Abstract
A newly established catalyst system for oxygen-oxidative polymerization of diphenyl disulfide is reported. Combination of vanadyl compounds (e.g., VO(acac)<inf>2</inf>) and triphenylmethylium tetrakis(pentafluorophenyl)borate (TrB(C<inf>6</inf>F<inf>5</inf>)<inf>4</inf>) proceeds the polymerization to give poly(1,4-phenylene sulfide) (PPS) at 100 °C. When triphenylmethylium tetrafluoroborate (TrBF<inf>4</inf>) is applied with vanadyl tetraphenylporphyrin (VO(TPP)) or N,N′-(ethylenebis(salicylideneaminato))oxovanadium (VO(salen)), PPS is also given via polymerization under conditions near 160 °C. Combination of the vanadyl complex and the borate affords the first protic-acid-free catalytic system for the polymerization of the disulfide, suggesting the overall reaction to produce PPS and H<inf>2</inf>O from O<inf>2</inf> and protons that are eliminated from the monomer. Strong-acid-free oxygen-oxidative polymerization of PhSSPh is presented, catalyzed by a vanadyl and TrBR<inf>4</inf> system. TrB(C<inf>6</inf>F<inf>5</inf>)<inf>4</inf> is found to activate VO(acac)<inf>2</inf> at 100 °C and the catalyst gives poly(1,4-phenylene sulfide) (PPS) from PhSSPh. TrBF<inf>4</inf> has stronger nucleophilicity, but is found to activate VO(salen) and VO(TPP) at 160 °C for preparing PPS.
| Original language | English |
|---|---|
| Pages (from-to) | 1850-1855 |
| Number of pages | 6 |
| Journal | Macromolecular Chemistry and Physics |
| Volume | 216 |
| Issue number | 18 |
| DOIs | |
| Publication status | Published - 2015 Sep 1 |
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Keywords
- borates
- Lewis acids
- oxidative polymerization
- poly(1 4-phenylene sulfide)
- vanadyl complexes
ASJC Scopus subject areas
- Materials Chemistry
- Polymers and Plastics
- Organic Chemistry
- Physical and Theoretical Chemistry
- Condensed Matter Physics
Cite this
Vanadyl-TrBR<inf>4</inf>-Catalyzed Oxidative Polymerization of Diphenyl Disulfide. / Aida, Fuyuki; Yamaguchi, Souske; Takatori, Yohei; Nagamatsu, Kentaro; Kiyokawa, Daichi; Oyaizu, Kenichi; Nishide, Hiroyuki.
In: Macromolecular Chemistry and Physics, Vol. 216, No. 18, 01.09.2015, p. 1850-1855.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Vanadyl-TrBR4-Catalyzed Oxidative Polymerization of Diphenyl Disulfide
AU - Aida, Fuyuki
AU - Yamaguchi, Souske
AU - Takatori, Yohei
AU - Nagamatsu, Kentaro
AU - Kiyokawa, Daichi
AU - Oyaizu, Kenichi
AU - Nishide, Hiroyuki
PY - 2015/9/1
Y1 - 2015/9/1
N2 - A newly established catalyst system for oxygen-oxidative polymerization of diphenyl disulfide is reported. Combination of vanadyl compounds (e.g., VO(acac)2) and triphenylmethylium tetrakis(pentafluorophenyl)borate (TrB(C6F5)4) proceeds the polymerization to give poly(1,4-phenylene sulfide) (PPS) at 100 °C. When triphenylmethylium tetrafluoroborate (TrBF4) is applied with vanadyl tetraphenylporphyrin (VO(TPP)) or N,N′-(ethylenebis(salicylideneaminato))oxovanadium (VO(salen)), PPS is also given via polymerization under conditions near 160 °C. Combination of the vanadyl complex and the borate affords the first protic-acid-free catalytic system for the polymerization of the disulfide, suggesting the overall reaction to produce PPS and H2O from O2 and protons that are eliminated from the monomer. Strong-acid-free oxygen-oxidative polymerization of PhSSPh is presented, catalyzed by a vanadyl and TrBR4 system. TrB(C6F5)4 is found to activate VO(acac)2 at 100 °C and the catalyst gives poly(1,4-phenylene sulfide) (PPS) from PhSSPh. TrBF4 has stronger nucleophilicity, but is found to activate VO(salen) and VO(TPP) at 160 °C for preparing PPS.
AB - A newly established catalyst system for oxygen-oxidative polymerization of diphenyl disulfide is reported. Combination of vanadyl compounds (e.g., VO(acac)2) and triphenylmethylium tetrakis(pentafluorophenyl)borate (TrB(C6F5)4) proceeds the polymerization to give poly(1,4-phenylene sulfide) (PPS) at 100 °C. When triphenylmethylium tetrafluoroborate (TrBF4) is applied with vanadyl tetraphenylporphyrin (VO(TPP)) or N,N′-(ethylenebis(salicylideneaminato))oxovanadium (VO(salen)), PPS is also given via polymerization under conditions near 160 °C. Combination of the vanadyl complex and the borate affords the first protic-acid-free catalytic system for the polymerization of the disulfide, suggesting the overall reaction to produce PPS and H2O from O2 and protons that are eliminated from the monomer. Strong-acid-free oxygen-oxidative polymerization of PhSSPh is presented, catalyzed by a vanadyl and TrBR4 system. TrB(C6F5)4 is found to activate VO(acac)2 at 100 °C and the catalyst gives poly(1,4-phenylene sulfide) (PPS) from PhSSPh. TrBF4 has stronger nucleophilicity, but is found to activate VO(salen) and VO(TPP) at 160 °C for preparing PPS.
KW - borates
KW - Lewis acids
KW - oxidative polymerization
KW - poly(1 4-phenylene sulfide)
KW - vanadyl complexes
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U2 - 10.1002/macp.201500154
DO - 10.1002/macp.201500154
M3 - Article
VL - 216
SP - 1850
EP - 1855
JO - Macromolecular Chemistry and Physics
JF - Macromolecular Chemistry and Physics
SN - 1022-1352
IS - 18
ER -