Rational Entry to Cyclic Polymers via Thermally Induced Radical Ring-Expansion Polymerization of Macrocycles with One Bis(hindered amino)disulfide Linkage

Takashima, Rikito; Aoki, Daisuke; Otsuka, Hideyuki

doi:10.1021/acs.macromol.0c00798

Cited by 19 publications

(22 citation statements)

References 40 publications

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“…By virtue of the unique dynamic behavior, BITEMPS-S2 were utilized to impart the specific features such as self-healing and reprocessable cross-linked polymers, the fusion of different cross-linked polymers, the topological rearrangement from linear to cyclic polymers, and self-strengthening of cross-linked elastomers. [10][11][12][13][14][15][16] Afterward, we reported that the trisulfide analogue of BITEMPS-S2, bis(2,2,6,6-tetramethylpiperidin-1-yl)trisulfide (BITEMPS-S3), also behave as an DCB to produce air-stable thiyl and dithiyl radicals upon heating at mild temperature (as shown in Scheme 1b). 17 Additionally, poly(n-hexylmethacrylate) network containing BITEMPS-S3 units at cross-linking points afforded nearly quantitative damage healability only by simple hot pressing at 110 °C for 24 h, which were almost comparable to one containing BITEMPS-S2 units (100 °C for 24 h).…”

Section: Introductionmentioning

confidence: 99%

Effect of bulky 2,6-bis(spirocyclohexyl)-substituted piperidine rings in bis(hindered amino)trisulfide on thermal healability of polymethacrylate networks

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Section: Introductionmentioning

confidence: 99%

Effect of bulky 2,6-bis(spirocyclohexyl)-substituted piperidine rings in bis(hindered amino)trisulfide on thermal healability of polymethacrylate networks

et al. 2021

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“…Similar tendency was observed in our previous literature. 37 The UV− vis spectra of the Copolymer in dilute CDCl 3 were almost identical to those of the CP(NDI) and CP(DAN) mixture (Figure S37). Similarly, the aromatic region of the 1 H NMR spectra at the same concentration showed no significant changes (Figure S38).…”

Section: ■ Results and Discussionmentioning

confidence: 79%

“…Bulk Polymerization Behavior. In our previous reports, 37,38 all MMs were crystalline compounds with high melting points that did not polymerize when heated to 100 °C in the bulk state. However, MM(NDI) and MM(DAN) are both amorphous compounds that can flow at high temperature.…”

Section: ■ Results and Discussionmentioning

confidence: 86%

Synthetic Strategy for Mechanically Interlocked Cyclic Polymers via the Ring-Expansion Polymerization of Macrocycles with a Bis(hindered amino)disulfide Linker

2021

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Mechanically interlocked polymers that contain rotaxane and catenane structures have attracted much attention on account of their unique properties arising from the restricted mobility of their interlocked structure and their robustness which are comparable to those of covalent bonds. Among these polymers, mechanically interlocked cyclic polymers (MICPs) exhibit great potential as a novel type of polymer with a large movable area of the interlocked structure. However, synthetic routes to MICPs are not well developed, and it is still challenging to create MICPs. The present study has resulted in an effective method for the synthesis of MICPs from the combination of the ring-expansion polymerization (REP) of cyclic disulfide monomers with supramolecular interactions. Macrocyclic monomers (MMs) that consist of a bis(hindered amino)disulfide (BiTEMPS) linker and a supramolecular moiety, such as naphthalenediimide (NDI) and dialkoxynaphthalene (DAN), capable of forming a strong 1/1 charge-transfer complex, were synthesized as the monomers for the subsequent REP. These MMs were used in a heat-induced REP in the bulk state, which led to their swift polymerization via an intermolecular exchange reaction of BiTEMPS. The change in mechanical properties during the polymerization was monitored by rheological measurements of the increase of the storage modulus, G′. Importantly, the bulk copolymerization of the MMs containing NDI and DAN increased the hydrodynamic volume of the resulting copolymers, which is due to the spatial entanglement of the polymer chains. The change in the physical properties of the resulting polymers stands in sharp contrast to that observed in polymers with a linear topology made from the same monomers, thus supporting the formation of MICPs. The results provide guidelines for the successful design of MICPs, that is, a combination of the dynamic nature of the MMs and supramolecular interactions. Given that the present method is highly versatile, it can be expected to be applicable to various molecular skeletons and supramolecular systems.

