Precursor polymers to poly(p-phenylene vinylene) and its heteroaromatic derivatives. Polymerization mechanism

Bong Rae Cho

doi:10.1016/S0079-6700(01)00036-3

Precursor polymers to poly(p-phenylene vinylene) and its heteroaromatic derivatives. Polymerization mechanism

Bong Rae Cho

Research output: Contribution to journal › Article › peer-review

23 Citations (Scopus)

Abstract

Mechanism of polymerization reactions forming the precursor polymers of poly(p-phenylenevinylene) (PPV) and its heteroaromatic derivatives are summarized. Reactions of α,α′-bis(tetrahydrothiophenio)-p-xylene dichloride with OH^- in H₂O proceed via 1,6-elimination-free radical polymerization mechanism. The rate of elimination reaction increased and that of subsequent polymerization decreased as the aromatic moiety was changed from phenyl to thienyl to furyl. Also, the elimination reaction mechanism changed from (E1cb)_R to (E1cb)_irr for the same variation of the aromatic moiety, whereas the polymerization mechanism remained the same. The polymerization mechanism for the Gilch route was proposed to be ionic. However, it might actually proceed by a free radical mechanism. The mechanism of the polymerization pathway of the sulfo(i)nyl route changed from a free radical to a competing ionic and free radical by the change in the solvent from protic to aprotic. The thermal decomposition of the bis-sulfonium salts proceeds by the S_N2 displacement of the tetrahydrothiophene by chloride followed by the thermal elimination of HCl. On the other hand, the elimination of the sulfi(o)nyl group is considered to proceed via a syn-elimination.

Original language	English
Pages (from-to)	307-355
Number of pages	49
Journal	Progress in Polymer Science (Oxford)
Volume	27
Issue number	2
DOIs	https://doi.org/10.1016/S0079-6700(01)00036-3
Publication status	Published - 2002 Mar

Bibliographical note

Funding Information:
The author is indebted to the students and collaborators whose names appear in the joint publications listed herein. This work was supported by KOSEF (Project 995-0300-001-2) and a NRL grant from MOST and CRM-KOSEF.

Keywords

Elimination
Free radical mechanism
Gilch route
Mechanism
Poly(2,5-furanovinylene)
Poly(2,5-thienylene vinylene)
Poly(p-phenylenevinylene)
Precursor route
Sulfi(o)nyl route
Thermal elimination

ASJC Scopus subject areas

Ceramics and Composites
Surfaces and Interfaces
Polymers and Plastics
Organic Chemistry
Materials Chemistry

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10.1016/S0079-6700(01)00036-3

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title = "Precursor polymers to poly(p-phenylene vinylene) and its heteroaromatic derivatives. Polymerization mechanism",

abstract = "Mechanism of polymerization reactions forming the precursor polymers of poly(p-phenylenevinylene) (PPV) and its heteroaromatic derivatives are summarized. Reactions of α,α′-bis(tetrahydrothiophenio)-p-xylene dichloride with OH- in H2O proceed via 1,6-elimination-free radical polymerization mechanism. The rate of elimination reaction increased and that of subsequent polymerization decreased as the aromatic moiety was changed from phenyl to thienyl to furyl. Also, the elimination reaction mechanism changed from (E1cb)R to (E1cb)irr for the same variation of the aromatic moiety, whereas the polymerization mechanism remained the same. The polymerization mechanism for the Gilch route was proposed to be ionic. However, it might actually proceed by a free radical mechanism. The mechanism of the polymerization pathway of the sulfo(i)nyl route changed from a free radical to a competing ionic and free radical by the change in the solvent from protic to aprotic. The thermal decomposition of the bis-sulfonium salts proceeds by the SN2 displacement of the tetrahydrothiophene by chloride followed by the thermal elimination of HCl. On the other hand, the elimination of the sulfi(o)nyl group is considered to proceed via a syn-elimination.",

keywords = "Elimination, Free radical mechanism, Gilch route, Mechanism, Poly(2,5-furanovinylene), Poly(2,5-thienylene vinylene), Poly(p-phenylenevinylene), Precursor route, Sulfi(o)nyl route, Thermal elimination",

author = "Cho, {Bong Rae}",

note = "Funding Information: The author is indebted to the students and collaborators whose names appear in the joint publications listed herein. This work was supported by KOSEF (Project 995-0300-001-2) and a NRL grant from MOST and CRM-KOSEF. ",

year = "2002",

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doi = "10.1016/S0079-6700(01)00036-3",

