high strength, acid‐resistant composites from canola
TRANSCRIPT
OR I G I N A L AR T I C L E
High strength, acid-resistant composites from canola,sunflower, or linseed oils: Influence of triglycerideunsaturation on material properties
Claudia V. Lopez | Menisha S. Karunarathna | Moira K. Lauer |
Charini P. Maladeniya | Timmy Thiounn | Edward D. Ackley | Rhett C. Smith
Department of Chemistry and Center forOptical Materials Science and EngineeringTechnology, Clemson University,Clemson, South Carolina
CorrespondenceRhett C. Smith, Department of Chemistryand Center for Optical Materials Scienceand Engineering Technology, ClemsonUniversity, Clemson, SC 29634.Email: [email protected]
Funding informationNational Science Foundation, Grant/Award Number: CHE-1708844
Abstract
Here 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 compres-
sive 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 with the value of 17 MPa required for
residential building using traditional Portland cement. The plant oil compos-
ites are recyclable over many cycles and can retain up to 100% of strength after
24 hr 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 pro-
vides a simple, nearly 100% atom economical route to convert plant oils and
waste sulfur to composites having enhanced performance over commercial
structural materials.
KEYWORD S
inverse vulcanization, polymerization, sulfur, sustainable composites, triglyceride
1 | INTRODUCTION
Plant oils, comprised primarily of triglycerides(Figure 1a), represent a bountiful organic resource tosupplant petrochemical olefins for the production ofmore sustainable plastics and fuels. In addition to plantoils that are now widely produced specifically for use aspetrochemical replacements (most commonly for biodie-sel production), the North American Renderers Associa-tion reports that over 4.4 billion pounds of used cookingoil are produced annually from the US and Canadianmarkets alone.[1] Given the abundant available
resources and promising technoeconomic analysis ofplant oils as industrial feedstocks,[2] many efforts havetargeted plant oil-derived composites. These efforts aresummarized in some insightful reviews.[3–5] Theseefforts establish significant insight into the reactivityand capability of triglyceride starting materials, butsome plant oil-derived composites require stepwisemanipulations and separation processes to convert plantoil triglycerides to appropriate monomers prior to theirpolymerization. These steps add to the cost of productsand detract from atom economy and overall greennessof such processes.
Received: 27 April 2020 Revised: 9 June 2020 Accepted: 11 June 2020
DOI: 10.1002/pol.20200292
J Polym Sci. 2020;58:2259–2266. wileyonlinelibrary.com/journal/pol © 2020 Wiley Periodicals LLC 2259
The nearly 100% atom-economical polymerization oftriglycerides[6–13] or fatty acids[14–16] by their reactionwith elemental sulfur has recently emerged as a facileand green way to convert plant oils into composites. Thisis an especially attractive route because it employs sulfur,itself a waste product of fossil fuel refining. The polymeri-zation of triglycerides with sulfur relies on the initialthermal generation of polymeric sulfur radicals, whichsubsequently react with and crosslink olefin functional
groups in unsaturated chains in the triglycerides (Figure 1b).This process, known as inverse vulcanization,[17–19] occursat temperatures of 90–180�C, and produces materials thatare often melt processable over many cycles without degra-dation of their mechanical strength.[13,20–23] Similar reactiv-ity of triglyceride derivatives with sulfur radicals has alsobeen reported by the thiol-ene reaction.[24–32]
Triglyceride-sulfur materials prepared by inversevulcanization have proven highly effective as adsorbentsfor water purification, as cathode materials in Li-Sbatteries,[33] and as fertilizers. Less work has been doneto elucidate the mechanical strength and chemicalresilience of triglyceride-sulfur composites, although sig-nificant progress on elucidating monomer composition-mechanical property relationships has been made forhigh sulfur-content materials in general.[6] We haveundertaken several studies that demonstrate highstrength of sulfur-crosslinked composites that can addi-tionally be thermally healable/recyclable and displayimpressive durability to oxidizing acids.[34–40]
In the current report, sulfur-crosslinked compositeswere prepared from commercial canola (rapeseed) oil, sun-flower oil or linseed (flax) oil to yield composites CanS,SunS, and LinS, respectively. The extent to which the oil'sunsaturation number, and thus crosslink density, influencesthe mechanical strength of the materials was evaluated. Theability of each material to resist mechanical degradation byoxidizing acid was also assessed. Finally, premade Portlandcement blocks were pressure-treated with each materialand the resultant CanS-, SunS-, and LinS- infused Portlandcements (CanIP and SunIP, respectively) were tested forimprovements in resilience to oxidative acid challenge.
