Sulfur‐Limonene Polysulfide: A Material Synthesized Entirely from Industrial By‐Products and Its Use in Removing Toxic Metals from Water and Soil

Crockett, Michael P.; Evans, Austin M.; Worthington, Max J. H.; Albuquerque, Inês S.; Slattery, Ashley; Gibson, Christopher T.; Campbell, Jonathan A.; Lewis, David A.; Bernardes, Gonçalo J. L.; Chalker, Justin M.

doi:10.1002/anie.201508708

Cited by 255 publications

(217 citation statements)

References 36 publications

(8 reference statements)

Supporting

Mentioning

211

Contrasting

Order By: Relevance

“…Thes ynthesis of the NBD2 monomer was prepared according to literature procedures [14] and was then subjected to inverse vulcanization [15][16][17][18] with liquid sulfur (T = 130-160 8 8C) to afford poly(sulfur-random-NBD2)(poly(S-r-NBD2)), at two different feed ratios (70-wt %S /30-wt % NBD2 &5 0-wt %S /50-wt %N BD2). Copolymerization of these comonomers afforded amorphous,yellow,g lassy crosslinked networks.Structural characterization of these thermosets was done using 13 CC P-MAS solid-state NMR spectroscopy (Figure 3b), which confirmed that the norbornyl skeletal framework remained intact after polymerization, as indicated by the upfield resonances at 44 and 48 ppm from methylene and methine protons from NBD2.…”

Section: Angewandte Chemiementioning

confidence: 99%

Infrared Fingerprint Engineering: A Molecular‐Design Approach to Long‐Wave Infrared Transparency with Polymeric Materials

et al. 2019

View full text Add to dashboard Cite

Optical technologies in the long-wave infrared (LWIR) spectrum (7-14 mm) offer important advantages for high-resolution thermal imaging in near or complete darkness. The use of polymeric transmissive materials for IR imaging offers numerous cost and processing advantages but suffers from inferior optical properties in the LWIR spectrum. A major challenge in the design of LWIR-transparent organic materials is that nearly all organic molecules absorb in this spectral windoww hichl ies within the so-called IR-fingerprint region. We report on an ew molecular-design approacht o prepare high refractive index polymers with enhanced LWIR transparency.Computational methods were used to accelerate the design of novel molecules and polymers.U sing this approach,w eh ave prepared chalcogenide hybrid inorganic/ organic polymers (CHIPs) with enhanced LWIR transparency and thermomechanical properties via inverse vulcanization of elemental sulfur with new organic co-monomers.

show abstract

Section: Angewandte Chemiementioning

confidence: 99%

Infrared Fingerprint Engineering: A Molecular‐Design Approach to Long‐Wave Infrared Transparency with Polymeric Materials

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Similarly, inverse vulcanization is the treatment of molten sulfur at temperatures above 160 °C with vinylic monomers affording stable polymeric materials that could be scaled up to kilograms 60–62 . Several different materials have already been synthesized using this method ranging from IR lenses to mercury sorbents 63–67 . The process is relatively simple and sulfur can be used as much as 90%-wt.…”

