Copolymers by Inverse Vulcanization of Sulfur with Pure or Technical‐Grade Unsaturated Fatty Acids

Smith, Ashlyn D.; McMillen, Colin D.; Smith, Rhett C.; Tennyson, Andrew G.

doi:10.1002/pol.20190138

Cited by 45 publications

(42 citation statements)

References 35 publications

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“…Although inverse vulcanization was reported only a few years ago, its potential for facile production of versatile materials was quickly recognized. In a very short time, olefins derived from petroleum [8][9][10][11][12][13][14][15][16], plant and animal sources [11,[17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] bacteria [28] and algae [35] have all proven to be successful monomers for the production of HSMs by inverse vulcanization. These HSMs have garnered significant attention for their potential as IR transparent lenses for thermal imaging [36], electrode materials [37,38] absorbents [11,13,[39][40][41], fertilizers [18,22], and structural materials [29,[42][43][44][45][46].…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of a Bisphenol a Derivative and Elemental Sulfur by the RASP Process

Thiounn

Lauer

Karunarathna

et al. 2020

Sustainable Chemistry

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Fossil fuel refining produces over 70 Mt of excess sulfur annually from for which there is currently no practical use. Recently, methods to convert waste sulfur to recyclable and biodegradable polymers have been delineated. In this report, a commercial bisphenol A (BPA) derivative, 2,2′,5,5′-tetrabromo(bisphenol A) (Br4BPA), is explored as a potential organic monomer for copolymerization with elemental sulfur by RASP (radical-induced aryl halide-sulfur polymerization). Resultant copolymers, BASx (x = wt% sulfur in the monomer feed, screened for values of 80, 85, 90, and 95) were characterized by thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. Analysis of early stage reaction products and depolymerization products support proposed S–Caryl bond formation and regiochemistry, while fractionation of BASx reveals a sulfur rank of 3–6. Copolymers having less organic cross-linker (5 or 10 wt%) in the monomer feed were thermoplastics, whereas thermosets were accomplished when 15 or 20 wt% of organic cross-linker was used. The flexural strengths of the thermally processable samples (>3.4 MPa and >4.7 for BAS95 and BAS90, respectively) were quite high compared to those of familiar building materials such as portland cement (3.7 MPa). Furthermore, copolymer BAS90 proved quite resistant to degradation by oxidizing organic acid, maintaining its full flexural strength after soaking in 0.5 M H2SO4 for 24 h. BAS90 could also be remelted and recast into shapes over many cycles without any loss of mechanical strength. This study on the effect of monomer ratio on properties of materials prepared by RASP of small molecular aryl halides confirms that highly cross-linked materials with varying physical and mechanical properties can be accessed by this protocol. This work is also an important step towards potentially upcycling BPA from plastic degradation and sulfur from fossil fuel refining.

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Section: Introductionmentioning

confidence: 99%

Copolymerization of a Bisphenol a Derivative and Elemental Sulfur by the RASP Process

Thiounn

Lauer

Karunarathna

et al. 2020

Sustainable Chemistry

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“…The physical properties of composites prepared by reaction of sulfur with unsaturated organic molecules depend strongly on the crosslink density in the materials. 2,16,17,[35][36][37][38][39]41 In one study, an increase of 1% in the unsaturation content led to an 8-fold increase in the material's storage modulus, for example. 17 Given this observation, plant oils spanning a range of unsaturation numbers (number of C=C bond units per fatty acid chain in the composite triglycerides) were selected for polymerization so that the extent to which unsaturation number influences composite properties.…”

Section: Resultsmentioning

confidence: 99%

“…The nearly 100% atom-economical polymerization of triglycerides [7][8][9][10][11][12][13][14] or fatty acids [15][16][17] by their reaction with elemental sulfur has recently emerged as a facile, green way to convert plant oils into composites. This is an especially attractive route because it employs sulfur, itself a waste product of fossil fuel refining.…”

