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Sulfur-Containing Polymers Prepared from Fatty Acid-Derived

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Sulfur-Containing Polymers Prepared from Fatty Acid-Derived Review Sulfur-Containing Polymers Prepared from Fatty Acid-Derived Monomers: Application of Atom-Economical Thiol-ene/Thiol-yne Click Reactions and Inverse Vulcanization Strategies Ashlyn D. Smith 1,2,*, Andrew G. Tennyson 2,3,* and Rhett C. Smith 2,* 1 Department of Chemistry, Anderson University, Anderson, SC 29621, USA 2 Department of Chemistry, Clemson University, Clemson, SC 29634, USA 3 Department of Materials Science and Engineering, Clemson University, Clemson, SC 29634, USA * Correspondence: [email protected] (A.D.S.); [email protected] (A.G.T.); [email protected] (R.C.S.) Received: 23 July 2020; Accepted: 22 September 2020; Published: 3 October 2020 Abstract: 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. Keywords: sustainable polymers; fatty acids; thiol-ene; inverse vulcanization 1. Introduction 1.1. Motivation for this Review Plastics pervade modern life [1–5], yet their accumulation in the environment is a threat to ecosystems globally [6–9] and only a small fraction of post-consumer plastics are recycled [10]. Strategies to use bio-derived precursors to prepare polymers and to assure the biodegradability or facile recyclability of polymers are at the forefront of sustainable chemistry and materials science [11–13]. Plant oils and their component fatty acids can be produced in all inhabited regions of the world, an important consideration for resilience and equity in resource distribution as it relates to sustainability. In this review, the focus is on plant oil-derived free fatty acids as precursors to organosulfur polymers. Free fatty acids are of interest because they are found in high percentages in waste products such as acid oil by-product of biodiesel production, used food grease waste, and low value products of animal fat rendering [14–22]. Sustain. Chem. 2020, 1, 209–237; doi:10.3390/suschem1030015 www.mdpi.com/journal/suschem Sustain. Chem. 2020, 1 210 Sustain.waste products Chem. 2020, such1 as acid oil by-product of biodiesel production, used food grease waste, and low210 value products of animal fat rendering [14–22]. PreparingPreparing modernmodern polymerspolymers from plantplant oil-derivedoil-derived precursors has been ofof interestinterest forfor severalseveral decadesdecades [[23,24],23,24], andand therethere havehave beenbeen severalseveral insightfulinsightful reviewsreviews coveringcovering variousvarious aspectsaspects ofof materialsmaterials derivedderived from triglycerides [25–31] [25–31] and and fatty fatty acids acids [32–35]. [32–35]. The The current current review review centers centers specifically specifically on onorganosulfur organosulfur polymers polymers derived derived from from fatty fatty acids. acids. These These materials materials are are especially especially attractive attractive from from a asustainability sustainability standpoint standpoint because because of ofthe the high high atom atom economy economy with with which which they they can can be prepared be prepared by the by themethods methods discussed discussed in the in next the nexttwo twosections. sections. A review A review on this on particular this particular niche nicheis timely is timely because because in the inlast the few last years few yearsseveral several important important advances advances have capitalized have capitalized on the on facile the facilereversibility reversibility of S–S of bond S–S bondformation formation to access to access healable healable and and readily-recyclable readily-recyclable materials materials with with high high strength strength and chemicalchemical resistance.resistance. ThisThis new class of recyclable and healable fatty acid-derived materials hashas notnot been covered previouslypreviously inin thethe aforementionedaforementioned reviewsreviews onon fattyfatty acid-derivedacid-derived polymers.polymers. 