Journal of the American Chemical Society
·
2019
·
IF 14.695
Cheng-Jian Zhang,Tian-Cheng Zhu,Xiao-Han Cao,Xin Hong,Xing-Hong Zhang
The synthesis of poly(thioether), a highly desired sulfur-containing polymer, is still a key challenge. Herein, we report a simple and facile approach to poly(thioether)s by closed-system one-pot reaction of carbonyl sulfide (COS) and epoxides. This route underwent the coupling reaction of COS with epoxides, followed by decarboxylative ring-opening polymerization (ROP) of the generated mixed cyclic thiocarbonates with releasing of CO2 and a little bit of COS. Organic base was used as catalyst and initiator in the two steps, respectively. The oxygen/sulfur exchange reaction was driven by successive regioselective elementary reactions and spontaneous releasing of CO2 (COS), leading to the sulfur atom of COS transferring to poly(thioether)s, which was well demonstrated by DFT studies. This work provides an easy-to-handle, metal-free route to poly(thioether)s bearing diverse structures by using readily available chemicals.
研究领域:
高分子化学
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
MACROMOLECULAR CHEMISTRY AND PHYSICS
·
2020
·Vol. 221
·期 6
·1900557
·
IF 2.335
Yiran Wang,Xianhong Zhang,Yuhong Ma,Dong Chen,Changwen Zhao,Wantai Yang
This study reports a step-growth click-polymerization of 1,4-benzenedimethane (BDMT) and diethylene glycol divinyl ether (DEGVE) with 4-( N,N -diphenylamino)-benzaldehyde (DPAB) as a photoredox catalyst under irradiation of visible light. DPAB exhibits a strong UV–vis absorption at 350 nm and a strong fluorescence emission at 480 nm in anisole. There is a strong fluorescence quenching between BDMT and DPAB. The molecular weight of the polythiolether can be controlled by reaction time and monomer feed ratios. More importantly, α,ω-dithiol and α,ω-divinyl telechelic polythiolether oligomers are successfully synthesized by simply changing the molar ratios of BDMT to DEGVE. 1 H NMR and MALDI-TOF MS spectra demonstrate that the oligomers have high end group fidelity. In addition, strong fluorescence is observed when the α,ω-dithiol terminated polythiolether adds with N -(1-pyrenyl) maleimide, indicating that the as-prepared polythiolether bears reactive thiol end groups. Furthermore, high molecular weight polythiolether are prepared by chain extension with reactive polythiolether oligomers as macro-monomers. For example, α,ω-divinyl oligomer ( M n = 2000 g mol −1 ) could further react with α,ω-dithiol oligomer ( M n = 2400 g mol −1 ) to form high molecular weight polythiolether ( M n = 6000 g mol −1 ).
研究领域:
材料科学
·
化学工程
·
高分子化学
✓ 已验证
DOI
高影响因子
MACROMOLECULES
·
2019
·
IF 5.997
Cheng-Jian Zhang,Xing-Hong Zhang
Utilization of carbon disulfide (CS2), a low-cost and sulfur-rich one-carbon (C1) feedstock, for making sulfur-containing polymers is important for both polymer chemistry and applied environmental science. However, the production of well-defined sulfur-containing polymers from CS2 and epoxides remains a key challenge. Here, we report a robust coupling reaction of CS2 and epoxides for chemoselectively producing poly(thioether)s and carbonyl sulfide (COS) in one pot. The resultant polymer has exclusive thioether units and a thiol (−SH) terminal. This route takes advantage of oxygen/sulfur exchanges through two consecutive reactions, i.e., cycloaddition of CS2 to epoxides and dethiocarboxylative ring-opening polymerization of the generated cyclic dithiocarbonates. The process can be conducted in ambient air with several commercially available organic bases as catalysts (initiators) and extended to a variety of epoxides, yielding COS and diverse poly(thioether)s with tens of grams. This work furnishes an original and practical strategy for utilizing CS2 as a sulfur feedstock in polymer synthesis.
