Polymerization of coordinated monomers. XII. Alternating copolymerization of γ‐crotonolactone with styrene with the use of stannic chloride

Komiyama, Makoto; Hirai, Hidefumi

doi:10.1002/pol.1976.170140816

Cited by 4 publications

(2 citation statements)

References 23 publications

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“…For practical purposes, such a route is not likely to be fruitful since the monomers do not polymerize or copolymerize readily under conventional radical polymerization conditions. 4 As an alternative synthesis, intramolecular reactions between neighbor-However, y-crotonolactone and styrene 7 were reported to give an alternating copolymer in the presence of stannic chloride. This implies the possibility of using Q(,p-unsaturated lactone monomers.…”

Section: •mentioning

confidence: 99%

Copolymerization Behavior of β-Angelica Lactone and Styrene in the Presence of Organoaluminum Chlorides

Hirabayashi

Yokota

1982

Polym J

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In order to synthesize polymers containing lactone units in the backbone chains and use them as membranes, copolymerization of /3-angelica lactone (/3-AL) with styrene was carried out. Using 0(,0('-azobisisobutyronitrile at 60°C, /3-AL did not copolymerize readily. In the presence of ethylaluminum sesquichloride or diethylaluminum chloride as a complexing reagent in toluene at 20°C, however, /3-AL copolymerized much more readily. Spontaneous initiation took place and a copolymer containing about 50 mol% of /3-AL units was obtained under the most favorable conditions. Nevertheless, it seemed unlikely that regular, highly alternating sequences could be achieved in this manner, in contrast to the well-known Lewis acid-complexed copolymerization of acrylic esters and styrene. NMR studies demonstrated that, while the binary complex between /3-AL and ethylaluminum sesquichloride was formed almost instantly and completely, the ternary complex between styrene, /3-AL and ethylaluminum sesquichloride had a rather low stability constant (,;:; 0.05 dm 3 mol-1) which accounts for the imperfectly alternating sequences.

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Section: •mentioning

confidence: 99%

Copolymerization Behavior of β-Angelica Lactone and Styrene in the Presence of Organoaluminum Chlorides

Hirabayashi

Yokota

1982

Polym J

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“…complex are confirmed by the fact that the ternary molecular complex exhibits the charge-transfer absorption, which is not observed on the MMA-styrene system. 15 The small distance between the styrene and the coordinated methyl methacrylate, compared with that between the styrene monomer and the free methyl methacrylate monomer in the binary molecular complex, facilitates interactions between the orbitals of the styrene monomer and those of the coordinated methyl methacrylate monomer. The charge-transfer absorption can be attributed to the interaction mainly between the lowest vacant orbital of the coordinated methyl methacrylate monomer and the highest occupied orbital of the styrene monomer.…”

Section: High Reactivity Of the Ternary Molecular Complexmentioning

confidence: 99%

Polymerization of coordinated monomers. XI. Structure and reactivity of the ternary molecular complex composed of stannic chloride, methyl methacrylate, and styrene

Komiyama

Hirai

1976

J. Polym. Sci. Polym. Chem. Ed.

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The time‐averaged orientation of styrene in the ternary molecular complex composed of stannic chloride, methyl methacrylate, and styrene was determined by use of the chemical shift changes of the protons in the methyl methacrylate on the ternary molecular complex formation. The observed chemical shift change for each of the protons in the methyl methacrylate is expressed by the weighted average of the shifts due to the anisotropic shielding of the benzene ring of styrene for conformations I and II, using the common statistical weight. Conformations I and II correspond to the cis and trans rotational isomers, respectively, of methyl methacrylate with respect to the rotation of the methoxymethyl group around the carbonyl carbon‐ether oxygen bond. Extended Hückel calculations were made on the methyl methacrylate monomer coordinated to stannic chloride and styrene monomer as well as the growing radicals corresponding to the monomers. The energy levels of the frontier orbitals of the species were determined by use of the ionization potentials, the absorption maxima, and the results of the extended Hückel calculations. The high reactivity of the ternary molecular complex is discussed in terms of the interactions between the frontier orbitals of the styrene and those of the coordinated methyl methacrylate.

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Polymerization of coordinated monomers. XIII. Binding in the ternary molecular complex composed of γ‐crotonolactone, styrene, and stannic chloride

Kcmiyama

Hirai

1976

J. Polym. Sci. Polym. Chem. Ed.

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The time‐averaged orientation of the styrene molecule in the ternary molecular complex composed of stannic chloride, γ‐crotonolactone, and styrene is determined by use of 1H‐chemical shifts of the nonequivalent protons of the γ‐crotonolactone. The chemical shift change for each of the various protons of the γ‐crotonolactone on the ternary molecular complex formation can be represented by the anisotropic shielding effect of the benzene ring of one oriented styrene molecule. This fact indicates that the ternary molecular complex has a definite time‐averaged conformation, though the “complexing” styrene molecule exchanges between in the oriented state and in the free state more rapidly than the time scale of the 1H‐NMR spectrometry. The magnitudes of the Coulomb, induction, dispersion, charge‐transfer, and exchange‐repulsion energies between the γ‐crotonolactone and the styrene in the ternary molecular complex are estimated by use of the result of the extended Hückel calculation and that of absorption spectrometry. The Coulomb and dispersion forces between the carboryl group of the coordinated γ‐crotonolactone and the benzene ring of the styrene function mainly in the ternary molecular complex formation. Both the induction force and the charge‐transfer force make a small contribution to the ternary molecular complex formation.

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Polymerization of coordinated monomers. XII. Alternating copolymerization of γ‐crotonolactone with styrene with the use of stannic chloride

Cited by 4 publications

References 23 publications

Copolymerization Behavior of β-Angelica Lactone and Styrene in the Presence of Organoaluminum Chlorides

Copolymerization Behavior of β-Angelica Lactone and Styrene in the Presence of Organoaluminum Chlorides

Polymerization of coordinated monomers. XI. Structure and reactivity of the ternary molecular complex composed of stannic chloride, methyl methacrylate, and styrene

Polymerization of coordinated monomers. XIII. Binding in the ternary molecular complex composed of γ‐crotonolactone, styrene, and stannic chloride

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