Section: Introductionmentioning

confidence: 99%

Recycling and Self-Healing of Polybenzoxazines with Dynamic Sulfide Linkages

Arslan

Kışkan

Yaǧcı

2017

Sci Rep

View full text Add to dashboard Cite

In this work, a recycling and self-healing strategy for polybenzoxazines through both S-S bond cleavage-reformation reaction and supramolecular attractions is described. Both recyclable and selfhealable polybenzoxazines can be prepared from low cost chemicals with a simple procedure in only 30 minutes. For this purpose, inverse vulcanization of poly(propylene oxide)benzoxazine (PPOB) and diallybenzoxazine (B-al) with elemental sulfur was performed at 185 °C. The obtained cross-linked polymer films exhibited thermally driven recycling ability up to 5 cycles. Moreover, the self-healing ability of a test specimen was shown. Spectral characterizations, thermal stability and fracture toughness of the films were investigated after each recycling.In the past few decades, polybenzoxazines (PBZs), also known as benzoxazine resins, emerged as a superior alternative to classical resol and novolac type phenolic resins. The main structural difference of PBZs from classical phenolics is the tertiary amine groups in each repeating unit, which generates immense effect especially on hydrogen bonding types and strength. Due to these unique structural characteristics, PBZs exhibit high tensile strength and modulus (100-125 MPa, and 3.8-4.5 GPa, respectively), and high glass transition temperatures (T g ) (170-340 °C). Accordingly, these materials, particularly rigid ones or those admixed with transition metals, have high service temperatures, char yields, and are stable under acidic/alkali conditions. Unlike the general nature of phenolics, PBZs have low water adsorption stemming from strong intra-molecular hydrogen bonding. Another important aspect is related to their dimensional stability during synthesis. These resins are obtained by ring-opening polymerization of benzoxazine monomers at temperatures between 160-250 °C, sometimes higher, without any additive (Scheme 1) [1][2][3][4][5][6] . It should be emphasized that 1,3-isomers are the only active benzoxazines to undergo such polymerization. According to mechanistic studies, polymerization proceeds via the cationic pathway as oxazine rings have N and O atoms, which are capable of stabilizing cations during polymerization 7-9 .The other appealing side of PBZs is the synthesis of corresponding benzoxazine monomers, which can be accomplished using any suitable phenol, a primary amine, and formaldehyde; therefore, the number of possible benzoxazines is large (Fig. 1) [10][11][12][13][14][15][16] . Apparently, this design flexibility brings about a huge molecular diversity and control of structure and properties of PBZs. For example, crosslinking density of the resins can be increased by introducing dimerizable or polymerizable functionalities on benzoxazines 17,18 . The toughness of PBZs can be manipulated by using long chain amines and other soft or conversely rigid groups [19][20][21][22] . Gas forming moieties can be attached to benzoxazines causing macroporosity to occur during curing; thus, sponge-like materials can be obtained, etc 23,24 . Such suppleness in the properties ...

show abstract

“…[17] Only recently has the inverse vulcanization methodb een extendedt ot he use of the more common divinylbenzene [18] cross-linkers or naturalm olecules. [20] In parallel, different efforts were made to carry out the inverse vulcanization process in green solvents such as supercritical CO 2 . [19] However,a n additional step in modifying Cardanol into ar eactive benzoxazine wasr equired.…”

Section: Introductionmentioning

confidence: 99%

“…Chalker and co-workerss tudied the polymerization of sulfur with limonened irectly without using any prior modification step, but no battery tests were performed. [20] In parallel, different efforts were made to carry out the inverse vulcanization process in green solvents such as supercritical CO 2 . [21] In this work the inverse vulcanization of sulfur is investigated using two natural dienes, diallyl disulfide (DAS) and 7methyl-3-methylene-1,6-octadiene (myrcene).…”

Section: Introductionmentioning

confidence: 99%

Inverse Vulcanization of Sulfur using Natural Dienes as Sustainable Materials for Lithium–Sulfur Batteries

et al. 2016

View full text Add to dashboard Cite

Lithium-sulfur batteries are among the most promising next-generation battery systems due to the high capacity of sulfur as cathodic material. Beyond its interesting intrinsic properties, sulfur possesses a very low conductivity and complex electrochemistry, which involves the high solubility of the lithium sulfides in the electrolyte. These two characteristics are at the core of a series of limitations of its performance as active cathode material, which leads to batteries with low cyclability. Recently, inverse vulcanized sulfur was shown to retain capacity far better than elemental sulfur, leading to batteries with excellent cyclability. Nevertheless, the diene co-monomers used so far in the inverse vulcanization process are man-made molecules. Herein, a tentative work on exploring inverse vulcanization using two naturally available monomers, diallyl sulfide and myrcene, is presented. The inverse vulcanization of sulfur was successfully completed, and the resulting polymers were characterized by FTIR, NMR spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Afterwards these polymers were tested as cathodic materials in lithium-sulfur cells. The sulfur-natural dienes materials exhibited high capacity at different C rates and high lifetime over 200 cycles with very high capacity retention at a moderate C rate of C/5. Altogether, these materials made from inexpensive and abundant chemicals are an excellent option as sustainable materials for electrochemical energy storage.

show abstract

Sulfur‐Limonene Polysulfide: A Material Synthesized Entirely from Industrial By‐Products and Its Use in Removing Toxic Metals from Water and Soil

Cited by 255 publications

References 36 publications

Infrared Fingerprint Engineering: A Molecular‐Design Approach to Long‐Wave Infrared Transparency with Polymeric Materials

Infrared Fingerprint Engineering: A Molecular‐Design Approach to Long‐Wave Infrared Transparency with Polymeric Materials

Recycling and Self-Healing of Polybenzoxazines with Dynamic Sulfide Linkages

Inverse Vulcanization of Sulfur using Natural Dienes as Sustainable Materials for Lithium–Sulfur Batteries

Contact Info

Product

Resources

About