研究领域:
高分子化学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
International Journal of Electrochemical Science
·
2023
·
IF 1.5
Haoran Xu,Kai Han,Meng Li,Wen Li,Xiaoqi Chen,Jijun Xiao,Yantao Li
We describe a sandwich-like composite separator with two sheath layers of polythioetherimide (PTEI) and a core layer of Celgard2400 to improve the heat-resistance and wettability properties of polypropylene (Celgard2400) separators for lithium-ion batteries (LIBs). The porous PTEI membranes were prepared by a wet phase inversion process and coating with Celgard2400 via engaging a simple process without adhesive. The separators were characterized by thermogravimetric analysis, scanning electron microscopy, and contact angle measurements, and the electrochemical performances were evaluated. The results showed that the PTEI/Celgard2400/PTEI composite separators exhibited excellent thermal stabilities (-37% at 180°C), improved wettabilities, liquid electrolyte uptakes (298%) and ionic conductivities (0.59 mScm -1 ) relative to Celgard2400. Compared to the Celgard2400 separator cell, the PTEI/Celgard2400/PTEI composite separators exhibited almost identical electrochemical properties. Such composite separators with high heat-resistance and wettability properties have a great potential for applications in high-safety LIBs.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
EUROPEAN POLYMER JOURNAL
·
2023
·
IF 6
Zhanbin Feng,Guofei Feng,Xinchen Yue,Xing-Hong Zhang
Dielectric elastomers (DEs) with high actuated strains at low electric fields have been a great challenge over the past few decades. In this work, we report the preparation of poly(thioether) grafted Ti 3 C 2 T x MXene DE nanocomposites (MXeneK-FGE-BMI) with high area strain at low driving voltage (17.1 %@11.9 V/μm) by two steps: the pretreated MXene (MXeneK) initiated decarboxylative ring-opening polymerization (ROP) of furfuryl glycidyl ether (FGE) and carbonyl sulfide (COS), followed by the Diels-Alder (DA) crossslinking reaction between furan groups and bismaleimide (BMI). The grafting of poly(thioether) chains onto the MXeneK surfaces enables MXeneK well dispersed in the matrix, leading to the significant decrease of dielectric loss (tan δ, below 0.04@10 3 Hz). Low content of MXeneK (below 1.0 wt%) resulted in high ε’ (∼12.3@10 3 Hz) and low elastic modulus (Y, below 0.5 MPa). Therefore, the resultant DE nanocomposite present a high area strain of 17.1 % at a driving voltage of 11.9 V/μm, superior to the previous reports (0.7 %∼10 %@12 V/μm). This work provides a facile strategy to prepare DE nanocomposites with excellent electromechanical performances at low driving voltage.
研究领域:
材料科学
·
高分子化学
·
纳米技术
✓ 已验证
DOI
高影响因子
JOURNAL OF POLYMER SCIENCE
·
2020
·Vol. 58
·期 12
·1664-1674
·
IF 0
Yaochen Zheng,Jian Liu,Yan Guo,Qian Zhang,Xuan Gao,Zhengguo Gao,Tao He,Qingfu Ban
Cationic compounds often serve as antibacterial materials for a wide range of applications. However, the relationship of topology−antibacterial activity has been rarely revealed. Herein, three cationic polythioethers (CPTEs) with hyperbranched topologies are well designed and facilely synthesized via an all-click chemistry strategy (including thiol-ene and epoxy-amine additions). These as-prepared CPTEs were found to exhibited outstanding antibacterial activity against Escherichia coli and Staphylococcus aureus with minimum inhibitory concentrations against E. coli of 7.3, 14.6, and 14.6 μg ml −1 , and against S. aureus of 14.6, 29.2, and 29.2 μg ml −1 , respectively. The antibacterial activity is coincident with their degree of branching (DB, their DB values of 0.81, 0.48, and 0.27), which is mainly attributed to the inherent three-dimensional structure. The present strategy reveals the relationship of polymer topology and antibacterial activity, providing a novel possibility for designing and/or synthesis of high-efficiency antibacterial agents. Graphical In this study, three cationic polythioethers (CPTEs) with hyperbranched topologies were synthesized via click chemistry. The obtained CPTEs exhibit outstanding antibacterial activity against Escherichia coli and Staphylococcus aureus with minimum inhibitory concentrations. The results demonstrate the relationship between polymer topology and antibacterial activity. It also provides a potential pathway to design antibacterial agents with high efficiency.
