Polymerization of Acetaldazine

Kamachi, Mikiharu; Murahashi, Shunsuke

doi:10.1295/polymj.4.651

Cited by 16 publications

(13 citation statements)

References 17 publications

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“…However, there is still arguments in literature about whether the aromatic ring is activated through an intramolecular or an intermolecular complex. [ 34,35 ] Although the exact mechanism is uncertain, the reduced reactivity of VBz is consistent with results obtained from an ongoing study using smallscale batch experiments. As shown in Figure 7 , at 60 °C with 1.0 wt% 2,2′azobis-(2-methylbutyronitrile) (V-67) initiator and 50 vol% EAc solvent, VBz reaches a conversion of less than 5% in 60 min, compared to 34% for VAc.…”

Section: Resultssupporting

confidence: 83%

Vinyl pivalate Propagation Kinetics in Radical Polymerization

Monyatsi

Hutchinson

2015

Macro Chemistry & Physics

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Radical propagation kinetics of the bulk homopolymerizations of vinyl pivalate (VPi) and vinyl benzoate (VBz) have been studied using pulsed‐laser polymerization (PLP) combined with size exclusion chromatography (SEC). As part of the study, the Mark–Houwink parameters of poly(VPi) and poly(VBz) in tetrahydrofuran are determined using a triple detector SEC. The observed significant increase (by ≈ 20%) of the bulk VPi propagation rate coefficient (kp) as pulse repetition rate is increased from 200 to 500 Hz is similar to that reported for vinyl acetate (VAc). Data collected in the temperature range of 25–85 °C for VPi is well fit by the Arrhenius relation ln(kp/L mol−1 s−1) = 15.73−2093(T/K). The activation energy is similar to that found for vinyl acetate (VAc), with kp values higher by ≈ 50%. PLP studies in ethyl acetate and in heptane find no substantial solvent effect on VPi or VAc kp values. Attempts to measure the propagation kinetics of VBz by PLP are not successful, suggesting that significant radical stabilization occurs for the system. Small‐scale batch polymerization experiments demonstrate relative polymerization rates of these vinyl ester monomers that are consistent with the PLP results.

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Section: Resultssupporting

confidence: 83%

Vinyl pivalate Propagation Kinetics in Radical Polymerization

Monyatsi

Hutchinson

2015

Macro Chemistry & Physics

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“…The low molecular weights are ascribed to chain transfer caused by proton transfer from the a-carbon to propagating anions. [41][42][43] Optimization of polymerization conditions led to polymers of alkyl aldehyde azines initiated by Grignard reagents. [44][45][46] Various spectroscopies indicated that the polymers obtained consisted of trans-1,4-addition units and the polymers were crystalline.…”

Section: 3-diazabutadienes (Azines)mentioning

confidence: 99%

Synthesis and polymerizability of CN monomers

Hall

Padías

Kamachi

et al. 2012

J. Polym. Sci. A Polym. Chem.

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The synthesis and polymerizability of imine C¼ ¼N monomers is surveyed. The investigated imines were either far more reactive than similarly substituted C¼ ¼C or C¼ ¼O monomers, or too stable to polymerize. Imines with electron-attracting substituents on N favor polymerization by anionic mechanism, but led only to low molecular weight polymers. Imines with a donor substituent on N, such as N-arylmethyleneimines, polymerized by cationic or anionic mechanism. 1-and 2-Aza-1,3-butadienes were also rather unstable and polymerized to oligomers. The symmetrically substituted 2,3-diaza-1,3-butadienes could be purified and polymerized successfully using anionic initiators, resulting in both 1,4-and 1,2-structures in the polymer backbone, depending on the substituents. KEYWORDS: anionic polymerization; azo polymers; oligomers; polyimines INTRODUCTION Polymerizations involving olefin C¼ ¼C monomers are a major sector of polymer chemistry, while polymerizations of carbonyl C¼ ¼O monomers are also well established. In contrast, polymerizations involving imine C¼ ¼N monomers have received much less attention. In this review, we shall survey existing knowledge in the area of imines and azabutadienes.

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“…Although a number of compounds containing CC or CO double bonds have been polymerized to high molecular weight polymers by radical or ionic initiators, there are no papers on the addition polymerization of compounds with CN double bonds, to our knowledge, except for carbodiimide, 1, 2 isocyanates, − imines, 1-azabutadiene, and azine compounds. − Although 2,3-diaza-1,3-butadiene, formaldehyde azine (CH 2 N−NCH 2 ), which is the simplest azine, was prepared in 1959, there had been no systematic studies concerning the polymerization of the azine compound before the study by Kamachi et al , We have systematically investigated polymerizabilities of other azine compounds to understand polymerizabilities of the CN double bond and to obtain new polymers. − As a result, we have succeeded in the formation of trans -1,4-polymer from alkyl azine compounds (RCHN−NCHR, R = CH 3 , C 2 H 5 , n -C 3 H 7 ) 13-15 and in that of 1,2-polymer from trifluoroacetaldehyde azine (R = CF 3 ) …”

Section: Introductionmentioning

confidence: 99%