2 | RESULTS AND DISCUSSION
The physical properties of composites prepared byreaction of sulfur with unsaturated organic moleculesdepend strongly on the crosslink density in thematerials.[15,16,34–39,41] In one study, an increase of 1% inthe unsaturation content led to an eightfold increase inthe material's storage modulus, for example.[16] Given thisobservation, plant oils spanning a range of unsaturationnumbers (number of C C bond units per fatty acid chainin the composite triglycerides) were selected for polymeri-zation so that the extent to which unsaturation numberinfluences composite properties could be assessed. Analy-sis of plant oil triglyceride content by the conventionalFAMES method[42] reveals the fatty acid compositionssummarized in Table 1, leading to average unsaturationnumbers of 1.3, 1.5, and 1.8 unsaturated units per fattyacid chain for canola, sunflower (high linoleic) and lin-seed oils, respectively.
(a)
(b)
FIGURE 1 General structure of triglycerides and their
primary fatty acid substituents (a) and the inverse vulcanization of
unsaturated units upon their reaction with thermally-generated
sulfur radicals (b) [Color figure can be viewed at
wileyonlinelibrary.com]
2260 LOPEZ ET AL.
Polymerization of the plant oils with sulfur followedthe reported procedures[6–12,43] in which sulfur and plantoil were heated to an eventual temperature of 180 �Cwith rapid stirring for 35 min. The reaction of 90 wt% sul-fur with 10 wt% of either canola oil or sunflower oil ledto the formation of composites CanS and SunS, respec-tively. These composites were brown-colored, remeltablesolids (Figure 2). When the analogous reaction wasattempted with linseed oil, however, only some of thecomposite could be remelted following synthesis, whilesome thermoset pieces remained suspended in the mix-ture. This observation is likely a result of the highercrosslinking density enabled by the more unsaturated lin-seed oil compared to the other plant oil monomers.Because the proposed downstream experiments rely onthe ability to re-shape the composites by melt processing,the amount of linseed oil crosslinker in the polymeriza-tion monomer feed had to be reduced. Polymerization of95 wt% sulfur with 5 wt% linseed oil led to compositeLinS as a remeltable solid (Figure 2) similar in its pro-cessability and slightly darker brown in appearance com-pared to the other two composites. Comparison ofinfrared spectra of the plant oils to those of the compos-ites confirmed near complete consumption of olefin units
in the reaction process (spectra are provided in theSupporting Information).
The aforementioned prior work on triglyceride-sulfurinverse vulcanization revealed that the materials consistof some free sulfur commingled with the sulfur-crosslinked triglyceride network, so that the materials arebest described as composites. In the current study, differ-ential scanning calorimetry (DSC) likewise confirmed thepresence of 79–85 wt% free sulfur in the composites. DSCdata with integration to quantify sulfur content of thematerials can be found in Figure S5 and Table S1.
Plant oil-sulfur composites have proven valuable asadsorbents or fertilizers,[4–10] and a recent assessment ofthe impact of triglyceride structure on adsorption kineticsproperties of sulfur-plant oil composites has beenreported.[43] In contrast, the main goal of the currentstudy was to evaluate strength and chemical resistance ofthe composites, so once prepared, samples of CanS,SunS, and LinS were melted down and poured into sili-cone molds for shaping into cylinders appropriate forcompressive strength measurements. The densities of thecylinders were first determined. The density of a materialis an important consideration if it is to be used as a struc-tural component in infrastructure. Low-density materialsare preferred to cut down on transportation and handlingcosts as well as the load of the composite structure thatmust be supported by its foundation. To meet buildingcode requirements such as American Concrete Institute(ACI) standard ACI-213R and ASTM 169C, the density ofnormal weight structural material like cement must be2,240–2,400 kg/m3 whereas a lightweight cement has adensity in the range of 1,440–1,840 kg/m3.[44,45] In thecurrent case, the densities fall into the range of1,700–1,800 kg/m3 (Table 2). These values classify theplant oil-sulfur composites as lightweight building com-ponents in terms of density.
