Nature Communications
·
2024
·Vol. 15
·期 1
·1-17
·
IF 14.7
Zheng Botuo,Zhong Liling,Wang Xiaoxiao,Lin Peiyao,Yang Zezhou,Bai Tianwen,Shen Hang,Zhang Huagui
Inverse vulcanization exploits S 8 to synthesize polysulfides. However, evolution of products and its mechanism during inverse vulcanization remains elusive. Herein, inverse vulcanization curves are obtained to describe the inverse vulcanization process in terms of three stages: induction, curing and over-cure. The typical curves exhibit a moduli increment before declining or plateauing, reflecting the process of polysulfide network formation and loosing depending on monomers. For aromatic alkenes, in the over-cure, the crosslinked polysulfide evolves significantly into a sparse network with accelerated relaxation, due to the degradation of alkenyl moieties into thiocarbonyls. The inverse vulcanization product of olefins degrades slowly with fluctuated relaxation time and modulus because of the generation of thiophene moieties, while the inverse vulcanization curve of dicyclopentadiene has a plateau following curing stage. Confirmed by calculations, the mechanisms reveal the alkenyl groups react spontaneously into thiocarbonyls or thiophenes via similar sulfur-substituted alkenyl intermediates but with different energy barriers.
研究领域:
材料科学
·
化学
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DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Hang Shen,Huawei Qiao,Huagui Zhang
The growing cost of petroleum derivatives and the increasingly stringent environmental regulations have led the adhesive industry to re-seek solutions from natural resources in the past decades. However, most currently available natural adhesives (e.g. polysaccharides) are conflicted with low performances such as weak adhesion and easy microbial degradation, etc. On the other hand, owning self-repairability has become a popular way for a new material to extend its lifetime, to reduce its environmental footprint, and to meet the increasing demands of smart functions. This is also true to adhesive industry with self-repairable adhesive highly desirable. In this work, plant resourced urushiol and industrial waste of elemental sulfur (S) was used to prepare sulfur-urushiol copolymers (IVurux) as a high-strength, self-repairable and antimicrobial adhesive through inverse vulcanization, a facile and green approach free of solvent and catalyst. The polymerization between unsaturated bonds of urushiol and sulfur in forming a reversibly crosslinked network with polysulfide segments has been verified by FTIR and 1 H NMR analysis. The adaptable covalent S-S bonds from polysulfide segments endow the copolymer networks with a distinct self-healing property, while the rich catechol groups from urushiol moiety guarantee the material with an outstanding adhesive property. The adaptable covalent networking was well validated by a distinct rubbery plateau in rheological measurements of both temperature ramping test and frequency sweep test. The crosslinking density was revealed to increase with sulfur content, with frequency scaling exponent of G’ in the plateau regime varying from G’∼ω 0.27 in IVuru70 (S content 30 wt%) to G’∼ω 0 in IVuru50 (S 50 wt%) and IVuru40 (S 60 wt%), while when S >60 wt% few unreacted sulfur presented in the product as indicated from XRD and DSC analysis. Moreover, the self-healing property was well demonstrated in a repeated breaking-healing cycle test with 92.7% recovery obtained after 4 breaking cycles for IVuru50, and the dynamic S-S bond exchange was studied by stress relaxation to be temperature dependent with an activation energy of metathesis ∼100 kJ/mol. Furthermore, the P(sulfur-r-urushiol)s were examined to exhibit a considerable adhesion strength ∼3.0 MPa, about 6 times of a commercial hide glue, with IVuru60 being the best as a balanced contribution between catechol groups and covalent networking for adhesive and cohesive bonding. Meanwhile, a very good self-repairability of the adhesive was demonstrated with heating being the trigger for S-S metathesis. Ultimately, the P(sulfur-r-urushiol) copolymers were found to be hydrophobic with a contact angle ∼ 85° and have an excellent antimicrobial activity against S. aureus and S. cerevisiae with a high inhibition efficiency >80% and >52%, respectively. Such a high-strength, self-repairable and antimicrobial adhesive material foresees promising applications in broad fields in light of its advantages of fabrication simplicity, environmentally friendliness and good durability.
