Thermal Polymerization of 1,2-Dithiane

Endo, Kiyoshi; Shiroi, Tomotsugu; Murata, Naoki

doi:10.1295/polymj.37.512

Cited by 29 publications

(24 citation statements)

References 18 publications

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“…Similar to 1,2‐dithiane, 1,4‐dihydro‐2,3‐benzodithine, another six‐membered cyclic disulfide containing a benzene ring, was also homopolymerized to yield high molar mass polydisulfides ( M napp ≈ 90.000 g·mol −1 ), either via thermal or thiol‐initiated pathways. Interestingly, the thermal polymerization of 1,2‐dithiane does not proceed at monomer concentration below 4.0 m . The mechanistic investigations performed by Endo et al .…”

Section: Chemistrymentioning

confidence: 99%

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Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

258

220

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/marc.201800650. ChemistryBefore moving to the recent advances within the last 5 years in the diverse applications of sulfur chemistry in polymer and Sulfur-Containing PolymersSulfur and its functional groups are major players in an area of exciting research taking place in modern polymer and materials science, both in academia and industry. In fact, manifold sulfur-based reactions that are both exceptionally versatile as well as tremendously useful have been implemented, and further utilized for the design and preparation of polymeric materials that lead to a plethora of applications ranging from medicine to optics and nanotechnology to separation science. Hence, within this review, an overview of strategies and developments used over the last 5 years to reinforce the importance of the sulfur functional group in modern polymer and materials science is presented. In particular, many important references in the primary literature of sulfur chemistry are referred to, including thiol-ene, thiol-yne, thiol-Michael addition, disulfide cross-linking, and thiol-disulfide exchange, among others, by explaining and illustrating the important principles. Last but not least, the grand aim to underpin the importance of sulfur in modern polymer and materials science is achieved by presenting selected examples in diverse fields and postulating the respective potential for real-world applications. he is now a full professor at KIT.sulfur atoms, and tetraphenylethene-bearing di(alkyl bromide) (Scheme 3). The yield of the polymerization was dependent on the di(alkyl bromide) monomer; the longer spacer between the aromatic moiety and the reactive bromide end groups Scheme 1. The discussion henceforth focuses on the synthesis of polymers possessing the depicted sulfur functional groups. Scheme 2.Representative examples of polythioethers prepared via A) the nucleophilic substitution reaction between an electrophilic dihalide with nucleophilic derivatives of dithiols under alkaline conditions; B) the thiol-ene/yne addition reaction between AA and BB type monomers (i.e., dithiols and dienes/diynes); and C) radical or ionic ring-opening of sulfurcontaining strained rings.Scheme 3. The thiol-bromo polymerization of conformationally fixed monomers to provide multifunctional polymers. [19] Macromol. Rapid Commun. 2019, 40, 1800650 Scheme 4. The regioselective selective nucleophilic aromatic substitution between thiol and fluorinated aromatic compounds, the para-fluorothiol reaction (PFTR).Scheme 5. Synthesis of a linear polymer via PFTR-reaction. [21]

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Section: Chemistrymentioning

confidence: 99%

“…Interestingly, the thermal polymerization of 1,2‐dithiane does not proceed at monomer concentration below 4.0 m . The mechanistic investigations performed by Endo et al . revealed that the thermal polymerization was inhibited by addition of radicals, indicating that the propagation step proceeded by a radical intermediate.…”

Section: Chemistrymentioning

confidence: 99%

Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

258

220

View full text Add to dashboard Cite

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“…This degradation was observed even in cases when the polymers were not synthesized by ROP of cyclic disulfides but by other means, for example, step‐growth (nucleophilic substitution) polymerizations. Kinetic studies of the thermal ROP of 1,2‐dithiane also suggested that the reaction was reversible 27 …”

Section: Resultsmentioning

confidence: 99%

“…For instance, a single disulfide bond can be introduced in the polymer backbone by using suitable disulfide-containing difunctional initiators, for example, for atom transfer radical polymerization. 13,14 Multiple disulfide groups can be introduced by both (i) step-growth processes, such as nucleophilic substitution of aliphatic dihalides with salts containing the disulfide anion (S 2 2− ) 15,16 or oxidation of dithiols [17][18][19][20] (of either low 21 or high 22 molecular weight), and (ii) chain-growth reactions (which typically give high molecular weight polymers), such as the ring-opening polymerization (ROP) of cyclic disulfides 15,[23][24][25] by either radical 26,27 or anionic [28][29][30][31] mechanism. ROPs are attractive for several reasons.…”

Section: Introductionmentioning

confidence: 99%

Radical ring‐opening polymerization of lipoates: Kinetic and thermodynamic aspects

Raeisi

Tsarevsky

2021

Journal of Polymer Science

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The radical ring‐opening polymerization of a lipoate‐based monomer, ethyl lipoate, in bulk and in solution was studied at various temperatures and it was found that in all cases, only limited (plateau) conversions were reached, which were lower at higher temperatures and/or at higher dilutions. It was established that a monomer‐polymer equilibrium exists with a corresponding ceiling temperature of 139°C. Due to the reversibility of the lipoate polymerization, when poly(ethyl lipoate) was heated to 150°C, it degraded and within 3 h, the molecular weight decreased to less than 15% of the initial value. Likewise, when the polymer was dissolved in anisole and a radical initiator was added, degradation was observed even at 60°C and it became increasingly pronounced at higher concentrations of the radical source. Due to the presence of multiple disulfide groups in the backbone, poly(ethyl lipoate) also degraded in the presence of reducing agents, such as tributylphosphine, yielding the reduced (dithiol) form of the monomer, ethyl dihydrolipoate.

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“…Nevertheless, we found a convenient synthesis of polycatenane polymer from the bulk polymerization of cyclic disulfides such as 1,2-dithiane (DT) without any initiators. [9][10][11] The polymer was confirmed to contain a polycatenane structure (Scheme 1) from the characterizations of the polymer such as thermal and physical properties of the polymers. The polymer consisted of about 60 numbers of the non-interlocked cyclic polymer of DT, but the polymer dissolves in organic solvent such as CHCl 3 and THF even though it is hardly soluble in the organic solvents.…”

mentioning

confidence: 99%

Network Formation of Interlocked Copolymer Obtained from Copolymerization of 1,2-Dithiane and Lipoic Acid by Metal Salt

Yamanaka

Endo

2007

Polym J

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ABSTRACT:Network formation of interlocked copolymer obtained from the thermal ring-opening copolymerization of 1,2-dithiane (DT) and liopic acid (LPA) was investigated by the reaction of the poly(LPA-co-DT) and Zn(acetate) 2 . From the IR spectra of the reaction products, the reaction was induced readily to make a enough high degree of cross-linking in which the cross-linking points are polycatenane using a bifunctional metal salts by effective an ionomeric network. The cross-linking reaction of the precursor copolymer gave more thermo-stable product by the formation of the enough high degree of cross-linking structure.

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Thermal Polymerization of 1,2-Dithiane

Cited by 29 publications

References 18 publications

Sulfur Chemistry in Polymer and Materials Science

Sulfur Chemistry in Polymer and Materials Science

Radical ring‐opening polymerization of lipoates: Kinetic and thermodynamic aspects

Network Formation of Interlocked Copolymer Obtained from Copolymerization of 1,2-Dithiane and Lipoic Acid by Metal Salt

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