New Acyl-Group Transfer Polymerization of Thiiranes Using Carboxylic Acid Derivatives and Quaternary Onium Salts

Kameyama, Atsushi; Shimotsuma, Katsuya; Nishikubo, T.

doi:10.1295/polymj.28.68

Cited by 17 publications

(10 citation statements)

References 15 publications

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“…Despite the various REP systems reported to date, there are limited reports of controlled REP to produce well‐defined cyclic polymers with narrow polydispersity . Recently, Kudo and Nishikubo have reported that thiazolidine‐2,4‐dione (TZD), a cyclic aliphatic carbamate thioester, effectively works as the cyclic initiator for controlled REP of thiiranes to afford cyclic polysulfides with relatively narrow polydispersity of 1.2–1.4, based on the controlled acyl‐transfer polymerization of thiiranes developed by Kameyama and Nishikubo . The TZD‐initiated REP system was further investigated in detail and applied to a functional molecular system by Vana and co‐workers .…”

Section: Introductionmentioning

confidence: 99%

“…[25][26][27][28][32][33][34][35] Recently, Kudo and Nishikubo have reported that thiazolidine-2,4-dione (TZD), a cyclic aliphatic carbamate thioester, effectively works as the cyclic initiator for controlled REP of thiiranes to afford cyclic polysulfides with relatively narrow polydispersity of 1.2-1.4, 35 based on the controlled acyltransfer polymerization of thiiranes developed by Kameyama and Nishikubo. [36][37][38] The TZD-initiated REP system was further investigated in detail and applied to a functional molecular system by Vana and co-workers. 39,40 On the other hand, N-(4-tolyl)-S-phenyl thiocarbamate has been demonstrated to work as an efficient initiator for the controlled acyl-transfer polymerization of thiiranes to obtain linear polysulfides with further narrow polydispersity, 35,41 indicating the good potential of aromatic thiourethane structure as the initiator.…”

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confidence: 99%

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Controlled ring‐expansion polymerization of thiiranes based on cyclic aromatic thiourethane initiator

Takahashi

Yuzaki

Ishida

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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Ring‐expansion polymerization (REP) of thiiranes was investigated using 3H‐benzothiazol‐2‐one (BT) as the cyclic aromatic thiourethane initiator in the presence of tetrabutylammonium chloride (TBAC) catalyst. The polymerization proceeded in a well‐controlled manner to afford cyclic polysulfides with one BT moiety per macrocycle, as confirmed by MALDI‐TOF MS spectroscopy. Differential scanning calorimetry (DSC) measurement of the obtained cyclic polysulfides revealed slight decrease in the glass‐transition temperature as the increase in the molecular weight, supporting the cyclic topology of the products. Postpolymerization of thiiranes using the BT‐initiated cyclic polysulfide as the macroinitiator afforded the ring‐expanded product while maintaining the narrow polydispersity and well‐defined cyclic structure, which enabled precise synthesis of cyclic block copolymer with different thiirane combination. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2442–2449

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Controlled ring‐expansion polymerization of thiiranes based on cyclic aromatic thiourethane initiator

Takahashi

Yuzaki

Ishida

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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“…Various thiiranes such as BPS and cyclohexene sulfide (CHS) can be polymerized using PTA as the initiator and TBAB as the catalyst. 46 In addition to the thiiranes, four-membered cyclic sulfide, thietane (TE) 47 was also polymerized in similar reaction systems. The spectral data of the obtained polysulfides proved that the cyclic sulfides were polymerized easily in this reaction system to afford the corresponding polysulfides with terminal S-thioester groups.…”

Section: Acyl-transfer Polymerization Of Thiiranesmentioning

confidence: 99%

Novel Synthesis of Polymers with Well-Defined Structures Based on Selective Reaction of Cyclic Sulfides and Cyclic Ethers Catalyzed by Quaternary Onium Salts

Kameyama

Nishikubo

2009

Polym. J.

