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Inverse vulcanization
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<h2 id="synthesis">Synthesis</h2> <p>Like <a href="/facts/Thiokol/alHU0yG6">Thiokols</a> and <a href="/facts/Sulfur_vulcanization/QmXUTjXk">sulfur-vulcanization</a>, inverse vulcanization uses the tendency of <a href="/facts/Sulfur/IK0amTfM">sulfur</a> <a href="/facts/Catenation/vm7k4zsv">catenate</a>. The polymers produced by inverse <a href="/facts/Sulfur_vulcanization/QmXUTjXk">vulcanization</a> consist of long sulfur linear chains interspersed with organic linkers. Traditional <a href="/facts/Sulfur_vulcanization/QmXUTjXk">sulfur vulcanization</a> produces a cross-linked material with short sulfur bridges, down to one or two sulfur atoms. </p><p>The <a href="/facts/Polymerization/1hmBz7Ur">polymerization</a> process begins with the heating of elemental <a href="/facts/Sulfur/IK0amTfM">sulfur</a> above its melting point (115.21 °C), to favor the <a href="/facts/Ring-opening_polymerization/VQsgojQQ">ring-opening polymerization</a> process (ROP) of the S8 <a href="/facts/Monomer/Gw3CltMb">monomer</a>, occurring at 159 °C. As a result, the liquid sulfur is constituted by linear polysulfide chains with diradical ends, which can be easily bridged together with small <a href="/facts/Diene/F5NxrLPW">dienes</a>, such as <a href="/facts/1,3-Diisopropylbenzene/8bmo3UFo">1,3-Diisopropylbenzene</a>(DIB),<a class="footnote-ref" id="fnref:2" href="#fn:2"><sup>2</sup></a> <a href="https://pubchem.ncbi.nlm.nih.gov/compound/1_4-Diphenylbutadiyne">1,4-diphenylbutadiyne</a>,<a class="footnote-ref" id="fnref:3" href="#fn:3"><sup>3</sup></a> <a href="/facts/Limonene/8qBaxvyv">limonene</a>,<a class="footnote-ref" id="fnref:4" href="#fn:4"><sup>4</sup></a> <a href="/facts/Divinylbenzene/5bueSnj4">divinylbenzene</a> (DVB),<a class="footnote-ref" id="fnref:5" href="#fn:5"><sup>5</sup></a> <a href="/facts/Dicyclopentadiene/vck23a49">dicyclopentadiene</a>,<a class="footnote-ref" id="fnref:6" href="#fn:6"><sup>6</sup></a> <a href="/facts/Styrene/B8uXm78L">styrene</a>,<a class="footnote-ref" id="fnref:7" href="#fn:7"><sup>7</sup></a> <a href="/facts/4-Vinylpyridine/7WDWtyEw">4-vinylpyridine</a>,<a class="footnote-ref" id="fnref:8" href="#fn:8"><sup>8</sup></a> <a href="/facts/Cycloalkene/uLQcHy3c">cycloalkene</a><a class="footnote-ref" id="fnref:9" href="#fn:9"><sup>9</sup></a> and <a href="/facts/Ethylidene_norbornene/NPtwLsGn">ethylidene norbornene</a>,<a class="footnote-ref" id="fnref:10" href="#fn:10"><sup>10</sup></a> or longer organic molecules as <a href="/facts/Polybenzoxazines/kQz2yWUH">polybenzoxazines</a>,<a class="footnote-ref" id="fnref:11" href="#fn:11"><sup>11</sup></a> <a href="/facts/Squalene/Ua31mYv4">squalene</a><a class="footnote-ref" id="fnref:12" href="#fn:12"><sup>12</sup></a> and <a href="/facts/Triglyceride/BQmjv4A0">triglyceride</a>.<a class="footnote-ref" id="fnref:13" href="#fn:13"><sup>13</sup></a> Chemically, the <a href="/facts/Diene/F5NxrLPW">diene</a> carbon-carbon <a href="/facts/Double_bond/qDemMn0c">double bond</a> (C=C) of the substitutional group disappears, forming the <a href="/facts/Carbon-sulfur_bond/sUxSSXwD">carbon-sulfur single bond</a> (C-S) which binds together the sulfur linear chains. The advantage of such a <a href="/facts/Polymerization/1hmBz7Ur">polymerization</a> is the absence of a solvent; <a href="/facts/Sulfur/IK0amTfM">Sulphur</a> acts as <a href="/facts/Comonomer/PYXAYpNC">comonomer</a> and <a href="/facts/Solvent/LoMPMz8S">solvent</a>. This makes the process highly scalable at the industrial level, and kilogram-scale synthesis of the poly(S-r-DIB) has already been accomplished.