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T1 - Precursor polymers to poly(p-phenylene vinylene) and its heteroaromatic derivatives. Polymerization mechanism

AU - Cho, Bong Rae

N1 - Funding Information: The author is indebted to the students and collaborators whose names appear in the joint publications listed herein. This work was supported by KOSEF (Project 995-0300-001-2) and a NRL grant from MOST and CRM-KOSEF.

PY - 2002/3

Y1 - 2002/3

N2 - Mechanism of polymerization reactions forming the precursor polymers of poly(p-phenylenevinylene) (PPV) and its heteroaromatic derivatives are summarized. Reactions of α,α′-bis(tetrahydrothiophenio)-p-xylene dichloride with OH- in H2O proceed via 1,6-elimination-free radical polymerization mechanism. The rate of elimination reaction increased and that of subsequent polymerization decreased as the aromatic moiety was changed from phenyl to thienyl to furyl. Also, the elimination reaction mechanism changed from (E1cb)R to (E1cb)irr for the same variation of the aromatic moiety, whereas the polymerization mechanism remained the same. The polymerization mechanism for the Gilch route was proposed to be ionic. However, it might actually proceed by a free radical mechanism. The mechanism of the polymerization pathway of the sulfo(i)nyl route changed from a free radical to a competing ionic and free radical by the change in the solvent from protic to aprotic. The thermal decomposition of the bis-sulfonium salts proceeds by the SN2 displacement of the tetrahydrothiophene by chloride followed by the thermal elimination of HCl. On the other hand, the elimination of the sulfi(o)nyl group is considered to proceed via a syn-elimination.

AB - Mechanism of polymerization reactions forming the precursor polymers of poly(p-phenylenevinylene) (PPV) and its heteroaromatic derivatives are summarized. Reactions of α,α′-bis(tetrahydrothiophenio)-p-xylene dichloride with OH- in H2O proceed via 1,6-elimination-free radical polymerization mechanism. The rate of elimination reaction increased and that of subsequent polymerization decreased as the aromatic moiety was changed from phenyl to thienyl to furyl. Also, the elimination reaction mechanism changed from (E1cb)R to (E1cb)irr for the same variation of the aromatic moiety, whereas the polymerization mechanism remained the same. The polymerization mechanism for the Gilch route was proposed to be ionic. However, it might actually proceed by a free radical mechanism. The mechanism of the polymerization pathway of the sulfo(i)nyl route changed from a free radical to a competing ionic and free radical by the change in the solvent from protic to aprotic. The thermal decomposition of the bis-sulfonium salts proceeds by the SN2 displacement of the tetrahydrothiophene by chloride followed by the thermal elimination of HCl. On the other hand, the elimination of the sulfi(o)nyl group is considered to proceed via a syn-elimination.

KW - Elimination

KW - Free radical mechanism

KW - Gilch route

KW - Mechanism

KW - Poly(2,5-furanovinylene)

KW - Poly(2,5-thienylene vinylene)

KW - Poly(p-phenylenevinylene)

KW - Precursor route

KW - Sulfi(o)nyl route

KW - Thermal elimination

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VL - 27

SP - 307

EP - 355

JO - Progress in Polymer Science (Oxford)

JF - Progress in Polymer Science (Oxford)

IS - 2

ER -

Precursor polymers to poly(p-phenylene vinylene) and its heteroaromatic derivatives. Polymerization mechanism

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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