Controlled Organocatalytic Ring-Opening Polymerization of ε-Thionocaprolactone

Datta, Partha Priya; Kiesewetter, Matthew K.

doi:10.1021/acs.macromol.6b00136

Cited by 46 publications

(53 citation statements)

References 27 publications

(79 reference statements)

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“…Mechanistically, it was postulated that the inversion of S/O substitution proceeded via an S N 2 propagation. Ultimately, the ROP of ε‐thionocaprolactone without carbonyl scrambling was furnished at ambient temperatures in the presence of alcohol (or thiol) as initiator (Scheme D) . Utilizing DBU as a base resulted in a linear evolution of M n versus time and an initially narrow Đ that broadens throughout the ROP.…”

Section: Chemistrymentioning

confidence: 99%

Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

255

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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.

255

220

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“…Notably, this synthetic approach differed in mechanism, scope, and compatibility from the documented organocatalytic ring-opening homopolymerizations of ε-thiocaprolactone (wherein monomer and polymer feature a thioester, C(=O)S) 30 and of ε-thionocaprolactone (wherein monomer and polymer feature a thionoester, C(=S)O). 31 To the best of our knowledge, pDOT-an unusual polymer featuring a biphenyl and a thioester in the backbone-had not previously been prepared and isolated by any method. The homopolymer was found to be soluble in DMSO, CDCl 3 , and THF, and insoluble in methanol, diethyl ether, and hexane.…”

Section: Dot Homopolymerizationmentioning

confidence: 99%

Fully Degradable Thioester-Functional Homo- and Alternating Copolymers Prepared through Thiocarbonyl Addition–Ring-Opening RAFT Radical Polymerization

et al. 2020

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The radical ring-opening polymerization (RROP) of thionolactones provides access to thioester backbone-functional copolymers but has, to date, only been demonstrated on acrylic copolymers. Herein, the thionolactone dibenzo[c,e]oxepane-5-thione (DOT) was subjected to AIBN-initiated free radical homopolymerization which produced a thioester-functional homopolymer with a glass transition temperature of 95 °C and the ability to degrade exclusively into predetermined small molecules. However, the homopolymerization was impractically slow and precluded the introduction of functionality. Conversely, the RAFT-mediated copolymerization of DOT with Nmethylmaleimide (MeMI), N-phenylmaleimide (PhMI), and N-2,3,4,5,6pentafluorophenylmaleimide (PFPMI) rapidly produced well-defined copolymers with the tendency to form alternating sequences increasing in the order MeMI ≪ PhMI < PFPMI, with estimated reactivity ratios of r DOT = 0.198 and r PFPMI = 0.0078 for the latter system. Interestingly, defects in the alternating structure were more likely caused by (degradable) DOT-DOT sequences rather than (non-degradable) MI-MI sequences, which was confirmed through paper spray mass spectrometric analysis of the products from aminolytic degradation. Upon the aminolysis of backbone thioesters, maleimide repeating units were ring-opened, forming bisamide structures. Conversely, copolymer degradation through a thiolate did not result in imide substitution but nucleophilic para-fluoro substitution on PFPMI comonomer units, indicating the ability of DOT-MI copolymers to degrade under different conditions and to form differently functional products. The RROP of thionolactones has distinct advantages over RROP of cyclic ketene acetals and is anticipated to find use in the development of well-defined degradable polymer materials.

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“…Although monomer scope has broadened recently, organocatalysts have most fre-quently been applied to the ROP of lactones, but these same systems have also been shown to be effective for the ROP of a thiolactone and a thionolactone. 11,12 Polythioesters have properties similar to those of their polyester analogues; [12][13][14] however, the altered materials properties of polythionolactones make them an especially enticing synthetic target. 11 Versus the corresponding polyesters, the polythionoesters possess altered physical properties, degradability and novel post polymerization functionalization abilities.…”

Section: Introductionmentioning

confidence: 99%