<a class="footnote-ref" id="fnref:14" href="#fn:14"><sup>14</sup></a> </p> <h2 id="products-characterization-and-properties">Products, characterization and properties</h2> <p>Vibrational spectroscopy was performed to investigate the chemical structure of the copolymers, and the presence of the C-S bonds was detected through <a href="/facts/Infrared_spectroscopy/u1Hzx617">Infrared</a> or <a href="/facts/Raman_spectroscopy/XY063k29">Raman</a> spectroscopies.<a class="footnote-ref" id="fnref:15" href="#fn:15"><sup>15</sup></a> The high amount of S-S bonds makes the copolymer highly IR-inactive in the near and mid-infrared spectrum. As a consequence, sulfur-rich materials made via inverse vulcanization are characterized by a high <a href="/facts/Refractive_index/yjkzvgeE">refractive index</a> (n~1.8), whose value depends again upon the composition and crosslinking species.<a class="footnote-ref" id="fnref:16" href="#fn:16"><sup>16</sup></a> As shown by <a href="/facts/Thermogravimetric_analysis/t3hdEok7">thermogravimetric analysis</a> (TGA), the copolymer thermal stability increases with the amount of added crosslinker; however, all the tested compositions degrade above 222 °C.<a class="footnote-ref" id="fnref:17" href="#fn:17"><sup>17</sup></a><a class="footnote-ref" id="fnref:18" href="#fn:18"><sup>18</sup></a> </p><p>Copolymer behavior included that, the <a href="/facts/Glass-transition_temperature/yVl3QzsT">glass-transition temperature</a> depends upon the composition and crosslinking species. For given <a href="/facts/Comonomer/PYXAYpNC">comonomers</a>, the behavior of the <a href="/facts/Copolymer/35D97DuV">copolymers</a> as a function of the temperature depends on the chemical composition; for example, the poly (sulfur-random-<a href="/facts/Divinylbenzene/5bueSnj4">divinylbenzene</a>) behaves as a <a href="/facts/Plastomer/mcXxlrU2">plastomer</a> for a <a href="/facts/Diene/F5NxrLPW">diene</a> content between 15 and 25%wt, and as a viscous <a href="/facts/Resin/r1uVThQ8">resin</a> with the 30–35%wt of DVB. On the other hand, the poly (sulfur-random-<a href="https://pubchem.ncbi.nlm.nih.gov/compound/1_3-Diisopropenylbenzene">1,3-diisopropenylbenzene</a>) acts as <a href="/facts/Thermoplastic/5KJB8dwN">thermoplastic</a> at 15–25%wt of DIB, while it becomes a <a href="/facts/Thermoplastic/5KJB8dwN">thermoplastic</a>-<a href="/facts/Thermosetting/EagnsydT">thermosetting</a> polymer for a diene concentration of 30-35%wt.<a class="footnote-ref" id="fnref:19" href="#fn:19"><sup>19</sup></a> The potential to break and reform the chemical bonds along the <a href="/facts/Polysulfide/PpfaUlw4">polysulfide</a> chains (S-S) allows the repair of the copolymer by simply heating above 100 °C. This increases the ability to reform and recycle the high molecular weight copolymer.<a class="footnote-ref" id="fnref:20" href="#fn:20"><sup>20</sup></a> </p> <h2 id="potential-applications">Potential applications</h2> <p>The sulfur-rich copolymers made via inverse vulcanization could in principle find diverse applications due to their simple synthesis process and <a href="/facts/Thermoplastic/5KJB8dwN">thermoplasticity</a>. </p> <h3>Lithium-sulfur batteries</h3> <p>This new way of sulfur processing has been exploited for the <a href="/facts/Cathode/tqdlGayU">cathode</a> preparation of long-cycling <a href="/facts/Lithium-sulfur_batteries/RPo9joIf">lithium-sulfur batteries</a>. Such electrochemical systems are characterized by a greater energy density than commercial <a href="/facts/Li-ion_batteries/3L22xFhB">Li-ion batteries</a>, but they are not stable for long service life. Simmonds et al. first demonstrated improved capacity retention for over 500 cycles with an inverse vulcanization copolymer, suppressing the typical capacity fading of sulfur-polymer composites.