Section: A)mentioning

confidence: 99%

High strength, acid‐resistant composites from canola, sunflower, or linseed oils: Influence of triglyceride unsaturation on material properties

Lopez

Karunarathna

Lauer

et al. 2020

Journal of Polymer Science

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Herein are reported composites made by crosslinking unsaturated units in canola, sunflower or linseed oil with sulfur to yield CanS, SunS and LinS, respectively. These plant oils were selected because the average number of crosslinkable unsaturated units per triglyceride vary from 1.3 for canola to 1.5 for sunflower and 1.8 for linseed oil. The remeltable composites show compressive strengths that increase with increasing unsaturation number from CanS (9.3 MPa) to SunS (17.9 MPa) to LinS (22.9 MPa). These values for SunS and LinS are competitive when compared to the value of 17 MPa required for residential building using traditional Portland cement. The plant oil composites are recyclable over many cycles and can retain up to 100% of strength after 24 h in oxidizing acid under conditions where Portland cement is dissolved in under 30 min. Infusion of the composites into premade cement blocks affords them with significantly improved acid resistance as well. This work thus provides a simple, nearly 100% atom economical route to convert plant oils and waste sulfur to composites having enhanced performance over commercial structural materials.

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“…In addition to petrochemically-derived olefins, many biologically-derived olefins have also been successfully exploited as comonomers with sulfur, including terpenoids [77][78][79][80]. Triglycerides [81][82][83][84][85][86][87][88], fatty acids [89][90][91][92], sorbitan esters [93], amino acid derivatives [94], guaiacol derivatives [95], and cellulose/lignin derivatives or lignocellulosic biomass [11,[96][97][98][99][100].…”

Section: Inverse Vulcanization Versus Classical Vulcanizationmentioning

confidence: 99%

Sulfur-Containing Polymers Prepared from Fatty Acid-Derived Monomers: Application of Atom-Economical Thiol-ene/Thiol-yne Click Reactions and Inverse Vulcanization Strategies

Smith

Tennyson

Smith

2020

Sustainable Chemistry

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This paper is review with 119 references. Approaches to supplant currently used plastics with materials made from more sustainably-sourced monomers is one of the great contemporary challenges in sustainable chemistry. Fatty acids are attractive candidates as polymer precursors because they can be affordably produced on all inhabited continents, and they are also abundant as underutilized by-products of other industries. In surveying the array of synthetic approaches to convert fatty acids into polymers, those routes that produce organosulfur polymers stand out as being especially attractive from a sustainability standpoint. The first well-explored synthetic approach to fatty acid-derived organosulfur polymers employs the thiol-ene click reaction or the closely-related thiol-yne variation. This approach is high-yielding under mild conditions with up to 100% atom economy and high functional group tolerance. More recently, inverse vulcanization has been employed to access high sulfur-content polymers by the reaction of fatty acid-derived olefins with elemental sulfur. This approach is attractive not only because it is theoretically 100% atom economical but also because elemental sulfur is itself an underutilized by-product of fossil fuel refining. The thiol-ene, inverse vulcanization, and mechanistically-related thiol-yne and classic vulcanization are therefore discussed as promising routes to access polymers and composites from fatty acid-derived precursors.

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Copolymers by Inverse Vulcanization of Sulfur with Pure or Technical‐Grade Unsaturated Fatty Acids

Cited by 45 publications

References 35 publications

Copolymerization of a Bisphenol a Derivative and Elemental Sulfur by the RASP Process

Copolymerization of a Bisphenol a Derivative and Elemental Sulfur by the RASP Process

High strength, acid‐resistant composites from canola, sunflower, or linseed oils: Influence of triglyceride unsaturation on material properties

Sulfur-Containing Polymers Prepared from Fatty Acid-Derived Monomers: Application of Atom-Economical Thiol-ene/Thiol-yne Click Reactions and Inverse Vulcanization Strategies

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