Water uptake is another important classification met-ric for structural materials. If a material absorbs water inan exterior application, the water can undergo cyclicexpansion and contraction over periodic freeze–thawevents, leading to the formation of fissures in the mate-rial. Water uptake of the plant oil-sulfur composites were
TABLE 1 Fatty acid composition
for plant oils used in the current studyCanola oil Sunflower oil Linseed oil
Saturated chains (%) 8 13 10
Oleic and other monounsaturated (%)a 60 22 19
Linoleic and other diunsaturated (%)a 22 65 17
Linolenic and other triunsaturated (%)a 10 <1 55
Unsaturated bonds per chain (average) 1.3 1.5 1.8
aIn each category of unsaturated chains, <2% of the oils are components other than oleic, lin-oleic, or linolenic acid chains.
FIGURE 2 Schematic for the preparation of plant oil-sulfur
composites and photographs of the resulting compressive strength
test cylinders [Color figure can be viewed at
wileyonlinelibrary.com]
LOPEZ ET AL. 2261
assessed by conditions outlined in ASTM D570 by 24 hrsubmersion at near room temperature. Under these testconditions, water uptake (%H2Oabs) is expressedaccording to Equation (1):
%H2Oabs = Wetweight –Dryweightð Þ=Dryweight½ �× 100
ð1Þ
As would be expected for a composite composed ofhydrophobic sulfur and oil components, the plant oil-sulfur composites absorb <0.3 wt% water (no wateruptake within the error of the experiment), quite lowcompared to familiar exterior building materials likebricks or Portland cement (up to 28 wt% H2Oabsorption).[34]
In terms of physical properties, the hallmark of Port-land cement that drives its widespread utility in infra-structure is its high compressive strength. A compressivestrength of at least 17 MPa is required for residentialbuilding for high strength components such as footingsand foundations.[46] Remarkably, the compressivestrength of the plant oil-sulfur composites range from55 to 135% of the 17 MPa compressive strength bench-mark (ACI 332.1R-06) for residential Portland cement(Table 2 and Figure 3a). The compressive strengthsincrease predictably with the unsaturation number andthus the crosslink density of the materials from CanS(9.3 MPa) to SunS (17.9 MPa) to LinS (22.9 MPa), in linewith aforementioned prior studies on sulfur-crosslinkedcomposites (Figure 3b).
Sulfur composites and sulfur cements often displaysuperior resistance to oxidation and acidic environmentswhen compared to Portland cement products.[47–53] To
TABLE 2 Physical parameters for plant oil-sulfur composites, Portland cement, and polymer-infused Portland cement. Each figure
represents the average of tests on three different samples
Density(kg/m3)
Wateruptake(wt%)
Compositeuptake(wt%)
Compressive strength
As-prepared(% of OPC)a
After acid(% of OPC)b
Retained strength(% of preacid)
CanS 1,700 0c NA 55 36 66
SunS 1,800 0c NA 105 91 87
LinS 1,800 0c NA 135 140 104
Portland cement(OPC)
1,500 Up to28%
NA 100a 0d 0
CanIP 1,500 5.5 14.8 87e 76e 87
SunIP 1,500 3.3 11.5 88e 62e 70
aHere a value of 17 MPa, the minimum allowed by ACI 330 for residential building, is used as the compressive strength of OPC.bAcid challenge involved submersion in 0.5 M H2SO4 for 24 hr.cNo water uptake within error of the experimental method.dA sample of OPC deteriorates under these conditions.eThe compressive strength of the OPC cylinders used to prepare CanIP and SunIP was 19 MPa. The strengths here are expressed as percent-ages of the original OPC strength.
FIGURE 3 Compressive strengths for ordinary Portland
cement (OPC) compared those of plant oil-sulfur cements and
polymer-infused Portland cement (a). After acid challenge, up to
100% of initial strength can be retained in plant oil-sulfur
composites under conditions under which OPC completely
degrades (b). Error bars represent standard deviations of three
measurements in each case [Color figure can be viewed at
wileyonlinelibrary.com]