研究领域:
材料科学
·
微生物学
✓ 已验证
产品关联
DOI
Polymer Chemistry
·
2014
·Vol. 6
·期 4
·625-632
·
IF 5.368
Daoyi Jiang,Gang Wang,Feng Zheng,Jin Han,Xuedong Wu
A novel “clawlike” dendritic monomer, 3, 2,3-bis((2,3-bis(ethylthio)propyl)-thio)propyl methacrylate was prepared and successfully incorporated into a thermosensitive poly(N-isopropylacrylamide) (PNIPAM) hydrogel system by free radical polymerization. The lower critical solution temperature (LCST) of these hydrogels can be altered in the range of 31.0 °C to 81.1 °C by varying the amount of dendritic monomers and oxidants. Fourier transform infrared spectroscopy (FTIR) demonstrated the successful preparation of hydrogels and the oxidation of the hydrogels. X-ray photoelectron spectroscopy (XPS) was used to confirm the molar ratio of thioether and sulfoxide groups. The hydrogels containing thioether or sulfoxide groups show excellent absorption towards Ag+ ions, and every dendritic monomer and its oxidized derivative can capture on average 1.31 and 1.62 Ag+ ions, respectively. These Ag+ ions in the hydrogel were in situ reduced by NaBH4. Thioether or sulfoxide groups in the hydrogel made the size of Ag nanoparticles (about 20 nm) much smaller than those nanoparticles in PNIPAM hydrogel. These hydrogels containing thioether groups as oxidant scavengers and broad spectrum antimicrobial Ag nanoparticles may have promising application in dealing with infected wounds.
研究领域:
材料科学
·
生物医学工程
✓ 已验证
产品关联
DOI
高影响因子
Polymer Chemistry
·
2022
·Vol. 13
·期 10
·1376-1386
·
IF 5.364
Zhanbin Feng,Jiafang Guo,Xiaohan Cao,Guofei Feng,Zheqi Chen,Xing-Hong Zhang
The key to achieving homogenous dielectric elastomers (DEs) with broader application prospects is obtaining a high dielectric constant (ε′), excellent mechanical properties, and self-healing abilities. Herein, we report thermo-reversible furfuryl poly(thioether)-b-polysiloxane-b-furfuryl poly(thioether) triblock copolymer based homogenous DEs with tunable dielectric and mechanical performances. The triblock copolymer (PSiFGE) is synthesized via the silicon alkoxide catalyzed ring-opening polymerization (ROP) of furfuryl glycidyl ether (FGE) and carbonyl sulfide (COS). The Diels–Alder (DA) reaction is then realized after the incorporation of bismaleimide (BMI), and the thermo-reversible homogenous DE (PSiFGE-BMI) is obtained. The introduction of DA bonds endows PSiFGE-BMI with a thermo-reversible crosslinking network and an adjustable crosslinking degree. The resultant material exhibits alterable mechanical strength (varying from 0.16 MPa to 11.2 MPa) and a variable elastic modulus (Y, from 0.6 MPa to about 79 MPa). Of significance is that PSiFGE-BMI possesses a high ε′ (up to 7.6), high electromechanical sensitivity (β, up to 11.8 MPa−1), and a high actuation area strain (9.3%@9.8 V μm−1). In addition, the homogenous DE exhibits excellent shape memory and shape reconfiguration behavior with a fixing ratio (Rf) and recovery ratio (Rr) of above 90%. This work provides a new strategy to prepare homogenous DEs with improved electromechanical performance and shape memory behavior, leading to promising application prospects in actuated devices.
