Abstract
Elemental sulfur, which is a by-product of crude oil, is a widely available, cost-effective element. The excess of the elemental sulfur increased the interest of researchers on different application of this element. Herein, sulfur content-crosslinked porous polymer networks were synthesized via two-step procedure combining emulsion templating and inverse vulcanization. For this purpose, β-myrcene was copolymerized with ethylene glycol dimethacrylate (EGDMA) by using high internal phase emulsion (HIPE) templating approach to synthesize hierarchical porous polyHIPEs, firstly. Then, inverse vulcanization was used as a post-polymerization process to consume the remaining –ene structures on the resulting crosslinked copolymer network. The formation of highly crosslinked, sulfur containing polyHIPE network was verified via FTIR, 1H NMR and elemental analysis. Accordingly, it was demonstrated that the specific surface area and thermal properties of the polyHIPE networks can be easily improved by using inverse vulcanization approach without compromising the pore morphology.
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References
Abraham AM, Kumar SV, Alhassan SM (2018) Porous sulphur copolymer for gas phase mercury removal and thermal insulation. Chem Eng J 332:1–7. https://doi.org/10.1016/j.cej.2017.09.069
Ansarifar A (2018) A review of sulfur vulcanization of rubber. Acad J Polym Sci 1(4):555568
Barbetta A, Cameron NR (2004) Morphology and surface area of emulsion-derived (PolyHIPE) solid foams prepared with oil-phase soluble porogenic solvents: span 80 as surfactant. Macromolecules 37(9):3188–3201. https://doi.org/10.1021/ma0359436
Bauer N, Brunke J, Kali G (2017) Controlled radical polymerization of myrcene in bulk: mapping the effect of conditions on the system. ACS Sustain Chem Eng 5(11):10084–10092. https://doi.org/10.1021/acssuschemeng.7b02091
Behr A, Johnen L (2009) Myrcene as a natural base chemical in sustainable chemistry: a critical review. Chem Sus Chem 2(12):1072–1095. https://doi.org/10.1002/cssc.200900186
Berezovska I, Kapilov K, Dhavalikar P, Cosgriff-Hernandez E, Silverstein MS (2021) Reactive surfactants for achieving open-cell polyHIPE foams from pickering emulsions. Macromol Mater Eng 306(6):2000825. https://doi.org/10.1002/mame.202000825
Bhattacharya A, Rawlins JW, Ray P (2008) Polymer grafting and crosslinking. Wiley, New Jersey. https://doi.org/10.1002/9780470414811
Blaker JJ, Lee KY, Li X, Menner A, Bismarck A (2009) Renewable nanocomposite polymer foams synthesized from pickering emulsion templates. Green Chem 11:1321–1326. https://doi.org/10.1039/B913740H
Blight L, Currell BR, Nash BJ, Scott RAM, Stillo C (1978) In: Gould RF, Bourne DJ (Ed) Preparation and properties of modified sulfur systems, New uses of sulfur—II. American Chemical Society, Washington
Cameron NR, Sherrington DC (1996) Advances in polymer science. Springer, Heidelberg. https://doi.org/10.1007/3-540-60484-7_4
Chassé W, Lang M, Sommer JU, Saalwächter K (2012) Cross-link density estimation of PDMS networks with precise consideration of networks defects. Macromol 45:899–912. https://doi.org/10.1021/ma202030z
Chung WJ, Griebel JJ, Kim ET, Yoon H, Simmonds AG, Ji HJ, Dirlam PT, Glass RS, Wie JJ, Nguyen NA, Guralnick BW, Park J, Somogyi A, Theato P, Mackay ME, Sung YE, Char K, Pyun J (2013) The use of elemental sulfur as an alternative feedstock for polymeric materials. Nat Chem 5:518–524. https://doi.org/10.1038/nchem.1624
