Cyclopolymerization of divinyloxy monomers by iodine

Seung, S. L. N.; Young, R. N.

doi:10.1002/pol.1978.130160709

Cited by 15 publications

(3 citation statements)

References 3 publications

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“…If the reaction conditions are properly selected, however, soluble polymers can be obtained by their cyclopolymerization. Seung and Young,3 Butler and Lien,4, 5 Mathias and Canterberry,6, 7 and Yokota et al8 demonstrated one of the easiest routes for the synthesis of soluble polymers with a chain ring structure via the cationic cyclopolymerization of divinyl ethers.…”

Section: Introductionmentioning

confidence: 99%

Cationic cyclopolymerization of new divinyl ethers: The effect of ether and ester neighboring functional groups on their cyclopolymerization tendency

Rahman

Hashimoto

Kodaira

2002

J. Polym. Sci. A Polym. Chem.

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The cationic polymerization of two new divinyl ethers, 1-(2-vinyloxyethoxy)-2-[(2-vinyloxyethoxy)carbonyl]benzene (2) and 1,2-bis[(2-vinyloxyethoxy)carbonyl]benzene (3), as well as 1,2-bis(2-vinyloxyethoxy)benzene (1), with BF 3 OEt 2 in CH 2 Cl 2 at 0°C at low initial monomer concentrations ([M] 0 ϭ 0.15 and 0.075 M) gave soluble polymers with relatively high molecular weights and broad molecular weight distributions (MWDs), whereas reactions with the HCl/ZnCl 2 initiating system yielded soluble polymers with relatively narrow MWDs (weight-average molecular weight/number-average molecular weight Շ 1.6) under similar reaction conditions. An NMR structural analysis of the HCl/ZnCl 2 -mediated polymers from the divinyl ethers showed that poly(1) had virtually no unreacted vinyl ether groups throughout the polymerization (monomer conversion ϭ 28 -98%), whereas poly(2) and poly(3) possessed some amount of unreacted vinyl ether groups in the initial stage of the polymerization; the content of the vinyl groups of poly(2) was 18 mol % at a 15% monomer conversion, and the content of the vinyl groups of poly(3) was 31 mol % at an 18% monomer conversion. Therefore, divinyl ether 1 underwent cyclopolymerization exclusively to give almost completely cyclized polymers [degree of cyclization (DC) ϳ 100%], whereas divinyl ethers 2 and 3 exhibited a lower cyclopolymerization tendency [DC for poly(2) ϭ 82%; DC for poly(3) ϭ 69%]. The differences in the cyclopolymerization tendencies among the divinyl ethers can be explained by the differences in the solvation powers of the neighboring functional groups adjacent to the vinyl ether moiety with the active center: the ether oxygen of the ether neighboring group solvates intramolecularly with the active center to accelerate the intramolecular propagation, but such an interaction is less effective with the more electron-deficient oxygen attached to the carbonyl group of the ester neighboring group.

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Section: Introductionmentioning

confidence: 99%

Cationic cyclopolymerization of new divinyl ethers: The effect of ether and ester neighboring functional groups on their cyclopolymerization tendency

Rahman

Hashimoto

Kodaira

2002

J. Polym. Sci. A Polym. Chem.

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“…Figure7 shows the NMR spectrum of the former triblock, indicating the existence of both MVE and CVE units.…”

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confidence: 99%

Synthesis of telechelic living poly(vinyl ethers)

