A stepping stone to stereospecific living cationic polymerization: Cationic polymerization of vinyl ethers using iron(II) sulfate

Kanazawa, Arihiro; Kanaoka, Shokyoku; Aoshima, Sadahito

doi:10.1002/pola.24144

Cited by 31 publications

(20 citation statements)

References 46 publications

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“…The 1 H NMR spectrum of poly(αNpOVE) contained some small peaks in the range of 5–6 ppm, whereas no peaks appeared in this region for poly(βNpOVE). The peaks were assigned to the methine protons ( p , Scheme ) of the structures resulting from Friedel–Crafts reactions36 and to the olefin protons ( q and r , Scheme ) owing to side‐chain alcohol abstraction 38,39. The comparison of the integral ratios of peak r and the other peaks ( p and q ) suggested that Friedel–Crafts reactions were the primary side reactions.…”

Section: Resultsmentioning

confidence: 99%

Living cationic polymerization of vinyl ethers with a naphthyl group: Decisive effect of the substituted position on naphthalene ring

Shinke

Kanazawa

Kanaoka

et al. 2012

J. Polym. Sci. A Polym. Chem.

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Living cationic polymerization of a vinyl ether with a naphthyl group [2‐(2‐naphthoxy)ethyl vinyl ether, βNpOVE] was achieved using base‐assisting initiating systems with a Lewis acid. The Et1.5AlCl1.5/1,4‐dioxane or ethyl acetate system induced the living cationic polymerization of βNpOVE in toluene at 0 °C. The living nature of this reaction was confirmed by a monomer addition experiment, followed by 1H NMR and matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry (MALDI‐TOF‐MS) analyses. In contrast, the polymerization of αNpOVE was not fully controlled; under similar conditions, it produced polymers with broad molecular weight distributions. The 1H NMR and MALDI‐TOF‐MS spectra of the resultant poly(αNpOVE) revealed that the products had undesirable structures derived from Friedel–Crafts alkylation. The higher reactivity of αNpOVE in electrophilic substitution reactions, such as the Friedel–Crafts reaction, was attributable to the greater electron density of the naphthyl ring, which was calculated based on frontier orbital theory. The naphthyl groups significantly affected the properties of the resultant polymer. For example, the glass transition temperatures (Tg) of poly(NpOVE)s are higher by approximately 40 °C than that of poly(2‐phenoxyethyl vinyl ether). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

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Section: Resultsmentioning

confidence: 99%

Living cationic polymerization of vinyl ethers with a naphthyl group: Decisive effect of the substituted position on naphthalene ring

Shinke

Kanazawa

Kanaoka

et al. 2012

J. Polym. Sci. A Polym. Chem.

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“…Conversely, the characteristic resonances at δ = 4.56 ppm and δ = 9.81 ppm are assigned to C H O (peak 7), and C H O (peak 10) terminal groups, respectively. The content of C H O terminal group was determined to be 74% as polymerization was quenched with CH 3 OH or i ‐BuOH 20, 21. There was no signal (δ = 6.1 ppm) belonging to the structure of CHC H O i Bu due to β‐elimination.…”

Section: Resultsmentioning

confidence: 99%

Cationic polymerization of isobutyl vinyl ether coinitiated with heteropolyacid or its salts in aqueous medium

Huang

Dan

2012

J. Polym. Sci. A Polym. Chem.

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The suspension cationic polymerization of isobutyl vinyl ether (IBVE) in aqueous medium could be achieved by using H3PW12O40, AlPW12O40, FePW12O40, K3PW12O40, or Na3PW12O40 as efficient water‐tolerant coinitiators in the presence of HCl. The addition reaction of IBVE with H2O occurred to form IBVE–H2O adduct and then subsequent decomposition immediately took place or turned to acetaldehyde diisobutyl acetal (A) in the presence of AlPW12O40, and (A) decomposed rapidly to form 2‐isobutanol (B) and acetaldehyde (C). Cationic polymerization of IBVE in aqueous medium was promoted greatly with increasing HCl concentration and proceeded extremely rapidly to get high polymer yield even at low concentration of AlPW12O40 of 0.3 mM. A sufficient amount of HCl was needed to decrease the hydrolysis of initiator IBVE–HCl and to accelerate the polymerization in aqueous medium simultaneously. The yield and molecular weight of poly(IBVE) increased with increasing concentrations of HCl and AlPW12O40 or with decreasing temperature. The isotactic‐rich poly(IBVE)s with m diad of around 60%, having Mn of 1200–4500 g mol−1 and monomodal molecular weight distribution could be obtained via cationic polymerization of IBVE in aqueous medium. This is the first example of cationic polymerization of IBVE in aqueous medium coinitiated by heteropolyacid and its salts. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

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“…For instance, addition of lanthanide Lewis acids such as Yb(OTf) 3 , Lu(OTf) 3 , and Sc(OTf) 3 induced it-specific radical polymerization of N-isopropylacrylamide (NIPAAm) (m ¼ 92 %, with Yb(OTf) 3 , in MeOH at À20 C). Vinyl ethers can be polymerized by cationic initiators; however, a limited number of reports on highly stereospecific cationic polymerization have been presented [8]. Cationic polymerization of tert-butyl vinyl ether with BF 3 -based initiators in toluene gave it-polymer (mm ¼ 79 %), which can readily be converted to it-poly(vinyl alcohol).…”

Section: Isotactic Specific Polymerizationmentioning

confidence: 99%

“…Nevertheless, they have the possibility of relative handedness [4,5,[7][8][9][10]. The simplest regular arrangements along a polymer chain are the isotactic (it-) stereostructure, in which all the substituents are located on the same side of the zigzag plane repeating the chain stretched out in an all-trans conformation.…”

Section: Vinyl Polymerization A-substituted and A A-disubstituted VImentioning

confidence: 99%

Stereospecific Polymerization

Hirano

Kitaura

2014

Encyclopedia of Polymeric Nanomaterials

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A stepping stone to stereospecific living cationic polymerization: Cationic polymerization of vinyl ethers using iron(II) sulfate

Cited by 31 publications

References 46 publications

Living cationic polymerization of vinyl ethers with a naphthyl group: Decisive effect of the substituted position on naphthalene ring

Living cationic polymerization of vinyl ethers with a naphthyl group: Decisive effect of the substituted position on naphthalene ring

Cationic polymerization of isobutyl vinyl ether coinitiated with heteropolyacid or its salts in aqueous medium

Stereospecific Polymerization

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