Dodd LJ, Omar Ö, Wu X, Hasell T (2021) Investigating the role and scope of catalysts in ınverse vulcanization. ACS Catal 11(8): 4441–4455. https://doi.org/10.1021/acscatal.0c05010
Flory PJ (1953) Principles of polymer chemistry. Cornell University Press, Ithaca
Flory PJ, Rehner J (1943) Statistical mechanics of cross-linked polymer networks I. Rubberlike elasticity. J Chem Phys 11:512. https://doi.org/10.1063/1.1723791
Gauthier MA, Gibson MI, Klok HA (2008) Synthesis of functional polymers by postpolymerization modification. Angew Chem Int Ed Engl 48:48–58. https://doi.org/10.1002/anie.200801951
Gomez I, Leonet O, Blazquez JA, Mecerreyes D (2016) Inverse vulcanization of sulfur using natural dienes as sustainable materials for lithium–sulfur batteries. Chemsuschem 9(24):3419–3425. https://doi.org/10.1002/cssc.201601474
Gundogan N, Okay O, Oppermann W (2004) Swelling, elasticity and spatial inhomogeneity of poly(N, N-dimethylacrylamide) hydrogels formed at various polymer concentrations. Macromol Chem Phys 205:814–823. https://doi.org/10.1002/macp.200300174
Hiranobe CT, Ribeiro GD, Torres GB, Prado dos Reis EA, Cabrera FC, Jobe AE, Paim LL, dos Santos RJ (2021) Cross-linked density determination of natural rubber compounds by different analytical techniques. Mater Res 24(suppl. 1):e20210041. https://doi.org/10.1590/1980-5373-MR-2021-0041
Hossain K, Chowdhury AS (2010) Grafting of n-butyl acrylate with natural rubber latex film by gamma radiation: a reaction mechanism. Daffodil Int Uni J Sci Tech 5(1):81–88. https://doi.org/10.3329/diujst.v5i1.4386
Hoti G, Caldera F, Cecone C, Pedrazzo AR, Anceschi A, Appleton SL, Monfared YK, Trotta F (2021) Effect of the cross-linking density on the swelling and rheological behavior of ester-bridged β–Cyclodextrin nanosponges. Mater 14:478. https://doi.org/10.3390/ma14030478
Je SH, Buyukcakir O, Kim D, Coskun A (2016) Direct utilization of elemental sulfur in the synthesis of microporous polymers for natural gas sweetening. Chem 1(3):482–493. https://doi.org/10.1016/j.chempr.2016.08.003
Kekevi B, Mert EH (2021a) Development of terpene based sorbents via emulsion templating: synthesis and swelling behavior. React Funct Polym 164:104912. https://doi.org/10.1016/j.reactfunctpolym.2021.104912
Kekevi B, Mert EH (2021b) Preparation of hypercrosslinked PolyHIPEs by using a bio-derived monomer. Eur Polym J 152:110474. https://doi.org/10.1016/j.eurpolymj.2021.110474
Kennedy SJ, Wheeler JC (1983) Free-radical concentration in doped sulfur. Theory and experiment. J Phys Chem 87:3961–3966. https://doi.org/10.1021/j100243a033
Kutney G (2013) Sulfur: history, technology, applications & industry, 2nd edn. ChemTec Publishing, Toronto
Mark JE, Erman B (2005) Science and technology of rubber. Academic Press, San Diego
Mautner A, Nawawi WMFW, Lee KY, Bismarck A (2020) High porosity cellulose nanopapers as reinforcement in multi-layer epoxy laminates. Compos A Appl Sci Manuf 131:105779. https://doi.org/10.1016/j.compositesa.2020.105779
Mert HH, Mert MS, Mert EH (2019) A statistical approach for tailoring the morphological and mechanical properties of polystyrene PolyHIPEs: looking through experimental design. Mater Res Express 6:115306. https://doi.org/10.1088/2053-1591/ab437f
Mert EH, Kekevi B (2020) Synthesis of polyHIPEs through high internal phase emulsions of β-myrcene. Col Polym Sci 298:1423–1432. https://doi.org/10.1007/s00396-020-04730-4