Miyamoto¹,

Sawamoto²,

Higashimura³

1985

Macromolecules

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Reaction of ethyl vinyl ether (EVE) with an equimolar amount of hydrogen iodide (HI) in nonpolar solvents at -30 °C gave an adduct [CH3CH(OEt)I] (1) in quantitative yield. Similarly to the HI/I2 initiating system, 1, in conjunction with iodine, initiated living polymerization of a series of vinyl ethers in nonpolar media at -5 to -40 °C to give monodisperse polymers. Treatment of l,4-bis(vinyloxy)butane with 2 equiv of HI led to a diadduct [CH3CH(I)0(CH2)40CH(I)CH3] (2) quantitatively, under the conditions similar to those for the EVE/HI system. In the presence of 2 equiv of iodine, 2 acted as an effective bifunctional initiator that generated monodisperse, telechelic living poly(vinyl ethers) in nonpolar solvents at -40 °C. These bifunctional living polymers were capable of polymerizing vinyl ethers to give ABA-type triblock copolymers with a narrow molecular weight distribution in a high blocking efficiency; e.g., poly(methyl vinyl ether-b-hexadecyl vinyl ether-b-methyl vinyl ether). Telechelic poly(EVE) having sec-amino termini was obtained by quenching the living ends with n-butylamine. Chain extension using hexamethylenediamine as coupling agent led to poly(EVE) with in-chain amino ether linkages and a broad molecular weight distribution extending from 104 to 106.

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“…Divinyl ethers undergo crosslinking polymerization1–3 or cyclopolymerization3–9 via a cationic mechanism depending on monomer structure and the reaction conditions. We have investigated cationic crosslinking polymerizations of 1,4‐bis[(2‐vinyloxy)ethoxy]benzene ( 1 )10 and 2,2‐bis{4‐[(2‐vinyloxy)ethoxy]phenyl}propane11 in methylene chloride solvent at 0 °C at a relatively low initial monomer concentration ([M] 0 = 0.15 M) mainly with the diphenyl phosphate [(C 6 H 5 O) 2 P(O)OH]/zinc chloride (ZnCl 2 ) initiating system and found that the polymerization gave crosslinked insoluble polymers, but before gelation, almost all unreacted vinyl groups of the soluble polymers were consumed.…”

Section: Introductionmentioning

confidence: 99%

Effect of central spacer chain structure on cationic cyclopolymerization tendency of divinyl ethers

Hashimoto

Ohashi

Kodaira

2002

J. Polym. Sci. A Polym. Chem.

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To clarify the effects of the central spacer chain structure of divinyl ethers on their cationic cyclopolymerization tendencies, 1,4‐bis[(2‐vinyloxy)ethoxy]benzene (1), 1,4‐bis[(2‐vinyloxy)ethoxy]butane (2), 1,6‐bis[(2‐vinyloxy)ethoxy]hexane (3), 1,8‐bis[(2‐vinyloxy)ethoxy]octane (4), and 1,4‐bis[(4‐vinyloxy)butoxy]butane (5) were polymerized with the hydrogen chloride/zinc chloride (HCl/ZnCl2) initiating system in methylene chloride (CH2Cl2) at 0 °C at low initial monomer concentration ([M]0 = 0.15 M). The polymerizations of divinyl ethers 2 and 3 gave soluble polymers quantitatively. In contrast, the polymerizations of divinyl ethers 1, 4, and 5 underwent gel formation at high monomer conversion. The content of the unreacted vinyl groups of the obtained soluble polymers was measured by 1H NMR spectroscopy. Judging from the relatively low vinyl contents of the polymers produced even in the early stage of the polymerization (monomer conversion < ∼20%), the cyclopolymerization occurred to some extent for 2, 3, and 4. On the contrary, the polymers produced from 1 and 5 exhibited the relatively high vinyl content, indicating that the cyclopolymerization tendencies of 1 and 5 were lower than those of 2, 3, and 4. These results are discussed in terms of the structural variety of the spacer chains: (1) the presence of benzene ring (1 vs 2), (2) their length (2 vs 3 and 4), and (3) the position of ether oxygen (4 vs 5). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4002–4012, 2002

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Cyclopolymerization of divinyloxy monomers by iodine

Cited by 15 publications

References 3 publications

Cationic cyclopolymerization of new divinyl ethers: The effect of ether and ester neighboring functional groups on their cyclopolymerization tendency

Cationic cyclopolymerization of new divinyl ethers: The effect of ether and ester neighboring functional groups on their cyclopolymerization tendency

Synthesis of telechelic living poly(vinyl ethers)

Effect of central spacer chain structure on cationic cyclopolymerization tendency of divinyl ethers

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