2262 LOPEZ ET AL.
evaluate the potential chemical stability of CanS, SunS,and LinS in this regard, cylindrical compression testsamples of each were submerged in 0.5 M H2SO4, astrong, oxidizing acid. For comparison, after only 30 mintest samples of Portland cement had lost their shape andall structural integrity under these conditions. In con-trast, after a full 24 hr submerged in the acid the plant oilcomposites retain up to 100% of their initial strength(Figure 3). The percentage of retained strength after acidchallenge increases with increasing crosslinks per triglyc-eride. This makes intuitive sense because the sulfur itselfis impervious to acid, so degradation of strength must bemediated by degradation of the organic domains.[54–58]
Given the beneficial properties of CanS, SunS, andLinS in terms of water uptake, strength, and chemicalresilience, these materials were further explored aspotential additives to Portland cement. The pressure-treatment infusion of the plant oil-sulfur compositesinto preformed, dry Portland cement cylinders wasaffected by submerging the cement cylinders into mol-ten composite samples and applying vacuum for 30 min.This pressure treatment gave CanS- and SunS-infusedPortland cement materials CanIP and SunIP, respec-tively. Molten LinS was determined to be too viscous toeffectively infuse into cement by this method. Theamount of composite that had been successfully infusedinto the cylinders, determined by weighing the cylindersbefore and after infusion, was 14.8% for CanIP and11.5% for SunIP. The lower uptake of SunIP is likely aresult of its greater viscosity. Even after 24 hr in theacid, the polymer-infused cement test samples retain87% (CanIP) or 70% (SunIP) of their initial strength,significantly improved acid stability over ordinary Port-land cement (OPC).
In addition to their structural properties, some highsulfur-content materials are also good thermal insulatorsowing to the low thermal conductivity of sulfur(0.269 W/m/K).[59,60] The strongest of the plant oil-sulfurcomposites, LinS, was thus selected for a qualitative ther-mal conductivity test. For this purpose, 19 mm-thickextruded polystyrene insulation boards were assembledinto an architectural model, the front face of which hadtwo ports cut into it (Figure 4). The port on the left wassealed with a 4.4 mm-thick OPC tile and the right portwas sealed with a 2.8 mm-thick LinS tile. The exteriorsurface temperature (Text) was initially 24.5 �C (76.1�F),while the internal temperature (Tint) was raised to38.3 �C (100.9 �F). A thermal imaging camera of the typeused by building inspectors to test for heat loss was thenused to monitor the thermal breakthrough of the twomaterials. Expectedly, the LinS tile allowed a significantimprovement in the 8 min thermal breakthrough, even
though the LinS tile is only 64% as thick as the OPC tile.After the 8 min trial, the LinS tile surface was only 2 �Chigher than that of the polystyrene insulation board,whereas the OPC tile surface was 8 �C higher (Figure 4).The thermal breakthrough data qualitatively demonstratethe much higher insulative ability of LinS.
3 | CONCLUSIONS
Remeltable composites prepared by the close to 100%atom economical polymerization of plant oils with wastesulfur have compressive strength that can exceed thatrequired of commercial cements lauded for their com-pressive strength. An increase in strength for morecrosslinkable sites per triglyceride unit is notable, as thecompressive strength of LinS is greater than either CanSor SunS despite its higher sulfur content. The plant oil-sulfur cements show density required for lightweightbuilding applications and exceedingly low water uptake.The plant oil-sulfur composites also display good stabilityto oxidizing acid and can be used as pressure-treatment
FIGURE 4 Two ports in the wall of an architectural model
were covered with tiles of ordinary Portland cement (OPC, left) or
LinS (right). The external temperature was 24.5 �C and the final
internal temperature was 38.3 �C. The thermal images show
progressive thermal breakthrough at the ordinary Portland cement
(OPC) tile significantly outpacing that of the LinS tile from the start
(top) to the end (bottom) of the 8 min trial. Blue represents the
coolest parts of the images, red the hottest [Color figure can be
viewed at wileyonlinelibrary.com]
LOPEZ ET AL. 2263
additives to preformed cement blocks to dramaticallyimprove their stability in low pH conditions.
4 | EXPERIMENTAL PROCEDURES
4.1 | General considerations
All materials were used as received: canola oil (Crisco),sunflower oil (Maple Holistics), linseed oil (FurnitureClinic, UK), and sulfur (Dugas Diesel). Portland cementtest specimens were prepared by mixing sifted residentialPortland cement (Quikcrete) with twice the mass ofwater and allowing to cure according to manufacturerinstructions for residential building purposes. Impregna-tion of cement was undertaken by placing a piece ofcured Portland cement into a vial of molten plant oil-sulfur composite CanS or SunS submerged in a 180�C oilbath and applying a dynamic vacuum for 2 min afterwhich time the vacuum line was closed and a static vac-uum was applied for 1 hr. Samples were removed whilehot and hand-sanded to dimensions like that of the origi-nal Portland cement cylinder (±0.05 mm for materialsanalyzed by stress–strain testing). The acid challenge wasperformed by submerging samples into 0.50 M H2SO4 for24 hr after which they were removed, rinsed gently withDI water, and blotted dry. Compressive strength testswere acquired using a Mark-10 ES30 Manual Test Standequipped with a Mark 10 M3-200 Force Gauge. Plant oil-sulfur composite materials were aged for 4 d prior tocompressive strength testing. Testing indicated that thematerial properties were constant (at least over a time-frame of several more days) after this aging time. Thelong-term stability of high sulfur-content materials canbe an issue as unstable polymeric sulfur domains canrevert back to orthorhombic sulfur in many instances.