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Novel syntheses of polymers with well-defined structures were developed on the basis of the selective reactions of thiiranes and oxiranes with carboxylic esters or active chlorides using quaternary onium salts. (1) A new type of reactive polymers with pendant chloromethyl groups was synthesized by polyaddition of difunctional thiiranes or oxiranes with various organic dichlorides. (2) Polysulfides with controlled molecular weight and narrow molecular weight distribution were synthesized by ring-opening polymerization of thiiranes with carboxylic acid derivatives as initiators and quaternary onium salts as catalysts, in which acyl-groups transfer to the propagating center in each propagation step. The ring-opening polymerization of thiiranes has an advantage in the synthesis of specific shaped polymers such as star polymers and cyclic polymers. (3) Novel A-B type sequence-ordered copolymers were synthesized by alternating ring-opening polymerization of oxiranes withthiobutyrolactone, or of oxetane with cyclic carboxylic anhydrides. (4) Sequence-ordered polymers were successfully synthesized on the basis of a new concept-''transformation of polymer backbones'' using insertion of thiiranes and oxiranes into poly(S-thioester)s in the aforementioned reaction systems. The reaction mechanism and advantages of the reaction systems are also discussed.KEY WORDS: Ring-opening Reaction / Thiirane / Oxirane / Quaternary Onium Salts / Acyl Transfer / Sequence-ordered Polymers / Addition reactions of cyclic compounds such as cyclic ethers with certain reagents are useful synthetic methods for preparing polymeric materials. The addition reactions of oxiranes (epoxy) compounds have been used for syntheses of functional polymers from reactive polymers containing pendant oxirane groups.1 Epoxy resins with multiple oxirane groups are widely utilized with certain curing reagents to obtain thermal cured materials.2 These polymer syntheses are based on the addition reaction of oxiranes with such reagents as amines, carboxylic acids, etc. In general, the reactions provide mixtures of -addition and -addition products (mixtures of regio-isomers).3 Regioselective ring-opening reactions of oxiranes are important research subjects in synthetic organic chemistry, 4 but it has been thought that the reactions of oxiranes with the reagents mentioned are not suitable for precise syntheses of polymers with well-defined structures.Recently, we have developed synthetic methods for functional polymers and chemical modification of polymers based on the regioselective ring-opening reactions of oxiranes with carboxylic esters catalyzed by quaternary onium salts. 5 In a series of studies on ring-opening reaction of cyclic compounds with several reagents; we found novel regioselective reactions of thiiranes or oxiranes to be useful for syntheses of polymers with well-defined structures.A significant advantage of the addition reactions of thiiranes or oxiranes with the reagents is the selective formation ofaddition products without ring-opening polymeriza...

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“…Controlled polymerization of episulfides is one of the most investigated methods for the synthesis of sulfur‐containing polymers with well‐defined structures and desired molecular weights 17–19. Recent researches enabled the synthesis of well‐defined star‐shaped polysulfides by anionic polymerization controlling the activity of chain ends 20–24.…”

Section: Introductionmentioning

confidence: 99%

“…15,16 Controlled polymerization of episulfides is one of the most investigated methods for the synthesis of sulfur-containing polymers with well-defined structures and desired molecular weights. [17][18][19] Recent researches enabled the synthesis of well-defined star-shaped polysulfides by anionic polymerization controlling the activity of chain ends. [20][21][22][23][24] For example, a initiating system based on the thiol-thiolate equilibrium with 1,8-diazabicyclo [5.4.0]-undec-7-ene (DBU) attained rapid and controlled polymerization under mild conditions.…”

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confidence: 99%

Synthesis of well‐defined and end‐polymerizable star‐shaped polysulfides and their application to negative photoresist

Hirata

Abe

Ochiai

et al. 2010

J. Polym. Sci. A Polym. Chem.

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Various star‐shaped poly(phenoxy propylene sulfide)s (PPSs) bearing curable end groups were synthesized by the functionalization of the propagating ends of star‐shaped poly(PPS) with various electrophilies. The functionalization with chloromethyl styrene proceeded quantitatively, and afforded polymers with Mn almost agreed with theoretical value and narrow Mw/Mn. The photocuring conditions were optimized, and the addition of 10 wt % of poly(ethylene glycol) diacrylate was effective to attain sufficient crosslinking. The photocuring reaction of the end‐functionalized poly(PPS) films cast on silicon wafers was conducted by UV irradiation. The cured poly (PPS)s became insoluble in THF, supporting the sufficient crosslinking. Developing of a cured polymer yielded a negative photoresist pattern. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

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New Acyl-Group Transfer Polymerization of Thiiranes Using Carboxylic Acid Derivatives and Quaternary Onium Salts

Cited by 17 publications

References 15 publications

Controlled ring‐expansion polymerization of thiiranes based on cyclic aromatic thiourethane initiator

Controlled ring‐expansion polymerization of thiiranes based on cyclic aromatic thiourethane initiator

Novel Synthesis of Polymers with Well-Defined Structures Based on Selective Reaction of Cyclic Sulfides and Cyclic Ethers Catalyzed by Quaternary Onium Salts

Synthesis of well‐defined and end‐polymerizable star‐shaped polysulfides and their application to negative photoresist

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