<a class="footnote-ref" id="fnref:21" href="#fn:21"><sup>21</sup></a> The poly (sulfur-random-1,3-diisopropenylbenzene), briefly defined as poly (S-r-DIB), showed a higher composition homogeneity compared with other cathodic materials, together with greater sulfur retention and an enhanced adjustment of the polysulfides' volume variations. These advantages made it possible to assemble a stable and durable Li-S cell. Subsequently, other copolymers were synthesized via inverse vulcanization and tested inside these electrochemical devices, again providing high stability over their cycles. </p> Battery performances<table><tbody><tr><th>Cathode</th><th>Date</th><th>Source</th><th>Specific Capacity after cycling</th></tr><tr><td>Poly (sulfur-random-<a href="/facts/1,3-Diisopropylbenzene/8bmo3UFo">1,3-diisopropylbenzene</a>)</td><td>2014</td><td><a href="/facts/University_of_Arizona/ehesIpKx">University of Arizona</a><a class="footnote-ref" id="fnref:22" href="#fn:22"><sup>22</sup></a></td><td>800 mA⋅h/g after 300 cycles (at 0.1 C)</td></tr><tr><td>Poly (sulfur-random-<a href="https://pubchem.ncbi.nlm.nih.gov/compound/trans_trans-1_4-Diphenyl-1_3-butadiene">1,4-Diphenyl-1,3-butadiene</a>)</td><td>2015</td><td><a href="/facts/University_of_Arizona/ehesIpKx">University of Arizona</a><a class="footnote-ref" id="fnref:23" href="#fn:23"><sup>23</sup></a></td><td>800 mA⋅h/g after 300 cycles (at 0.2 C)</td></tr><tr><td>Poly (sulfur-random-<a href="/facts/Divinylbenzene/5bueSnj4">divinylbenzene</a>)</td><td>2016</td><td><a href="/facts/University_of_the_Basque_Country/mSy3S8jl">University of the Basque Country</a><a class="footnote-ref" id="fnref:24" href="#fn:24"><sup>24</sup></a></td><td>700 mA⋅h/g after 500 cycles (at 0.25 C)</td></tr><tr><td>Poly (sulfur-random-<a href="/facts/Diallyl_disulfide/f3JAd8b9">diallyl disulfide</a>)</td><td>2016</td><td><a href="/facts/University_of_the_Basque_Country/mSy3S8jl">University of the Basque Country</a><a class="footnote-ref" id="fnref:25" href="#fn:25"><sup>25</sup></a></td><td>616 mA⋅h/g after 200cycles (at 0.2 C)</td></tr><tr><td>Poly (sulfur-random-<a href="/facts/Bismaleimide/96kezkLr">bismaleimide</a>-divinylbenzene)</td><td>2016</td><td><a href="/facts/Istanbul_Technical_University/xnT5QSEl">Istanbul Technical University</a><a class="footnote-ref" id="fnref:26" href="#fn:26"><sup>26</sup></a></td><td>400 mA⋅h/g after 50 cycles (at 0.1 C)</td></tr><tr><td>Poly (sulfur-random-<a href="/facts/Styrene/B8uXm78L">styrene</a>)</td><td>2017</td><td><a href="/facts/University_of_Arizona/ehesIpKx">University of Arizona</a><a class="footnote-ref" id="fnref:27" href="#fn:27"><sup>27</sup></a></td><td>485 mA⋅h/g after 1000 cycles (at 0.2 C)</td></tr></tbody></table> <p>In order to overcome the disadvantages related to the materials' low electrical conductivity (1015–1016 Ω·cm),<a class="footnote-ref" id="fnref:28" href="#fn:28"><sup>28</sup></a> researchers have started to add special carbon-based particles to increase electron transport inside the copolymer. Furthermore, such carbonaceous additives improve the polysulfides' retention at the cathode through the polysulfides-capturing effect, increasing the battery performances. Examples of employed <a href="/facts/Nanostructures/rkeQGqt7">nanostructures</a> are long <a href="/facts/Carbon_nanotube/atuDPPaG">carbon nanotubes</a>,<a class="footnote-ref" id="fnref:29" href="#fn:29"><sup>29</sup></a> <a href="/facts/Graphene/QDGUBaPt">graphene</a>,<a class="footnote-ref" id="fnref:30" href="#fn:30"><sup>30</sup></a> and <a href="/facts/Fullerene/LPdnl8ox">carbon onions</a>.<a class="footnote-ref" id="fnref:31" href="#fn:31"><sup>31</sup></a> </p> <h3>Capturing Mercury</h3> <p>The new materials could be used to remove toxic metals from soil or water. Pure sulfur cannot be employed to manufacture a functional filter because of its low mechanical properties; therefore, inverse <a href="/facts/Vulcanization/jmBUqGaz">vulcanization</a> was investigated to produce porous materials, in particular for the <a href="/facts/Mercury_(element)/WlxfoHva">mercury</a> capturing process. The liquid metal binds together with the sulfur-rich <a href="/facts/Copolymer/35D97DuV">copolymer</a>, remaining mostly inside the filter.