Synthesis of high-molecular-weight poly(phenylene sulfide) by oxidative polymerization via poly(sulfonium cation) from methyl phenyl sulfoxide

Tsuchida, Eishun; Shouji, Eiichi; Yamamoto, Kimihisa

doi:10.1021/ma00078a005

Cited by 50 publications

(44 citation statements)

References 11 publications

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“…Epichlorohydrin which is used as a monomer for the photoinitiated polymerization was distilled over calcium hydride before use. (2) 4-(Methylthio)diphenylmethylsulfonium triflate (1) was synthesized by the previously reported manner 12,13) . 1 (0.30 g, 0.76 mmol) was dissolved into 5 cm 3 of acetonitrile.…”

Section: Experimental Partmentioning

confidence: 99%

“…IR The counter anion of 8 was exchanged by using potassium hexafluorophosphate as described above to obtain 4-(phenylthio)triphenylsulfonium hexfluorophosphate (9 Poly(methylsulfonio-1,4-phenylenethio-1,4-phenylene triflate) (10) was synthesized by the previously reported manner 12,13) . The counter anion was exchanged by using potassium hexafluorophosphate in an acetonitrile/water mixture as solvent.…”

Section: Synthesis Of 4-(methylthio)diphenylmethylsulfonium Hexafluormentioning

confidence: 99%

“…IR Poly(propylsulfonio-1,4-phenylenethio-1,4-phenylene triflate) (12) was synthesized by the previously reported manner 29) . The counter anion was exchanged by using potassium hexafluorophosphate as described above.…”

Section: Synthesis Of 4-(methylthio)diphenylmethylsulfonium Hexafluormentioning

confidence: 99%

“…The syntheses of polymeric sulfonium compounds having methyl and propyl substituents by using 4-(phenylthio)phenyl methyl or propyl sulfoxide as a monomer have been described pre- viously 12,13,29) . In this work, the same methods are applied to polymerize 4-(phenoxy)diphenyl sulfoxide and 4-(phenylthio)diphenyl sulfoxide into poly(phenylsulfonio-1,4-phenyleneoxy-1,4-phenylene trifalte) (16) or poly(phenylsulfonio-1,4-phenylenethio-1,4-phenylene triflate) (18) in 100% yield, respectively (Scheme 2, 3).…”

Section: Synthesis Of Polymeric Sulfonium Saltsmentioning

confidence: 99%

“…They can be synthesized by numerous methods, including nucleophilic substitution between sulfides and alkylating agents, dehydration between sulfides and alcohols, electrophilic reaction of protonated sulfoxides with aromatics using Lewis acids, and reaction between alkoxysulfonium salts and Grignard reagents [1][2][3][4][5][6][7][8][9][10] . Recently, we have found that poly(methylsulfonio-1,4-phenylenethio-1,4-phenylene triflate) can be synthesized through a sulfoxide-acid system and converted to poly(p-phenylene sulfide) (PPS) through nucleophilic demethylation [11][12][13] . The polysulfonium salts are employed as a new type of polymeric alkylation reagent because, after the dealkylation, they are converted to insoluble PPS that can be easily removed from the reaction mixture 14) .…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and photochemical reaction of polyarylenesulfonium salts

Haryono

Miyatake

Tsuchida³

1999

Macromol. Chem. Phys.

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SUMMARY: A novel class of polyelectrolytes having triphenylsulfonio groups in its main chain was synthesized by the sulfoxide-acid system reaction from the corresponding aryl sulfoxide monomers. The photo-irradiation of ultraviolet light at the p-p* transition band resulted in the selective degradation of the polymer to the corresponding aryl or alkyl sulfide monomer. The photodegradation is accompanied by proton generation, which could be useful for the photoinitiated polymerization of epoxy compounds. The differences between the monomeric and the polymeric sulfonium salts in their photodegradation properties were examined on the basis of kinetics of photodegradation, quantum yields and the conversion in the photoinitiated polymerization of the epoxy monomer. The polymeric sulfonium salts are more effective than the monomeric ones due to larger e (extinction coefficient) at the irradiation wavelength.

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Section: Experimental Partmentioning

confidence: 99%

Section: Synthesis Of 4-(methylthio)diphenylmethylsulfonium Hexafluormentioning

confidence: 99%

Section: Synthesis Of 4-(methylthio)diphenylmethylsulfonium Hexafluormentioning

confidence: 99%

Section: Synthesis Of Polymeric Sulfonium Saltsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis and photochemical reaction of polyarylenesulfonium salts

Haryono

Miyatake

Tsuchida³

1999

Macromol. Chem. Phys.