研究领域:
材料科学
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化学工程
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生物医学
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DOI
高影响因子
POLYMERS & POLYMER COMPOSITES
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2023
·
IF 2.1
Ya Lyu,Qin Su
Inverse vulcanization is a cost-effective method for producing high sulfur-content copolymers by combining elemental sulfur with organic monomers, which has rapidly gained popularity due to its simplicity of synthesis and wide range of applications. Although numerous examples of sulfur-rich copolymers have been synthesized at different reaction rates and temperatures using various monomers, the precise reaction mechanism remains unclear. In this paper, we used tung oil containing conjugated triene as a monomer to synthesize sulfur-rich copolymers under six different reaction conditions and investigate the effects of oxygen and moisture. Our study, which employed DSC, XRD, 1H NMR, and XPS characterization methods, revealed that oxygen accelerated the reaction rate and decreased the free sulfur content of the products, while moisture shortened the gel times but increased the free sulfur content. These findings confirm that reverse vulcanization involves two simultaneous mechanisms: the free radical mechanism and the anion mechanism. With regard to the radical mechanism, we discuss the source, ease, and reactivity of radicals and show that the creation of radicals depends on the second monomer rather than sulfur. Tung oil not only acts as a comonomer in the reaction but also plays an initiating role in promoting the dissociation of sulfur chains to generate free radicals for addition of non-conjugated double bonds. The effect of the anion mechanism exceeds that of the radical mechanism once certain factors are stimulated, such as the presence of metal ions and sulfide ions. Understanding the detailed mechanisms involved in inverse vulcanization is essential for selecting optimal monomers, which can enhance not only the synthesis process but also the properties of sulfur-rich materials.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2025
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IF 9
Yongpeng Ma,Chaobin Shi,Qinyuan Hong,Jianghui Du,Hongzhong Zhang,Xuanhui Zheng,Zan Qu,Xiaojing Zhang,Haomiao Xu
This study presents the synthesis of a novel sulfur-based copolymer, S-Tha-Cy, through a unique approach involving graft copolymerization and inverse vulcanization, leveraging cyclooctadiene (Cy) as a crosslinking agent and thioacetamide (Tha) as a grafting monomer. The integration of Tha into the copolymer structure enhances sulfur coordination, exposing additional reactive sulfur sites and incorporating nitrogen-containing moieties. These modifications significantly boost the material’s electron-donating ability, promoting the formation of stable coordination covalent bonds with Hg 2+ ions. S-Tha-Cy demonstrates exceptional Hg 2+ removal efficiency, achieving nearly complete (99.99 %) removal within 30 s, even in competitive environments with other heavy metals. Density functional theory (DFT) calculations confirm a high adsorption energy of −0.508 eV for Hg 2+ , indicating a strong affinity of S-Tha-Cy for mercury. Furthermore, the hybrid material S-Tha-Cy-3-N-Al, which combines S-Tha-Cy with nano-Al 2 O 3 , exhibits sustained Hg 2+ removal capabilities from wastewater. This research presents a breakthrough in the design of sulfur-based materials, offering both innovative synthetic strategies and theoretical frameworks for the efficient capture of heavy metals.
研究领域:
材料科学
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环境科学
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2024
·
IF 7.1
Xingwei Xun,Dongping Chen,Xi-Cun Wang,Xiaofeng Wu,Zheng-Jun Quan
Organic polysulfides have garnered significant attention recently as functional materials due to their abundant S–S bonds and strong chemical bonding structures, with potential applications in heavy metal adsorption, antimicrobials, and lithium–sulfur batteries. However, the environmental concerns associated with petroleum-based polymers and the flammability of sulfur pose challenges for their applications. This study describes the successful preparation of an inverse vulcanization sulfur-rich polymer using biobased resveratrol allyl ether as a copolymerization monomer. The polymer exhibits an ultrahigh glass transition temperature (Tg = 148 °C) and thermal stability, excellent flame retardancy, highly efficient silver absorption (removal rate >99.9%), outstanding silver-regenerative antimicrobial properties (complete inhibition of the growth and propagation of Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli)), as well as excellent specific discharge capacity (1198 mAh g–1), cycling performance, and rate capability. In situ battery infrared and DFT studies indicate that during the electrochemical redox process, the structure of the polymer undergoes a reorganization. The high active sulfur loading electrodes (∼5 mg cm–2) are also prepared to exhibit a certain practical potential with good discharge capacity and capacity retention.