Mert EH, Kekevi B (2021) Synthesis of β-myrcene based macroporous nanocomposite foams: Altering the morphological and mechanical properties by using organomodified nanoclay. J Appl Polym Sci 138:50074. https://doi.org/10.1002/app.50074
Mert EH, Mert HH (2021) Preparation of polyHIPE nanocomposites: revealing the influence of experimental parameters with the help of experimental design approach. Polym Compos 42:724–738. https://doi.org/10.1002/pc.25861
Meyer B (1976) Elemental sulfur. Chem Rev 76:367–388. https://doi.org/10.1021/cr60301a003
Minoura Y, Asao M (1961) Studies on gamma rays irradiation of natural rubber latex. The effect of organic halogen compound on crosslinking by gamma irradiation. J Appl Polym Sci 5:401. https://doi.org/10.1002/app.1961.070051605
Naranda J, Sušec M, Maver U, Gradišnik L, Gorenjak M, Vukasović A, Ivković A, Rupnik MS, Vogrin M, Krajnc P (2016) Polyester type polyHIPE scaffolds with an interconnected porous structure for cartilage regeneration. Sci Rep 6:28695. https://doi.org/10.1038/srep28695
Omeir MY, Wadi VS, Alhassan SM (2020) Inverse vulcanized sulfur–cycloalkene copolymers: effect of ring size and unsaturation on thermal properties. Mater Lett 259:126887. https://doi.org/10.1016/j.matlet.2019.126887
Parker DJ, Jones HA, Petcher S, Cervini L, Griffin JM, Akhtar R, Hasell T (2017) Low cost and renewable sulfur-polymers by inverse vulcanisation, and their potential for mercury capture. J Mater Chem 5:11682–11692. https://doi.org/10.1039/C6TA09862B
Parker DJ, Chong ST, Hasell T (2018) Sustainable inverse-vulcanised sulfur polymers. RSC Adv 8:27892–27899. https://doi.org/10.1039/C8RA04446E
Pérez-García MG, Gutierrez MC, Mota-Morales JD, Luna-Barcenas G, del Monte F (2016) Synthesis of biodegradable macroporous poly(L-lactide)/ poly(δ-caprolactone) blend using oil-in-eutectic-mixture high internal phase emulsions as template. ACS Appl Mater Int 8(26):16939–16949. https://doi.org/10.1021/acsami.6b04830
Robles-Dutenhefner PA, Speziali MG, Sousa EMB, dos Santos EN, Gusevskaya EV (2005) Selective hydrogenation of myrcene catalyzed by sol–gel Pd/SiO2. Appl Catal A 295(1):52–58. https://doi.org/10.1016/j.apcata.2005.08.005
Rodger ER (1979) Vulcanization systems. In: Whelaw IA, Lee SK (eds) Developments in rubber technology. Applied Science Publishers Ltd., London, p 105–150
Safinia L, Mantalaris A, Bismarck A (2006) Nondestructive technique for the characterization of the pore size distribution of soft porous constructs for tissue engineering. Langmuir 22(7):3235–3242. https://doi.org/10.1021/la051762g
Sahu P, Sarkar P, Bhowmick AK (2018) Design of a molecular architecture via a green route for improved Silica reinforced nanocomposite using bio-resources. ACS Sust Chem Eng 6(5):6599–6611. https://doi.org/10.1021/acssuschemeng.8b00383
Sahu P, Bhowmick AK (2019) Sustainable self-healing elastomers with thermoreversible network derived from biomass via emulsion polymerization. J Polym Sci Part A: Polym Chem 57:738–751. https://doi.org/10.1002/pola.29320
Sahu P, Bhowmick AK, Kali G (2020) Terpene based elastomers: synthesis, properties, and applications. Processes 8(5):553. https://doi.org/10.3390/pr8050553
Sarkar P, Bhowmick AK (2014) Synthesis, characterization and properties of a biobased elastomer: Polymyrcene. RSC Adv 4:61343–61354. https://doi.org/10.1039/C4RA09475A
Silverstein MS (2014) PolyHIPEs: recent advances in emulsion-templated porous polymers. Prog Polym Sci 39(1):199–234. https://doi.org/10.1016/j.progpolymsci.2013.07.003