研究领域:
材料科学
·
高分子化学
✓ 已验证
DOI
高影响因子
POLYMERS FOR ADVANCED TECHNOLOGIES
·
2014
·Vol. 25
·期 3
·329-337
·
IF 1.964
Jiangtao Liu,Guofei Chen,Xingzhong Fang
A series of isomeric poly(thioether ether imide)s (PTEIs) containing both thioether and ether linkages were prepared by nucleophilic substitution reaction of isomeric bis(chlorophthalimide)s with 4,4′-thiobisbenzenethiol. The inherent viscosities of these polymers were in the range of 0.40–0.56 dL/g in m -cresol at 30°C. The T g values of PTEIs were 196–236°C; T 5% values reached up to 509–529°C in nitrogen and 508–534°C in air, which indicated this kind of polyimide possessed excellent thermal stability. The hydrolytic stability was arranged in the order: a > b > c > d > e, and improved with increasing the content of 3-substituted phthalimide unit in the polymer backbone. Flexible films could be cast from the polymer solution with a solid content of 10%. The PTEI films exhibited good mechanical properties with tensile strengths of 90–104 MPa, elongations at break of 6.6–7.9%, and tensile moduli of 2.3–2.6 GPa. The minimum complex viscosity of PTEIs c was about 100 Pa·s at 310°C and the minimum melt viscosity of PTEIs (a–e) decreased with increasing the content of unsymmetrical 3,4′-substituted phthalimide units. Copyright © 2014 John Wiley & Sons, Ltd.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
PROGRESS IN ORGANIC COATINGS
·
2020
·
IF 4.469
Jiandong Zuo,Zhao Liu,Chaoyun Luo,Feng Lin
Three kinds of biscitraconimide (BCI) monomers, 4,4′-(diaminodiphenylsulfone) biscitraconimide (DDS-BCI), 1,2-(ethylenediamine) biscitraconimide (EDA-BCI) and m-(xylylenediamine) biscitraconimide (MXDA-BCI), were respectively prepared from the reaction of citraconic anhydride with three different diamines by reflux dehydration in glacial acetic acid. As-prepared products further reacted with 4,4′-thiodibenzenethiol (TDBT) and 1,6-hexanedithiol (HDT) to synthesize a series of new transparent thermoplastic polythioetherimides (PTEI) films with excellent solubility, high refractive index and low birefringence. All PTEI films had the 5% weight loss temperature between 332 °C and 417 °C and the thermal expansion coefficient ranged from 39.4–94.8 ppm/°C, showing good thermal stability. Besides, the transmittance of PTEI film at 450 nm exceeded 85 %, the average refractive index (n av ) measured at 589 nm reached up to 1.6236 ∼1.6635 and in-plane/out of-plane birefringence (Δn) values were between 0.0014 and 0.0036. Especially DDS-BCI/TDBT sample exhibited the highest refractive index, relatively small birefringence and excellent thermal stability among all PTEI films, which is expected to be an ideal advanced optical material.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
HIGH PERFORMANCE POLYMERS
·
2014
·
IF 1.09
Jiangtao Liu,Guofei Chen,Xingzhong Fang
A series of isomeric poly(thioether ether imide)s (PTEIs) containing both thioether and ether linkages were prepared by aromatic nucleophilic substitution reaction of isomeric bis(chlorophthalimide)s (BCPIs) with bis(4-mercaptophenyl) ether (BMPE). The inherent viscosities of synthesized polymers were found in the range of 0.41–0.86 dL g−1 in N-methyl-2-pyrrolidone at 30°C. The glass transition temperature (Tg) of the isomeric PTEIs were 210–242°C and increased by increasing the content of 3-substituted phthalimide unit in the polymer backbone. The 5% weight loss temperature values reached up to 525–539°C under nitrogen and 523–534°C in air atmospheres, respectively, which indicated this kind of polyimide possessed excellent thermal stability. Flexible films could be cast from the polymer solution. The PTEI films exhibited moderate mechanical properties with tensile strengths of 106–127 MPa, elongations at break of 8.6–11.5%, and tensile moduli of 2.2–2.8 GPa, respectively. Dynamic mechanical thermal analysis results illustrated that the storage moduli (E′) of PTEI (a–e) almost completely maintained at about 2.3 GPa before reaching the corresponding Tg. It is noted that the minimum melt viscosity of isomeric PTEIs (a′–e′) decreased by increasing the content of unsymmetrical 3,4′-substituted phthalimide unit in the polymer main chain.
研究领域:
材料科学
·
高分子化学
✓ 已验证
DOI
高影响因子
REACTIVE & FUNCTIONAL POLYMERS
·
2023
·
IF 5.1
Liyang Zhao,Hongli Zhang,Gang Zou
Nonconventional luminogens, represented by clustering-triggered emission (CTE) materials, have attracted increasing attention owing to their unique intrinsic emission and promising applications. However, the influencing factors of clustering-triggered emission and gelation behavior remain poorly understood. Herein, a series of poly(thioether)s with different pendant groups were synthesized and their unique properties were studied. Owing to the similar molecular structure, all five poly(thioether)s exhibited visible photoluminescence , but the intensity varied when the pendant group or solvent changed, which could be attributed to different clustering degree between polymer chains. Moreover, poly(thioether)s with different pendant groups showed the diverse gelation behavior during polymerization process. The impact of pendant group on the clustering-triggered emission property and gelation behavior of poly(thioether) derivatives were investigated in detail, which might be of great fundamental value for the rational design of functional nonconventional luminogens for biological and medical applications.
研究领域:
材料科学
·
生物医学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）