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Sulfur‐Containing Polymers

Kultys¹

2005

Kirk-Othmer Encyclopedia of Chemical Technology

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This review describes methods of synthesis and some more interesting properties of the various new sulfur‐containing polymers, with particular regard for their potential application possibilities. Also, some new or improved methods of synthesizing already known polymers are discussed. Polysulfides, including poly(monosulfide)s and poly(disulfide)s are the subject of many detailed studies. In the last decade, extensive efforts have been devoted to the synthesis of cyclic oligomers (macrocyclic aromatic sulfides and disulfides) as precursors for the preparation of high molecular weight poly(thioarylene)s by ring‐opening polymerization. The coordination chemistry of macrocyclic polysulfides has also received considerable attention. The thiacrown ether polymer ligands can be used as ion‐exchange resins, metal ion adsorbents, and polymeric phase‐transfer catalysts. Molecular systems in which tetrathiafulvalene is incorporated into macrocycles with supplementary donor atoms are potential electroactive cation sensors. Perfluoro‐ and polyfluorothiophenes have been studied as precursors to novel electrically conductive polymers. Polysulfoxides are used as functional polymers. Polymers with sulfoxide group in the main chain can be used as novel polymeric oxidizing reagents, compatibilizers, and polymer solvents, and those with chiral sulfonyl groups as stationary phases of chiral hplc column or as polymeric reagents. Polysulfonium salts can be used as ion‐exchange resins, polymer supports in peptide synthesis, polymeric reagents, or conducting and photochemical polymeric materials. There have been reports of examples of polymers with sulfonium salt moieties applied as a catalyst to organic reactions and precursors of such polymers as PPS, perfluorinated PPS, PPV, and PPSA. Poly(thiophenium salt)s were found to act as a new type of polymeric alkylation reagents. Polymers substituted by sulfo groups have a wide range of applications. Water‐soluble polymers are used as emulsifiers, flocculants, thickeners, tanning agents, conductive polymers, etc. Sulfonated polyelectrolyte block copolymers are effective stabilizers in emulsion polymerization. Insoluble polymers are used as ion‐exchange resins and they find application as membrane materials. A great demand for chemically stable ion‐exchange membranes for electromembrane processes (such as electrodialysis, polymer electrolyte membrane electrolysis, and polymer electrolyte fuel cells) has, in the past years, stimulated investigations dealing with the developing of the sulfonation process of thermally and chemically stable engineering plastics. Sulfopolymers are employed in biomedical systems. Much effort has been expended to improve blood‐contacting biomaterials, eg, segmented polyurethanes, and develop various polysulfates and polysulfonates as antithrombotic or antiviral agents. Polysulfates also have potential biomedical applications, eg, as antithrombotic agents. Polysulfates in general, and sulfated polysaccharides in particular, are active against a wide variety of enveloped viruses. A major commercial sulfated polysaccharide is carrageenan, used in ice cream and other food products. Polythioesters, polythiocarbonates, as well as polythiourethanes are interesting thermoplastics. Thus, biphenyl‐based polythioesters are high thermal stability polymers. Polythiocarbonates showing a high refractive index are potentially interesting for optical applications. Polymers bearing five‐membered cyclic dithiocarbonate groups in the side chain are potentially the most versatile reactive polymers. Thiopolyurethanes bearing the thiol groups may be used as reactive polymers to produce optical materials. Segmented thiopolyurethanes based on simple thiodiols as chain extenders with poly(tetramethylene oxide) soft segment are high elasticity thermoplastic elastomers. Polymers containing diphenylmethane units with active methylene groups are new, potentially peroxide‐curable, HDI‐based thiopolyurethanes, whereas polymers containing benzophenone units may find use as interesting modifiers of photosensitive polyurethanes. Studies on polysulfoximines, the new potentially high performance engineering plastics, have recently been undertaken.

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Oxidative Polymerization

Higashimura

Kobayashi

2004

Encyclopedia of Polymer Science and Technology

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This article discusses oxidative polymerizations of aromatic compounds such as phenol, aniline, diphenyl disulfide, benzene, pyrrole, thiophene, and their derivatives, focusing on the reaction mechanism and coupling selectivity. Some of the properties of polymers synthesized by this method, such as, poly(phenylene oxide)s, polyphenols, polyanilines, poly(phenylene sulfide)s, polyphenylenes, polypyrroles, and polythiophenes, are also described.

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Synthesis of high-molecular-weight poly(phenylene sulfide) by oxidative polymerization via poly(sulfonium cation) from methyl phenyl sulfoxide

Cited by 50 publications

References 11 publications

Synthesis and photochemical reaction of polyarylenesulfonium salts

Synthesis and photochemical reaction of polyarylenesulfonium salts

Sulfur‐Containing Polymers

Oxidative Polymerization

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