Anionic Self-alternating Polymerization of 1-(4-Vinylphenyl)-1-phenylethylene

Kim, Hamin; Goseki, Raita; Ishizone, Takashi

doi:10.1021/acs.macromol.2c01515

Cited by 6 publications

(15 citation statements)

References 43 publications

(72 reference statements)

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“…This indicates that the anionic self-alternating polymerization of ClVD is also achieved with Ph 2 CHLi. In a previous report, we found that counterions have negligible effect on the proposed anionic self-alternating polymerization by estimating the polymerized unit in poly( VD ) …”

Section: Resultsmentioning

confidence: 99%

“…Relationship between the Hammett parameter and C β chemical shifts of St (red, C βSt ) and DPE (blue, C βDPE ) frameworks and polymer yields (Table , initiator: Ph 2 CHK; at −78 °C for 72 h). The yield of poly( VD ) was obtained from the previous result …”

Section: Resultsmentioning

confidence: 99%

“…MALDI-TOF-MS spectra of poly( VD ) obtained with Ph 2 CHK at −78 °C for 72 h (A) and poly( ClVD ) obtained with Ph 2 CHK at −78 °C for 168 h (B: run ClVD-2) (matrix: trans -2-[3-(4- tert -butylphenyl)-2-methyl-2-propenylidene]malononitrile (DCTB), ionizing agent: silver trifluoroacetate).…”

Section: Resultsmentioning

confidence: 99%

“…We recently discovered a unique polymerization behavior of a kind of AB-type divinyl monomer (4-vinyl-1,1-diphenylethylene, VD ), possessing two vinyl groups of styrene (St) and 1,1-diphenylethylene (DPE) frameworks, which results in the formation of a “sequence-controlled homopolymer” (Scheme ). The anionic copolymerization of St and DPE is known to yield a copolymer with an alternating sequence. − Although DPE derivatives also show nonhomopolymerizability under various conditions, − it is anionically copolymerizable with St derivatives. In fact, VD undergoes anionic “homo” polymerization by consuming two CC bonds, one of A and one of B, to produce a well-defined polymer possessing a controlled molecular weight and a narrow molecular weight distribution (MWD).…”

Section: Introductionmentioning

confidence: 99%

“…41 In this case, two polymerizable groups, vinyl (A) and cyclopropyl (B), were not independent in the polymerization (43) Even though n-BuLi and sec-BuLi were generally used in the anionic polymerization as an initiator, the anionic polymerization of VD with sec-BuLi showed relatively broaden MWD compared to with the Ph 2 CHK initiator. 18 Thus, we chose Ph 2 CHK as the optimized initiator to investigate the anionic polymerization behaviors of VD derivatives.…”

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confidence: 99%

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Synthesis of Sequence-Controlled Homopolymer via Anionic Self-Alternating and Chemoselective Polymerization of 4-Vinyl-1,1-diphenylethylene Derivatives

Kim,

Goseki,

Homma

et al. 2023

Macromolecules

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Anionic polymerization of AB-type difunctional monomers derived from 4-vinyl-1,1-diphenylethylene (VD) bearing styrene and 1,1-diphenylethylene (DPE) frameworks was examined using diphenylmethylpotassium (Ph2CHK) in THF at −78 to 0 °C. A series of substituents including chloro (ClVD), methyl (MeVD), methoxy (MeOVD), and dimethylamino (Me2NVD) groups were introduced at the 4′-position of the VD framework to vary the polymerizability of VD. In each case, the resulting polymer was soluble and possessed the predicted molecular weight and a narrow molecular weight distribution (Đ, M w/M n = 1.1–1.3). The 1H and 13C NMR measurements and MALDI-TOF-MS analysis revealed that a “self-alternating polymerization” of ClVD, MeVD, and MeOVD yielded a linear homopolymer with an (AB) n -type alternating sequence through the intermolecular cross-propagation chain-growth mechanism. In particular, the resulting poly(ClVD) exhibited only an odd-numbered degree of polymerization, indicating a mechanism of exclusive initiation and subsequent self-alternating polymerization of the VD derivative. In contrast, Me2NVD underwent the usual chemoselective polymerization in the styrene framework to yield an (A) n -type sequence because the electrophilicity of the DPE unit of Me2NVD was highly reduced. Thus, the electronic effect of the substituents determines the polymerization behavior of the VD derivatives.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Synthesis of Sequence-Controlled Homopolymer via Anionic Self-Alternating and Chemoselective Polymerization of 4-Vinyl-1,1-diphenylethylene Derivatives

Kim,

Goseki,

Homma

et al. 2023

Macromolecules

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Effect of tetrahydrofuran on the anionic copolymerization of 4‐trimethylsilylstyrene with isoprene

Fuchs,

Wadgaonkar,

Müller

et al. 2024

Polymers for Advanced Techs

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The statistical anionic copolymerization of 4‐trimethylsilylstyrene (TMSS) with isoprene (I) in cyclohexane was investigated using in situ near‐infrared (NIR) spectroscopy in the presence of various amounts of the polar modifier tetrahydrofuran (THF). Polymers with narrow molecular weight distribution of 85–138 kg/mol and dispersities of 1.09–1.22 were obtained. By increasing modifier content, the reactivity ratios can be adjusted over a wide range from rTMSS < rI to rTMSS >> rI. Compared to the system styrene/isoprene (S/I) only a minute amount of modifier (0.5 eq THF relative to lithium) is sufficient to alter the reactivity ratios, resulting in an ideally random copolymerization, which validates the higher reactivity of TMSS compared to styrene. Using these reactivity ratios, molar and volume composition gradients were calculated. Additionally, the glass transition temperature and microstructure of the polyisoprene units were investigated via differential scanning calorimetry and proton nuclear magnetic resonance. The results are encouraging for the use of these materials in high‐end applications like membranes.

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Living anionic polymerization of vinyl monomers using benzyltrimethylsilane‐metal alkoxide initiator systems

Hiraki,

Terasaki,

Adachi

2023

Journal of Polymer Science

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Well controlled living anionic polymerization of vinyl monomers was achieved by using the initiator system composed of desilylation of benzyltrimethylsilane (BnTMS) by potassium tert‐butoxide (t‐BuOK) in tetrahydrofuran and trapping the resulting benzyl anion with α‐methylstyrene or 1,1‐diphenylethylene in the initiator system in order to control the desilylation and polymerization reaction. This method led to high initiation efficiency and strict control of molecular weights of the obtained polymers. Furthermore, the initiator system could be applied to the synthesis of a block copolymer of PMMA‐b‐PtBMA. These results showed that living nature of the polymer obtained using BnTMS/t‐BuOK initiator system in the presence of the appropriate additives.

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Anionic Self-alternating Polymerization of 1-(4-Vinylphenyl)-1-phenylethylene

Cited by 6 publications

References 43 publications

Synthesis of Sequence-Controlled Homopolymer via Anionic Self-Alternating and Chemoselective Polymerization of 4-Vinyl-1,1-diphenylethylene Derivatives

Synthesis of Sequence-Controlled Homopolymer via Anionic Self-Alternating and Chemoselective Polymerization of 4-Vinyl-1,1-diphenylethylene Derivatives

Effect of tetrahydrofuran on the anionic copolymerization of 4‐trimethylsilylstyrene with isoprene

Living anionic polymerization of vinyl monomers using benzyltrimethylsilane‐metal alkoxide initiator systems

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