4.2 | General synthesis
CAUTION: Heating elemental sulfur with organics canresult in the formation of H2S gas. H2S is toxic, foul smell-ing, and corrosive. Although we did not observe any massloss attributable to gas generation, temperature must becarefully controlled to prevent thermal spikes, which con-tribute to the potential for H2S evolution. Rapid stirring,shortened heating times, and very slow addition of reagentscan help prevent unforeseen temperature spikes.
Composites of the plant-oil with sulfur materials weresynthesized. SunS, CanS, and LinS materials were pre-pared wherein sulfur feed ratios ranged from 90–95 wt%and 5–10 wt% plant-oils.
4.3 | Synthesis of CanS
In the reaction of 90 wt% sulfur and 10 wt% canola oil(10.0 g, d = 0.93 g/ml), sulfur (90.1 g, 0.35 Mol) wasmelted in an oil bath at 160�C with rapid mechanicalstirring. Then, the temperature was heated further to180�C, where sulfur exists primarily as polymericdiradicals. Once the temperature was stable, 10.88 ml ofcanola oil was added dropwise to the sulfur. The plant-oil with sulfur mixture reacted for 35 min at 180�C.Within 35 min of the reaction time, the desired product,a light-brown homogeneous solution was produced.Upon cooling to room temperature, the material solidi-fied to a brown solid in quantitative yield (100 g).ELEM. ANAL calc'd: C 7.74, H 1.16, S 90.00; found: C7.62, H 0.92, S 90.23.
4.4 | Synthesis of SunS
In the reaction of 90 wt% sulfur and 10 wt% sunfloweroil (10.0 g, d = 0.90 g/ml), sulfur (90.0 g, 0.35 Mol) wasmelted in an oil bath at 160�C with fast mechanical stir-ring. Then, the temperature was heated further to180�C, where sulfur exists primarily as polymericdiradicals. Once the temperature was stable, 10.76 ml ofsunflower oil was added dropwise to the sulfur. Theplant-oil with sulfur mixture reacted for 35 min at180�C. Within 35 min of the reaction time, the desiredproduct, a light-brown homogeneous mixture was pro-duced. Upon cooling to room temperature, the materialsolidified to a brown solid in quantitative yield (100 g).ELEM. ANAL calc'd: C 7.76, H 1.14, S 90.00; found: C7.58, H 1.00, S 90.44.
4.5 | Synthesis of LinS
In the reaction of 95 wt% sulfur and 5 wt% linseed oil(5.0 g, d = 0.91 g/ml), sulfur (95.0 g, 0.37 Mol) wasmelted in an oil bath at 160�C with fast mechanical stir-ring. Then, the temperature was heated further to180�C, where sulfur exists primarily as polymericdiradicals. Once the temperature was stable, 5.36 ml oflinseed oil was added dropwise to the sulfur. The plant-oil with sulfur mixture reacted for 35 min at 180�C.Within 35 min of the reaction time, the desired product,a dark-brown homogeneous mixture was observed.Upon cooling to room temperature, the material solidi-fied to a brown solid in quantitative yield (100 g).ELEM. ANAL calc'd: C 3.89, H 0.56, S 95.00; found: C3.51, H 0.39, S 95.24.
2264 LOPEZ ET AL.
ACKNOWLEDGMENTSWe thank the Animal Coproducts Research and Educa-tion Center and the National Science Foundation (CHE-1708844) for financial support.
ORCIDRhett C. Smith https://orcid.org/0000-0001-6087-8032
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SUPPORTING INFORMATIONAdditional supporting information may be found onlinein the Supporting Information section at the end of thisarticle.
How to cite this article: Lopez CV,Karunarathna MS, Lauer MK, et al. High strength,acid-resistant composites from canola, sunflower,or linseed oils: Influence of triglycerideunsaturation on material properties. J Polym Sci.2020;58:2259–2266. https://doi.org/10.1002/pol.20200292
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