<a class="footnote-ref" id="fnref:32" href="#fn:32"><sup>32</sup></a><a class="footnote-ref" id="fnref:33" href="#fn:33"><sup>33</sup></a><a class="footnote-ref" id="fnref:34" href="#fn:34"><sup>34</sup></a> </p> <h3>Infrared transmission</h3> <p>Sulfur-rich <a href="/facts/Copolymer/35D97DuV">copolymers</a>, made via inverse vulcanization, have advantages over traditional <a href="/facts/Infrared/44XdJNcc">IR optical</a> materials due to the simple manufacturing process, low cost <a href="/facts/Reagent/c3GLInCu">reagents</a>, and high <a href="/facts/Refractive_index/yjkzvgeE">refractive index</a>. As mentioned before, the latter depends upon the S-S bonds concentration, leading to the ability to tune the optical properties of the material by modifying the chemical formulation. The ability to change the material's <a href="/facts/Refractive_index/yjkzvgeE">refractive index</a> to fulfill the specific application requirements makes these <a href="/facts/Copolymer/35D97DuV">copolymers</a> applicable in military, civil or medical fields.<a class="footnote-ref" id="fnref:35" href="#fn:35"><sup>35</sup></a><a class="footnote-ref" id="fnref:36" href="#fn:36"><sup>36</sup></a><a class="footnote-ref" id="fnref:37" href="#fn:37"><sup>37</sup></a><a class="footnote-ref" id="fnref:38" href="#fn:38"><sup>38</sup></a> </p> <h3>Others</h3> <p>The inverse vulcanization process can also be employed for the synthesis of <a href="/facts/Activated_carbon/YAbaXCcb">activated carbon</a> with narrow pore-size distributions. The sulfur-rich <a href="/facts/Copolymer/35D97DuV">copolymer</a> acts as a template where the carbons are produced. The final material is doped with sulfur and exhibits a micro-porous network and high gas selectivity. Therefore, inverse vulcanization could also be used for <a href="/facts/Gas_separation/7vLrKGMU">gas separation</a> applications.<a class="footnote-ref" id="fnref:39" href="#fn:39"><sup>39</sup></a> </p> <h2 id="see-also">See also</h2> <ul><li><a href="/facts/Sulfur/IK0amTfM">Sulfur</a></li> <li><a href="/facts/Free-radical_polymerization/CbG5UqAd">Free-radical polymerization</a></li> <li><a href="/facts/Lithium-sulfur_batteries/RPo9joIf">Lithium-sulfur batteries</a></li></ul> <h2 id="external-links">External links</h2> <ul><li><a href="https://www.greencarcongress.com/2013/04/pyun-20130415.html/">"New “inverse vulcanization” process produces polymeric sulfur that can function as high performance electrodes for Li-S batteries"</a>. 15 April 2013.</li></ul> <h2 id="references">References</h2> <ol> <li id="fn:1"><p>Chung, Woo Jin; Griebel, Jared J.; Kim, Eui Tae; Yoon, Hyunsik; Simmonds, Adam G.; Ji, Hyun Jun; Dirlam, Philip T.; Glass, Richard S.; Wie, Jeong Jae; Nguyen, Ngoc A.; Guralnick, Brett W.; Park, Jungjin; Somogyi, Árpád; Theato, Patrick; Mackay, Michael E.; Sung, Yung-Eun; Char, Kookheon; Pyun, Jeffrey (14 April 2013). "The use of elemental sulfur as an alternative feedstock for polymeric materials". Nature Chemistry. 5 (6): 518–524. Bibcode:2013NatCh...5..518C. doi:10.1038/NCHEM.1624. PMID 23695634. <a href="/w/index.php?title=Jeffrey_Pyun&action=edit&redlink=1" target="_blank">/w/index.php?title=Jeffrey_Pyun&action=edit&redlink=1</a> <a href="#fnref:1" class="footnote-back-ref">↩</a></p></li> <li id="fn:2"><p>Chung, Woo Jin; Griebel, Jared J.; Kim, Eui Tae; Yoon, Hyunsik; Simmonds, Adam G.; Ji, Hyun Jun; Dirlam, Philip T.; Glass, Richard S.; Wie, Jeong Jae; Nguyen, Ngoc A.; Guralnick, Brett W.; Park, Jungjin; Somogyi, Árpád; Theato, Patrick; Mackay, Michael E.; Sung, Yung-Eun; Char, Kookheon; Pyun, Jeffrey (14 April 2013). "The use of elemental sulfur as an alternative feedstock for polymeric materials". Nature Chemistry. 5 (6): 518–524. Bibcode:2013NatCh...5..518C. doi:10.1038/NCHEM.1624. 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