研究领域:
材料科学
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环境科学
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电化学
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DOI
高影响因子
ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH
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2024
·Vol. 31
·期 11
·16940-16957
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IF 0
Lyu Shiqi,Abidin Zurina Zainal,Yaw Thomas Choong Shean,Resul Mohamad Faiz Mukhtar Gunam
The applications of polysulfides derived from natural plant oil and sulfur via the inverse vulcanization in the removal of heavy metals from aqueous solutions suffered from their low porosity and scarce surface functionality because of their hydrophobic surfaces and bulk characteristics. In this study, polysulfides from sulfur and palm oil (PSPs) with significantly enhanced porosity (13.7–24.1 m 2 /g) and surface oxygen-containing functional groups (6.9–8.6 wt.%) were synthesized with the optimization of process conditions including reaction time, temperature, and mass ratios of sulfur/palm oil/NaCl/sodium citrate. PSPs were applied as sorbents to remove heavy metals present in aqueous solutions. The integration of porosity and oxygen modification allowed a fast kinetic (4.0 h) and enhanced maximum sorption capacities for Pb(II) (218.5 mg/g), Cu(II) (74.8 mg/g), and Cr(III) (68.4 mg/g) at pH 5.0 and T 298 K comparing with polysulfides made without NaCl/sodium citrate. The sorption behaviors of Pb(II), Cu(II), and Cr(III) on PSPs were highly dependent on the solution pH values and ionic strength. The sorption presented excellent anti-interference capability for the coexisting cations and anions. The sorption processes were endothermic and spontaneous. This work would guide the preparation of porous polysulfides with surface modification as efficient sorbents to remediate heavy metals from aqueous solutions.
研究领域:
环境科学
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材料科学
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DOI
PubMed
REACTIVE & FUNCTIONAL POLYMERS
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2017
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IF 3.151
Shuhui Zhang,Lili Pan,Lieyin Xia,Yanbin Sun,Xikui Liu
In this study, we demonstrate the synthesis of dynamic polysulfide networks through the solution polycondensation of pentaerythritol tetra(3-mercaptopropionate) (PTMP) with elemental sulfur by a reverse vulcanization process. Elemental sulfur content as high as 51% can be incorporated into the dynamic polysulfide networks. An important feature of the resulted polysulfide networks is their catalytic-free malleability, which implies that they have both thermo- and photo-induced solid-state plasticities to obtain a complex permanent shape due to the exchange of dynamic S S bonds. These dynamic polysulfide networks have great potentials in fabricating complex three-dimensional shape memory devices for biological and mechanical applications.
研究领域:
材料科学
·
高分子化学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2023
·
IF 15.1
Kailun Wei,Kefei Zhao,Yuxia Gao,Hao Zhang,Xia Yu,Min-Hui Li,Jun Hu
Functional carriers are appealing materials for pesticide formulations due to their superior role in improving pesticide utilization and reducing environmental pollution. Nevertheless, current carriers often involve tedious chemical synthesis and are time-consuming, which rise potential risks to environment and limit the large-scale industrialization. Here, taking advantage of inverse vulcanization reaction, a near-infrared responsive polysulfide carrier (SOCT) loading tebuconazole (Teb) is prepared in one-pot by using industrial waste sulfur (S 8 ), bio-based soybean oil (SO), and agricultural waste biochar as raw materials. The facile solvent- and surfactant-free processing and the low-cost of raw materials make SOCT be produced easily in kilogram-scale with a loading content of 34.1 wt%. The resulting SOCT exhibits good photothermal property upon irradiation of NIR light, and its release behavior is stable enough against different pH values and coexisting ions, implementing the controlled release of Teb. In vitro and in vivo experiments indicate that SOCT has excellent fungicidal activities against three pathogenic fungi and high biosafety for wheat seed germination and adult zebrafish. In addition, the carrier material is able to be degraded completely in the presence of alkaline or dithiothreitol molecules, due to the available dynamic ester and S-S bonds in polysulfides. These unique features endow our carriers with promising potentials in practical agro-productions. To the best of our knowledge, this is the first time to use inverse vulcanization to prepare carrier materials for pesticides, which provides an effective approach for pesticide formulations with multi-functionality and sustainability.
研究领域:
材料科学
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农业科学
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环境科学
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产品关联
DOI
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
·
2025
·
IF 4
Guo Hao-Jia,Wu Zhou-Liang,Liao Shuang-Quan,Luo Ming-Chao
Recycling of waste rubber (WR) is crucial for the sustainable development of the rubber industry. The enhancement of interfacial interactions is the main strategy for waste polymer recycling. However, there is a lack of methods for enhancing the interfacial interactions for WR recycling because WR contains abundant inert C—H bonds. Herein, we designed thioctic acid inverse vulcanization copolymers to endow recycled WR with dynamic disulfide interfacial interactions, significantly improving the mechanical properties of recycled WR. These disulfide interfacial interactions among the recycled WR tend to exchange, which dramatically increases the fractocohesive length and prevents stress concentration near the crack tips. When recycled WR is subjected to external stress, the loads are redistributed across a broad region of adjacent regions instead of being concentrated on a limited length scale, which resists crack propagation. This work effectively recycled WR, providing a strategy for solvent-free reaction-derived inverse vulcanization copolymers to improve the toughness of WR recycling.