1.2.1.2. Sources and ClassificationClassification ofof FattyFatty AcidsAcids FattyFatty acidsacids areare generallygenerally obtainedobtained byby thethe hydrolysishydrolysis ofof triglyceridestriglycerides (Figure(Figure1 1),), thethe primary primary constituentsconstituents ofof plantplant oilsoils andand animalanimal fats.fats. The typical fatty acid component breakdown for a varietyvariety ofof familiarfamiliar sourcessources isis summarizedsummarized inin TableTable1 1.. Common Common fatty fatty acids acids provide provide a a plethora plethora of of possibilities possibilities forfor chemicalchemical modification.modification. The The carboxylate carboxylate function functionalityality can can be esterified esterified or undergo amidation, whilewhile unsaturatedunsaturated fatty acids also aaffordfford thethe possibilitypossibility of functionalization at the olefin olefin units. Ricinoleate,Ricinoleate, primarilyprimarily foundfound inin castorcastor oil,oil, isis uniqueunique amongamong thethe structuresstructures shownshown inin FigureFigure1 1 in in that that it it alsoalso featuringfeaturing anan alcoholalcohol moiety,moiety, allowingallowing additionaladditional modificationmodification at at this this site. site. Figure 1. General structures for fatty acids derivedderived from naturally-occurringnaturally-occurring triglycerides.triglycerides. WhileWhile thethe relativerelative percentagespercentages ofof eacheach classclass ofof fattyfatty acidsacids variesvaries widelywidely byby species,species, itit isis notablenotable thatthat in a a wide wide range range of of species species ranging ranging from from tree-de tree-derivedrived sources sources (olive (olive oil) oil) to flowers to flowers (sunflower (sunflower and andsafflower safflower oil), oil),to underground to underground legumes legumes (peanut (peanut oil), oil), the the most most common common saturated saturated fatty fatty acid acid (SFA) componentcomponent isis palmiticpalmitic acidacid (16-carbon(16-carbon chain),chain), thoughthough coconutcoconut oiloil featuresfeatures predominantlypredominantly lauriclauric acidacid (12-carbon(12-carbon chain)chain) as as the the SFA SFA in its in triglycerides. its triglyceride Thes. mostThe commonmost common monounsaturated monounsaturated fatty acid fatty (MUFA) acid is(MUFA) generally is generally oleic acid oleic (18-carbon acid (18-carbon chain). Givenchain). that Given the that olefin the functionality olefin functionality plays a plays key role a key in role the reactivityin the reactivity of fatty of acids fatty with acids sulfur with species, sulfur oleicspecies, acid-derived oleic acid-derived monomers monomers are the most are well-studied the most well- for developmentstudied for development of polymers of discussed polymers herein. discussed The herein. most common The most polyunsaturated common polyunsaturated fatty acid (PUFA) fatty acid in common(PUFA) in oils common is diunsaturated oils is diunsaturated linoleic acid (18-carbonlinoleic acid chain (18-carbon with two chain olefins), with though two olefins), linseed though oil is a commonlinseed oil example is a common in which example linolenic in which acid (18-carbon linolenic ac chainid (18-carbon with three chain olefins) with is three the most olefins) common is the PUFA.most common Throughout PUFA. the Throughout course of the the current course review,of the current fatty acids review, available fatty acids from available many of thefrom sources many shownof the sources in Table 1shown, as well in theTable unique 1, as ricinoleate well the unique derivatives ricinoleate from castor derivatives oil, will fr beom discussed. castor oil, will be discussed. Sustain. Chem. 2020, 1 211 Sustain. Chem. 2020, 1 Table 1. Fatty acid chain type compositions of some common plant oils. 211 SFA Chains MUFA Chains PUFA Chains Source Content Predominant Content Predominant PUFA Content Predominant Chain (%Table of Total) 1. aFatty Chain acid Length chain (% type of Total) compositions Chain Length of some (% common of Total) plantLength oils. (Unsaturation) b Coconut 92 12 6 18 2 18 (2) Olive SFA15 Chains16 74 MUFA Chains18 10 PUFA Chains18 (2) Canola 8 16 62 18 32 18 (2) Predominant SourcePeanut Content18 Predominant16 Content50 Predominant18 32PUFA Content 18 (2) Safflower
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