Silverstein MS (2017) Emulsion-templated polymers: contemporary contemplations. Polymer 126:261–282. https://doi.org/10.1016/j.polymer.2017.07.046
Smith AD, Mcmillen CD, Smith RC, Tennyson AG (2020) Copolymers by inverse vulcanization of sulfur with pure or technical-grade unsaturated fatty acids. J Polym Sci 58(3):438–445. https://doi.org/10.1002/pol.20190138
Steudel R (2003) Elemental sulfur and sulfur-rich compounds I. Springer, Heidelberg
Tarasova NP, Zanin AA, Krivoborodov EG, Mezhuev YO (2021) Elemental sulphur in the synthesis of sulphur-containing polymers: reaction mechanisms and green prospects. RSC Adv 11:9008–9020. https://doi.org/10.1039/D0RA10507D
Tebboth M, Menner A, Kogelbauer A, Bismarck A (2014) Polymerised high internal phase emulsions for fluid separation applications. Curr Opin Chem Eng 4:114–120. https://doi.org/10.1016/j.coche.2014.03.001
Trumbo L (1993) Free radical copolymerization behavior of myrcene I. Copolymers with styrene, methyl methacrylate or p-florostyrene. Polym Bull 31:629–636. https://doi.org/10.1007/BF00300120
Wadi VS, Jena KK, Khawaja SZ, Ranagraj VM, Alhassan SM (2019) Preparation and processing of porous sulfur foams having low thermal conductivity. RSC Adv 9:4397–4403. https://doi.org/10.1039/C8RA09127G
Wang K, Groom M, Sheridan R, Zhang S, Block E (2013) Liquid sulfur as a reagent: synthesis of polysulfanes with 20 or more sulfur atoms with characterization by UPLC-(Ag+)-coordination ion spray-MS. J Sulfur Chem 34:55–66. https://doi.org/10.1080/17415993.2012.721368
Woodward RT, Jobbe-Duval A, Marchesini S, Anthony DB, Petit C, Bismarck A (2017) Hypercrosslinked polyHIPEs as precursors to designable, hierarchically porous carbon foams. Polymer 115:146–153. https://doi.org/10.1016/j.polymer.2017.03.042
Worthington MJH, Kucera RL, Chalker JM (2017) Green chemistry and polymers made from sulfur. Green Chem 19:2748–2761. https://doi.org/10.1039/C7GC00014F
Wu X, Smith JA, Petcher S, Zhang B, Parker DJ, Griffin JM, Hasell T (2019) Catalytic inverse vulcanization. Nat Commun 10:647. https://doi.org/10.1038/s41467-019-08430-8
Yan P, Zhao W, Zhang B, Jiang L, Petcher S, Smith JA, Parker DJ, Cooper AI, Lei J, Hasell T (2020) Inverse vulcanized polymers with shape memory, enhanced mechanical properties, and vitrimer behavior. Angew Chem Int Ed 59(32):13371–13378. https://doi.org/10.1002/anie.202004311
Yin D, Yin D, Fu Z, Li Q (1999) The regioselectivity of Diels-Alder reaction of myrcene with carbonyl-containing dienophiles catalysed by Lewis acids. J Mol Cat A Chem 148:87–95. https://doi.org/10.1016/S1381-1169(99)00113-2
Zhang T, Xu Z, Guo Q (2016) Closed-cell and open-cell porous polymers from ionomer-stabilized high internal phase emulsions. Polym Chem 7:7469–7476. https://doi.org/10.1039/C6PY01725H
Zhang H, Zhao R, Pan M, Deng J, Wu Y (2019) Biobased, porous poly(high internal phase emulsions): prepared from biomass-derived vanillin and laurinol and applied as an oil adsorbent. Ind Eng Chem Res 58(14):5533–5542. https://doi.org/10.1021/acs.iecr.9b00515
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Kekevi, B. Synthesis of a sulfur-containing polyHIPE from a sustainable monomer by using inverse vulcanization approach. Chem. Pap. 76, 6639–6651 (2022). https://doi.org/10.1007/s11696-022-02404-9
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DOI: https://doi.org/10.1007/s11696-022-02404-9