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DOI
高影响因子
ACS Applied Polymer Materials
·
2022
·
IF 4.855
Congcong Miao,Xingwei Xun,Liam J. Dodd,Shiquan Niu,Haoran Wang,Peiyao Yan,Xi-Cun Wang,Jian Li,Xiaofeng Wu,Tom Hasell,Zheng-Jun Quan
Sulfur-rich polymers generated from the inverse vulcanization of elemental sulfur with unsaturated monomers have emerged as a family of organic polymers with unique functionalities and broad potential applications. First described in 2013, inverse vulcanization is still in its infancy regarding its fundamental development, property exploration of the resultant polymers, and practical utilizations. Herein, the robust properties of sulfur-rich composites generated by inverse vulcanization with SiO2-embedded elemental sulfur are revealed, furnishing superhydrophobicity with static water contact angles of up to 154.7 ± 1.8°, a high anticorrosive effect of 98.9% protection efficiency for Mg alloy in 3.5 wt % NaCl solution, and a good antibacterial performance against Escherichia coli (81%) and Staphylococcus aureus (75%). The resulted composite also shows excellent self-cleaning functionalities. This has not only expanded the properties/functionalities and applications of the sulfur-rich polymers resulting from inverse vulcanization but also provided low-cost alternatives to superhydrophobic coating materials for practical applications.
研究领域:
材料科学
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聚合物化学
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表面科学
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腐蚀科学
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生物材料
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
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2025
·
IF 8.5
Aiping Zhan,Hou-Yong Yu
Human skin exhibits remarkable self-healing and responsiveness, attributed to dynamic disulfide (S S) bonds. However, traditional elastomer polymers often suffer from poor mechanical performance, low stability, and weak signal-capture capabilities due to metastability and insufficient interchain interactions. To overcome these limitations, a novel strategy combining inverse vulcanization and iron(III)-carboxylate coordination was proposed to construct a multifunctional, recyclable elastomer named PTCFe. In this system, thioctic acid (TA) undergoes inverse vulcanization with maleic acid-modified cellulose nanocrystals (MACNC), forming a robust dynamic network. Subsequently, ferric chloride (FeCl₃) induces multivalent Fe 3+ –carboxylate coordination, further reinforcing the polymer matrix. The presence of abundant hydrogen bonds and dynamic S S linkages synergistically enhance interchain interactions. As a result, PTCFe demonstrates high optical transparency (>90 %), exceptional stretchability (up to 1200 %), and strong adhesion (1368.56–1938.76 KPa) to diverse surfaces. It also exhibits outstanding self-healing efficiency (up to 89.6 %) and skin-friendly properties, maintaining stable signal detection during strenuous activities such as mountaineering, even under subzero conditions. Moreover, the elastomer is fully recyclable by thermal remelting and shows rapid biodegradability in soil. The PTCFe with above properties as a promising platform for next-generation wearable sensors and electronic skin (e-skin) technologies.
研究领域:
材料科学
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高分子化学
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柔性电子学
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可穿戴传感器
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生物降解材料
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
·
2024
·Vol. 42
·期 10
·1479-1487
·
IF 4.1
Chen Ke-Xiang,Cui Chen-Hui,Li Zhen,Xu Ting,Teng Hao-Qing,He Zhi-Yuan,Guo Yin-Zhou,Ming Xiao-Qing,Ge Zhi-Shen,Zhang Yan-Feng,Wang Tie-Jun
Sulfur-containing dynamic polymers had attracted significant attention due to their unique chemical structures with high reversibility. Utilizating sulfur, an inexpensive industrial waste product, to synthesize dynamic polysulfide polymers through reverse vulcanization has been a notable approach. However, this method required high temperatures and resulted in the release of unpleasant oders. In this study, we presented a robust method for the preparation of sulfur-rich polymers with dynamic polysulfide bonds from elemental sulfur and inexpensive epoxide monomers via a one-pot strategy at the mild room temperature. Different types of polysulfide molecules and polymers were synthesized by reacting various epoxide compounds with sulfur, along with the investigation of their structures and dynamic behaviors. It was noteworthy that the obatined polymers prepared from m -(2,3-epoxypropoxy)- N,N -bis(2,3-epoxypropyl)aniline and elemental sulfur exhibit multiple dynamic behaviors, including polysulfide metathesis and polysulfide-thiol exchange, enabling their rapid stress relaxation, self-healing, reprocessing and degradable properties of the cross-linked polymer. More importantly, the hydroxyl groups at the side chains from epoxide ring opening exhibited potential transesterification. This work provided a facile strategy for designing dynamic sulfur-rich polymers via a mild synthesis route.
研究领域:
材料科学
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聚合物化学
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可持续化学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）