers were stable at −78°C even after 168 h and at −40°C after 6 h, in which the intermolecular addition reaction of the chain-end anion to the pendant isopropenyl group could be completely suppressed. In contrast, the living polymerization of either the ortho-or metaisomer was not successful under the same conditions. The block copolymerization of p-DIPB with either styrene (S), 2-vinylpyridine (2VP), or tert-butyl methacrylate ( t BMA) by the sequential addition of such monomers was conducted. Four new PS-block-P(p-DIPB), P2VP-block-P(p-DIPB), P(p-DIPB)-block-P2VP, and P(p-DIPB)-block-P t BMA containing reactive P(p-DIPB) segments were synthesized. On the basis of the block copolymerization results, it is understood that p-DIPB is comparable to 2VP and located between S and t BMA in monomer reactivity. The reactivity increases as follows: S < 2VP ∼ p-DIPB < t BMA, while the nucleophilicity of the living chain-end anion decreases in the following order: PS − > P2VP − ∼ P(p-DIPB) − > P( t BMA) − . ■ INTRODUCTIONIt is known that the intermolecular addition reaction of the chain-end anion to the pendant CH 2 CH bond significantly occurs during the polymerization of 1,4-divinylbenzene (p-DVB). Such the addition reaction results in the formation of highly cross-linked polymers insoluble in solvents. Therefore, p-DVB is generally used as a cross-linking agent to prepare microand macro-gels, but not considered as a typical monomer. 1−9 In 2011, we successfully found that the oligo(α-methylstyryl)-lithium (αMSLi)-initiated anionic polymerization of p-DVB proceeds in a living manner by adding an excess potassium tertbutoxide (KOBu t ) (10 equiv or more). 10 In this polymerization, one of the two CH 2 CH bonds selectively participated the polymerization to quantitatively give the soluble poly(p-DVB)s with predictable M n values up to 60 500 g/mol and near monodisperse distributions (M w /M n ≤ 1.05). 11 The living nature of this system was also guaranteed by the quantitative formation of poly(p-DVB)-block-poly(2-vinylpyridine) and poly(p-DVB)-block-poly(tert-butyl methacrylate) by the sequential addition of p-DVB and then 2-vinylpyridine or tert-butyl methacrylate to the above initiator system. 12The success of the living anionic polymerization of p-DVB may possibly be attributed by ...

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Living Anionic Polymerization of 1,4-Divinylbenzene and Its Isomers

Cited by 28 publications

References 36 publications

Cationic polymerization of p-methylstyrene using various metal chlorides: design rationale of initiating systems for controlled polymerization of styrenes

Cationic polymerization of p-methylstyrene using various metal chlorides: design rationale of initiating systems for controlled polymerization of styrenes

Anionic Polymerization of Divinylbenzenes Possessing Methoxy Group

Living Anionic Polymerization of 1,4-Diisopropenylbenzene

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