Thermally-healable network solids of sulfur-crosslinked poly(4-allyloxystyrene)

Thiounn, Timmy; Lauer, Moira K.; Bedford, Monte S.; Smith, Rhett C.; Tennyson, Andrew G.

doi:10.1039/c8ra06847j

Cited by 37 publications

(48 citation statements)

References 61 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…S7). The decomposition event (210–250 °C) common to all samples is attributable to the decomposition of elemental sulfur. In ZOS 59 ‐ ZOS 96 , an additional decomposition event is observed attributable to decomposition of organic domains.…”

Section: Resultsmentioning

confidence: 99%

“…One of the motivations behind studying the ZOS x copolymers was the potential for healing and recyclability . To test the thermal healability, a sample of ZOS 96 was damaged by applying two parallel scratches, the larger of which measured 75 × 75 μm (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Inverse vulcanization (Scheme ) has emerged as an intriguing approach to valorizing agricultural waste through the combination of sulfur with plant‐derived olefins . The sulfur used in the inverse vulcanization process is itself a waste product from desulfurization of fossil fuels, so when sustainably sourced waste product olefins are employed the materials achieved can be comprised entirely of waste products.…”

Section: Introductionmentioning

confidence: 99%

“…In contrast, the term inverse vulcanization, coined by Pyun, is generally applied to the process by which thermally generated polymeric sulfur radicals react with olefins in the rubber to form crosslinked materials that are generally comprised primarily of sulfur (Scheme ). The high sulfur‐content materials prepared by the inverse vulcanization process can also provide the added sustainability benefit of being healable and recyclable by merit of the thermal reversibility of S─S bond formation …”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Combining agriculture and energy industry waste products to yield recyclable, thermally healable copolymers of elemental sulfur and oleic acid

Smith

Thiounn

Lyles

et al. 2019

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

Self Cite

View full text Add to dashboard Cite

Sulfur and oleic acid, two components of industrial waste/byproducts, were combined in an effort to prepare more sustainable polymeric materials. Zinc oxide was employed to serve the dual role of compatibilizing immiscible sulfur and oleic acid as well as to suppress evolution of toxic H2S gas during reaction at high temperature. The reaction of sulfur, oleic acid, and zinc oxide led to a series of composites, ZOSx (x = wt % sulfur, where x is 8–99). The ZOSx materials ranged from sticky tars to hard solids at room temperature. The ZOSx compositions were assessed by 1H NMR spectrometry, FTIR spectroscopy, and elemental microanalysis. Copolymers ZOS59‐99, were further analyzed for thermal and mechanical properties by thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. Remarkably, even ZOS99, comprising only 1 wt % of zinc oxide/oleic acid (99 wt % S) exhibits at least an eightfold increase in storage modulus compared to sulfur alone. The four solid samples (59–99 wt % S) were thermally healable and readily remeltable with full retention of mechanical durability. These materials represent a valuable proof‐of‐concept for sustainably sourced, recyclable materials from unsaturated fatty acid waste products. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1704–1710

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Combining agriculture and energy industry waste products to yield recyclable, thermally healable copolymers of elemental sulfur and oleic acid

Smith

Thiounn

Lyles

et al. 2019

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

Self Cite

View full text Add to dashboard Cite

show abstract

“…Although elemental sulfur itself is quite brittle, durable materials can be obtained for the copolymers comprising up to 90 wt.% sulfur [51][52][53][54]. These efforts have employed a wide range of starting materials including cellulose, lignin, amino acids, terpenoids, algae acids, polystyrene derivatives, and other olefins [55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70]. More recently, radical-induced aryl halide/sulfur polymerization (RASP) proved similarly effective for preparation of high sulfur-content materials (HSMs) but employing aryl halides in place of the olefins required for inverse vulcanization.…”

Section: Lignin In High Sulfur-content Materialsmentioning

confidence: 99%

Valorization of Lignin as a Sustainable Component of Structural Materials and Composites: Advances from 2011 to 2019

Karunarathna

Smith

2020

Sustainability

Self Cite

View full text Add to dashboard Cite

Lignin is the most abundant aromatic biopolymer and is the sustainable feedstock most likely to supplant petroleum-derived aromatics and downstream products. Rich in functional groups, lignin is largely peerless in its potential for chemical modification towards attaining target properties. Lignin’s crosslinked network structure can be exploited in composites to endow them with remarkable strength, as exemplified in timber and other structural elements of plants. Yet lignin may also be depolymerized, modified, or blended with other polymers. This review focuses on substituting petrochemicals with lignin derivatives, with a particular focus on applications more significant in terms of potential commercialization volume, including polyurethane, phenol-formaldehyde resins, lignin-based carbon fibers, and emergent melt-processable waste-derived materials. This review will illuminate advances from the last eight years in the prospective utilization of such lignin-derived products in a range of application such as adhesives, plastics, automotive components, construction materials, and composites. Particular technical issues associated with lignin processing and emerging alternatives for future developments are discussed.

show abstract

Durable Cellulose–Sulfur Composites Derived from Agricultural and Petrochemical Waste

Lauer

Estrada‐Mendoza

McMillen

et al. 2019

Advanced Sustainable Systems

Self Cite

View full text Add to dashboard Cite

Nature provides a rich panoply of structural motifs comprised of composites whose mechanical properties exceed those of their individual components. The human endeavor to likewise craft value‐added structural materials from underappreciated, sustainably sourced feedstocks remains a formidable challenge. Herein, efforts are made to achieve durable composites by synergistic combination of sulfur and cellulose. Composites are achieved in which bulk sulfur is reinforced by a network of 1–20% by mass cellulose cross‐linked with polysulfide chains. Composites described herein are remeltable and have flexural strength exceeding that of Portland cement. A thorough analysis of these materials has been undertaken through nuclear magnetic resonance, infrared spectroscopy, Raman spectroscopy, elemental analysis, thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. These analyses of both as‐prepared composites and fractionated materials unequivocally validate the formulation of these composites and the separability of the bulk sulfur from the reinforcing polysulfide‐cross‐linked cellulose network. The thermomechanical properties of these recyclable composites portend their tantalizing potential to supplant inherently unsustainable structural elements in numerous commercial applications. Further applications to improve the environmental resistance and flexural strength of Portland cement by treatment with the sulfur–cellulose composites are also discussed.

show abstract

Thermally-healable network solids of sulfur-crosslinked poly(4-allyloxystyrene)

Abstract: Sulfur and a polystyrene derivative were combined to form thermally-healable and recyclable composite materials with dramatically increased structural integrity versus sulfur alone.

Cited by 37 publications

References 61 publications

Combining agriculture and energy industry waste products to yield recyclable, thermally healable copolymers of elemental sulfur and oleic acid

Combining agriculture and energy industry waste products to yield recyclable, thermally healable copolymers of elemental sulfur and oleic acid

Valorization of Lignin as a Sustainable Component of Structural Materials and Composites: Advances from 2011 to 2019

Durable Cellulose–Sulfur Composites Derived from Agricultural and Petrochemical Waste

Contact Info

Product

Resources

About