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“…By virtue of their unique dissociation features, BiTEMPS were initially utilized as cross-linking point within polymer networks to impart a thermally induced healing property. [15] Despite the elegant achievements based on the dynamic behavior of BiTEMPS derivatives, [16] such as the fusion of different crosslinked polymers, [17] the topological rearrangement from linear to cyclic polymers, [18,19] and synthesis of end-functionalized Macromol. Rapid Commun.…”

Section: Introductionmentioning

confidence: 99%

“…By virtue of their unique dissociation features, BiTEMPS were initially utilized as cross‐linking point within polymer networks to impart a thermally induced healing property. [ 15 ] Despite the elegant achievements based on the dynamic behavior of BiTEMPS derivatives, [ 16 ] such as the fusion of different cross‐linked polymers, [ 17 ] the topological rearrangement from linear to cyclic polymers, [ 18,19 ] and synthesis of end‐functionalized polymers, [ 20 ] to the best of our knowledge, the protocols utilized for the preparation of BiTEMPS containing polymers has been limited to conventional free‐radical or step‐growth polymerization approaches. Critically, due to the thermal lability of the BiTEMPS unit at temperatures above 80 °C, [ 14 ] previously reported polymerizations were essentially performed at ambient temperatures (Scheme 1B,C).…”

Section: Introductionmentioning

confidence: 99%

Acyclic Diene Metathesis (ADMET) Polymerization of 2,2,6,6‐Tetramethylpiperidine‐1‐sulfanyl (TEMPS) Dimers

Hobich

Huber

Théato

et al. 2021

Macromol. Rapid Commun.

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of polymers with functional groups containing heteroatoms within the main chain. This reaches from carbon-oxygen bonds (e.g., ethers, esters, and carbonates) to carbon-nitrogen (e.g., imines, [3] hydrazones, [4] and oximes [5] ). Interestingly, their sulfur-containing analogues, [6] have been underestimated for long time, although the intrinsic characteristics of these polymers are offering a myriad of superior properties (e.g., degradation, flame retardancy, film-forming ability, good solubility in polar solvents, and high refractivity with small chromatic dispersions amongst other) compared to the carbon-derivatives. This is particularly the case for sulfurnitrogen based polymers. The distinctive characteristics of the sulfur-nitrogen based polymers result from the unique chemical properties of the sulfur-nitrogen bond (e.g., its polar character and the multiple valence states of sulfur). As one of the most intriguing dynamic covalent bonds featuring a simple redox chemistry, the disulfide bond has a crucial importance in organic and polymer chemistry. [7] On the contrary, the amino-and diaminodisulfide functional groups (-S-S-N-and -N-S-S-N-, respectively) are rarely studied in organic chemistry, and the respective polymers are very much in their infancy. At the same time, diaminodisulfide and its derivatives represented with the formula -N-S-S-N-, are known for their low S-S bond dissociation energies (e.g., BDE of 180 kJ mol −1 for the simplest diaminodisulfide H 2 N-S-S-NH 2 ) in reference to diaryl and dialkyl disulfide bonds (190-230 and 250-290 kJ mol −1 , respectively). In spite of this, diaminodisulfides are stable and readily handled at ambient temperature as a result of the high stability of the respective thiyl radicals that are formed via catalyst freethermally induced reversible dissociation. Literature survey also clearly depicts that polymers with sulfur-nitrogen bond (particularly, poly(sulfenamide)s, poly(diaminosulfide)s, and poly(diaminodisulfide)s [8,9] ) could be considered as sleeping beauties and (re)appear to be promising for new materials that combine the advantages of sulfur and nitrogen solely. While, the first synthesis of organic molecules decorated with disulfidediamine dates back to 1895, [10] it took almost a century until a pioneering study on polymeric diaminodisulfide derivatives was reported in 1991. [11] Whilst the study failed to provide any complementary characterization of the reported poly(diaminodisulfide) derivatives, the first report dealing with the in-depth characterization of this polymer class dates back to 2012. [12] In a recent study, Otsuka and co-workers, [13] The preparation of polymers containing sulfur-nitrogen bond derivatives, particularly 2,2,6,6-tetramethylpiperidine-1-sulfanyl (TEMPS) dimers (i.e., BiTEMPS), has been limited to free-radical or conventional step-growth polymerization as result of the inherent thermal lability of the BiTEMPS unit. Accordingly, a novel poly(diaminodisulfide) possessing the BiTEMPS functional group is synthesized via acyc...

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Rational Entry to Cyclic Polymers via Thermally Induced Radical Ring-Expansion Polymerization of Macrocycles with One Bis(hindered amino)disulfide Linkage

Cited by 19 publications

References 40 publications

Effect of bulky 2,6-bis(spirocyclohexyl)-substituted piperidine rings in bis(hindered amino)trisulfide on thermal healability of polymethacrylate networks

Effect of bulky 2,6-bis(spirocyclohexyl)-substituted piperidine rings in bis(hindered amino)trisulfide on thermal healability of polymethacrylate networks

Synthetic Strategy for Mechanically Interlocked Cyclic Polymers via the Ring-Expansion Polymerization of Macrocycles with a Bis(hindered amino)disulfide Linker

Acyclic Diene Metathesis (ADMET) Polymerization of 2,2,6,6‐Tetramethylpiperidine‐1‐sulfanyl (TEMPS) Dimers

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