Effect of substituent groups of diphenyl disulfide on novel cationic oxidative polymerization: examination of the electrophilic reaction of the cation by computational calculation

E. Shouji, K. Yamamoto, J. Katoh, Hiroyuki Nishide, E. Tsuchida

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Abstract

Substituent groups of the diphenyl disulfides (DPSs) influence the cationic oxidative polymerization in the formation of polyphenylene sulfides (PPSs). A semiempirical MO calculation (AM1) was performed on the model compounds of PPS, such as thioanisoles (TAs) and diphenyl sulfides (PSs), in order to elucidate the reactivity of the cation. Linear PPS is formed on polymerization because of the high electron density of the carbon in the para position. The ratios of the frontier electron density of the carbon in the para position on the disulfide to the sulfur atom are ordered as follows; 3,5‐dimethyl‐PS>2,5‐dimethyl‐PS‐3‐methyl‐PS>nonsubstituted PS>2‐methyl‐PS>2,6‐dimethyl‐PS. The formation energies of the σ‐complex, which is the intermediate of the reaction, also shows the same order. The theoretical calculation indicates that 3,5‐dimethyl disubstituted disulfide and 3‐methyl one are most preferable monomers of this cationic oxidative polymerization.

Original languageEnglish
Pages (from-to)149-154
Number of pages6
JournalPolymers for Advanced Technologies
Volume2
Issue number3
DOIs
Publication statusPublished - 1991

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Cations
Positive ions
Polymerization
Disulfides
Carrier concentration
Carbon
Sulfur
Monomers
Atoms
polyphenylene sulfide
diphenyl disulfide
Sulfides
diphenyl sulfide
methylphenylsulfide

Keywords

  • AM1
  • Cationic oxidative polymerization
  • Diphenyl disulfide
  • Poly(phenylene sulfide)s
  • π‐Frontier electron density

ASJC Scopus subject areas

  • Polymers and Plastics

Cite this

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title = "Effect of substituent groups of diphenyl disulfide on novel cationic oxidative polymerization: examination of the electrophilic reaction of the cation by computational calculation",
abstract = "Substituent groups of the diphenyl disulfides (DPSs) influence the cationic oxidative polymerization in the formation of polyphenylene sulfides (PPSs). A semiempirical MO calculation (AM1) was performed on the model compounds of PPS, such as thioanisoles (TAs) and diphenyl sulfides (PSs), in order to elucidate the reactivity of the cation. Linear PPS is formed on polymerization because of the high electron density of the carbon in the para position. The ratios of the frontier electron density of the carbon in the para position on the disulfide to the sulfur atom are ordered as follows; 3,5‐dimethyl‐PS>2,5‐dimethyl‐PS‐3‐methyl‐PS>nonsubstituted PS>2‐methyl‐PS>2,6‐dimethyl‐PS. The formation energies of the σ‐complex, which is the intermediate of the reaction, also shows the same order. The theoretical calculation indicates that 3,5‐dimethyl disubstituted disulfide and 3‐methyl one are most preferable monomers of this cationic oxidative polymerization.",
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author = "E. Shouji and K. Yamamoto and J. Katoh and Hiroyuki Nishide and E. Tsuchida",
year = "1991",
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T1 - Effect of substituent groups of diphenyl disulfide on novel cationic oxidative polymerization

T2 - examination of the electrophilic reaction of the cation by computational calculation

AU - Shouji, E.

AU - Yamamoto, K.

AU - Katoh, J.

AU - Nishide, Hiroyuki

AU - Tsuchida, E.

PY - 1991

Y1 - 1991

N2 - Substituent groups of the diphenyl disulfides (DPSs) influence the cationic oxidative polymerization in the formation of polyphenylene sulfides (PPSs). A semiempirical MO calculation (AM1) was performed on the model compounds of PPS, such as thioanisoles (TAs) and diphenyl sulfides (PSs), in order to elucidate the reactivity of the cation. Linear PPS is formed on polymerization because of the high electron density of the carbon in the para position. The ratios of the frontier electron density of the carbon in the para position on the disulfide to the sulfur atom are ordered as follows; 3,5‐dimethyl‐PS>2,5‐dimethyl‐PS‐3‐methyl‐PS>nonsubstituted PS>2‐methyl‐PS>2,6‐dimethyl‐PS. The formation energies of the σ‐complex, which is the intermediate of the reaction, also shows the same order. The theoretical calculation indicates that 3,5‐dimethyl disubstituted disulfide and 3‐methyl one are most preferable monomers of this cationic oxidative polymerization.

AB - Substituent groups of the diphenyl disulfides (DPSs) influence the cationic oxidative polymerization in the formation of polyphenylene sulfides (PPSs). A semiempirical MO calculation (AM1) was performed on the model compounds of PPS, such as thioanisoles (TAs) and diphenyl sulfides (PSs), in order to elucidate the reactivity of the cation. Linear PPS is formed on polymerization because of the high electron density of the carbon in the para position. The ratios of the frontier electron density of the carbon in the para position on the disulfide to the sulfur atom are ordered as follows; 3,5‐dimethyl‐PS>2,5‐dimethyl‐PS‐3‐methyl‐PS>nonsubstituted PS>2‐methyl‐PS>2,6‐dimethyl‐PS. The formation energies of the σ‐complex, which is the intermediate of the reaction, also shows the same order. The theoretical calculation indicates that 3,5‐dimethyl disubstituted disulfide and 3‐methyl one are most preferable monomers of this cationic oxidative polymerization.

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KW - Cationic oxidative polymerization

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KW - Poly(phenylene sulfide)s

KW - π‐Frontier electron density

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