α‐Halogenated carboxylic acids and their corresponding zinc salts in the living polymerization of isobutyl vinyl ether

Kim, Young H.; Heitz, Thomas

doi:10.1002/marc.1990.030111102

Cited by 14 publications

(9 citation statements)

References 19 publications

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“…Polymerization of IBVE was then examined with other cationogens such as IBVE–TFA,31, 32 IBVE–AcOH,20, 21 and H 2 O. These function as initiating species for cationic polymerization by liberating trifluoroacetoxy, acetoxy, and hydroxy anions, respectively, with the help of Lewis acid catalysts.…”

Section: Resultsmentioning

confidence: 99%

Living cationic polymerization of isobutyl vinyl ether using a variety of metal oxides as heterogeneous catalysts: Robust, reusable, and environmentally benign initiating systems

Kanazawa

Kanaoka

Aoshima

2010

J. Polym. Sci. A Polym. Chem.

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Cationic polymerization of isobutyl vinyl ether (IBVE) was examined using a variety of metal oxides in conjunction with IBVE–HCl adduct as a cationogen in toluene at 0 °C. Iron oxides (α‐Fe2O3, γ‐Fe2O3, and Fe3O4) induced living polymerization in the presence of an added base, ethyl acetate or 1,4‐dioxane, to give polymers with very narrow molecular weight distributions (MWDs). Conversely, with other metal oxides such as Ga2O3, In2O3, ZnO, Co3O4, and Bi2O3, polymers with bimodal MWDs, including long‐lived species along with uncontrolled higher molecular weight portions, were produced in the presence of an added base. A small amount of nBu4NCl or 2,6‐di‐tert‐butylpyridine (DTBP) suppressed the uncontrolled portion to induce controlled reactions with Ga2O3, In2O3, and ZnO. The roles of these reagents are discussed in terms of the nature of the active sites of the catalyst surface and the polymerization mechanisms. In addition, the reusability of the catalyst, the effect of stirring before and during polymerization, and the estimation of the number of active sites are also described. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 916–926, 2010

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Section: Resultsmentioning

confidence: 99%

Living cationic polymerization of isobutyl vinyl ether using a variety of metal oxides as heterogeneous catalysts: Robust, reusable, and environmentally benign initiating systems

Kanazawa

Kanaoka

Aoshima

2010

J. Polym. Sci. A Polym. Chem.

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“…IBVE (TCI; >99.0%), ethyl acetate (Wako; >99.5%), dichloromethane (Nacalai Tesque; 99%), and 1,2-dichloroethane (Wako; >99.5%) were distilled twice over calcium hydride before use. Toluene-d 8 4 , a stock solution in dichloromethane was prepared from commercial anhydrous GeCl 4 (Wako; 99.99%). For NbCl 5 , a stock solution in a mixture of dichloromethane and ethyl acetate was prepared from commercial anhydrous NbCl 5 (Strem; 99.99%).…”

Section: Methodsmentioning

confidence: 99%

Living Cationic Polymerization of Vinyl Ether with Methanol/Metal Chloride Initiating Systems: Relationship between Polymerization Behavior and the Nature of Lewis Acids

2010

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Cationic polymerization of vinyl ether (VE) was examined with methanol/metal chloride initiating systems instead of those with the conventionally used VE-protonic acid adduct initiators. With MoCl 5 , a highly oxophilic metal halide, the polymerization of isobutyl VE (IBVE) using methanol proceeded in a living fashion in the presence of ethyl acetate, although the reaction was not controlled in conjunction with IBVE-HCl adduct. Furthermore, in the methanol-initiated polymerization, the Lewis acids used could be classified mainly into three categories in terms of polymerization behavior: those producing long-lived species (e.g., MoCl 5 , NbCl 5 , and ZrCl 4 ), those inducing uncontrolled polymerization (e.g., GaCl 3 and FeCl 3 ), or those showing no activity at all (e.g., ZnCl 2 and InCl 3 ). The matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) spectra of the product polymers and the direct 1 H NMR analysis of the reaction mixtures revealed that the controlled polymerization starts with an exchange reaction between the methoxy group of methanol and the chloride anion of a metal chloride to generate HCl, the true initiator. With some Lewis acids such as NbCl 5 , the polymerization proceeds only via thus produced C-Cl terminals as dormant species, whereas rapid equilibrium between the C-Cl ends and acetal structures is involved in the propagation reaction with other Lewis acids such as ZrCl 4 . The trends in Lewis acids correlated with the nature of their central metals, i.e., their "oxophilicity" and "chlorophilicity".

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“…Isobutyl vinyl ether reacts instantaneously with a-haloacetic acid in hydrocarbon solvents and in halogenated solvents to give 1-(haloacetoxy)-l-[(2-methylpropyl)oxy] ethane (1), which is stable in the presence of excess vinyl ether. 3 The detailed study was undertaken in hydrocarbon solvents, since the -alkoxy esters were less stable in chlorinated solvents. The methylene resonance in the NMR spectra shows the expected two doublets, with lJ = -9 Hz and 2J = 7 Hz.…”

Section: Polymerization16mentioning

confidence: 99%

α‐Halogenated carboxylic acids and their corresponding zinc salts in the living polymerization of isobutyl vinyl ether

Cited by 14 publications

References 19 publications

Living cationic polymerization of isobutyl vinyl ether using a variety of metal oxides as heterogeneous catalysts: Robust, reusable, and environmentally benign initiating systems

Living cationic polymerization of isobutyl vinyl ether using a variety of metal oxides as heterogeneous catalysts: Robust, reusable, and environmentally benign initiating systems

Living Cationic Polymerization of Vinyl Ether with Methanol/Metal Chloride Initiating Systems: Relationship between Polymerization Behavior and the Nature of Lewis Acids

Nucleofugality of halogenated acetates for mechanism study of vinyl ether polymerization

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