Polymerization of thietane

Price, Charles C.; Blair, E.

doi:10.1002/pol.1967.150050115

Cited by 29 publications

(6 citation statements)

References 4 publications

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“…Contrarily, the anionic ring‐opening polymerization of four‐membered rings of cyclic sulfides, that is, thietanes, ( Scheme ) is far more limited . Nevertheless, thietane and its derivatives were successfully polymerized to high molar mass polymers only by initiation with Grignard reagents, such as butyl lithium .…”

Section: Chemistrymentioning

confidence: 99%

Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

278

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%

Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

278

220

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“…Ether‐containing four‐membered rings (oxetanes) are generally supposed to be more prone than three‐membered ones (epoxides) to undergo ring opening through a cationic mechanism, mostly due to their higher basicity (ring strain and steric hindrance being substantially similar) 73. However, their well‐known cationic ring‐opening polymerisation74 fails when applied to thietanes,75 providing highly branched/cross‐linked materials: the active four‐membered sulfonium ions undergo not only propagation, due to the attack by monomers, but also termination due to the attack by thioethers of the polymer chains formed, which produce non‐cyclic and, therefore, unreactive sulfonium ions and short branches in the main chain (Scheme ). Therefore, other than in a few isolated cases, such as the production of core cross‐linked core‐shell block‐copolymeric structures,76 or the polymerisation of 3‐chorothietane77 (where the electron‐withdrawing effect of chlorine may reduce the nucleophilicity of the main chain sulfur atoms), this mechanism has seldom been used.…”

Section: Preparative Strategies For Polysulfidesmentioning

confidence: 99%

“…Although oxetanes can undergo anionic ring‐opening polymerisation, this takes place most commonly after the activation of the ring through complexation with Lewis acids 78. On the other hand, early polymerisation experiments had demonstrated that polymers can be obtained from thietanes utilising simple nucleophiles, such as Grignard reagents, as initiators 75. Further studies on the anionic polymerisation of thietanes have highlighted a peculiar behaviour: unless very polar solvents and high monomer concentrations are used, thiolates79 or delocalised anions (such as sodium naphthalene,79 styryl lithium70) are incapable of or ineffective in initiating this polymerisation.…”

Section: Preparative Strategies For Polysulfidesmentioning

confidence: 99%

“…It is worth mentioning that, in contrast to the “monomer route” (i.e., the use of sulfone‐containing monomers), at the beginning of the '70s a “polymer route” to polysulfones was proposed (Figure 3), which allowed to convert preformed aromatic polysulfides into the corresponding polysulfones by the help of hydrogen peroxide 59. Literature offers a number of later examples of this approach, which has been applied to the oxidation of aliphatic [such as poly(thietane),75 poly(ethylene sulfide)153, 154 and poly(hexene sulfide)155] and aromatic55, 57, 156 polysulfides to polysulfones. It is noteworthy that the “polymer route” may be the only way to produce main‐chain aliphatic polysulfones with the narrow MW dispersion typical of “living” chain polymerisation mechanisms, since the synthesis of sulfone‐contained strained rings (analogous to episulfides) is generally non‐trivial 157…”

Section: Preparative Strategies For Polysulfidesmentioning

confidence: 99%

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Polymers and Sulfur: what are Organic Polysulfides Good For? Preparative Strategies and Biological Applications

Kilcher

Tirelli

2009

Macromol. Rapid Commun.

106

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Sulfur(II)-containing polymers (polysulfides) combine flexible synthetic and processing techniques with a unique responsiveness to oxidants. Here, the polysulfide oxidative sensitivity is put into the biological context of the development of new anti-inflammatory therapies - the development of new anti-inflammatory methodologies, adopted interactions and the minimisation of foreign-body reactions - through the review of 50 years of research on polysulfide synthetic methodologies. Attention is paid to the identification of the most flexible and robust preparative techniques.

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“…1,3,4 Oxidative metamorphosis of polymer backbone has not been much studied except for reports on the oxidation of some polymonosulfides. [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] We wish to examine here successive oxidative metamorphosis of a disulfide polymer backbone to its respective mono-, di-, tri-and tetraoxide counterparts. Such backbone modifications on sulfide polymers is of considerable technological importance because the resultant oxidized polymers may find wide applications as oxidizing agents, compatibilizers, polymeric solvents, insulating materials, biocompatible membranes, etc.…”

Section: Introductionmentioning

confidence: 99%

Oxidative Metamorphosis of Poly(Styrenedisulfide) Backbone

2000

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This is the first report on the oxidation of a disulfide polymer, viz., poly(styrenedisulfide) (PSD). Oxidation was performed using KMnO 4 and KHSO4, which are strong and mild oxidizing agents, respectively. Fourier transform-infrared spectroscopy (FT-IR) and intrinsic viscosity ([η]) measurements revealed that degradation of PSD occurs to some extent during oxidation when KMnO4 was used. Further, FT-IR and [η] results indicated that the oxidation of PSD using KMnO4 is better in heterogeneous conditions than under phase-transfer medium because the degradation was curtailed in the former case. Direct pyrolysis-mass spectrometry (DP-MS), Fast atom bombardment mass spectrometry (FABMS) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) analyses of the oxidized PSD was carried out and the obtained results corroborate well with the FT-IR and [η] studies. Increased rigidity of the oxidized polymers which is reflected in their T g and [η] values, compared to PSD, was further confirmed by the radius of gyration (Rg) and trans percentage data calculated from the molecular dynamics simulations studies.

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Polymerization of thietane

Cited by 29 publications

References 4 publications

Sulfur Chemistry in Polymer and Materials Science

Sulfur Chemistry in Polymer and Materials Science

Polymers and Sulfur: what are Organic Polysulfides Good For? Preparative Strategies and Biological Applications

Oxidative Metamorphosis of Poly(Styrenedisulfide) Backbone

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