Pub Date : 2024-11-06DOI: 10.1016/j.polymer.2024.127787
Feng Luo , Jichun Zhao , Long Jiao , Zhijun Du , Zhixin Dong , Yanna Zhang , Zhaoyan Sun , Xuepeng Qiu
In recent years, with the development of the flexible display field, there has been an increasing demand for colorless polyimide (CPI) that can be used for transparent displays. In this work, two cis- and trans-isomers of diamines 2,2'-((1r, 4r)-cyclohexane-1,4-diyl)bis (benzoxazol-5-amine) (trans-CHDB) and 2,2'-((1s, 4s)-cyclohexane-1,4-diyl)bis (benzoxazol-5-amine) (cis-CHDB) containing benzoxazole and cyclohexane structures were synthesized, and two series of polyimides CPI were prepared with three commercial dianhydrides: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA) and cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA). Presence of bisbenzoxazole structure enhanced rigidity and linearity of CPI molecular chain. CPI trans-CHDB/CBDA exhibited excellent comprehensive performance with a high Tg of 404 °C, coefficient of thermal expansion of 27.4 ppm K−1 Outstanding tensile modulus of 4.0 GPa. By introducing cyclohexane structure to suppress charge transfer interaction, optical transparency of CPI was increased. The transmittance of trans-CHDB/CBDA at 450 nm reached to 83.7 %, which was supposed to a promising application prospect for flexible display substrates.
{"title":"Preparation and properties of high temperature colorless transparent polyimide containing semi-alicyclic and bisbenzoxazole structure","authors":"Feng Luo , Jichun Zhao , Long Jiao , Zhijun Du , Zhixin Dong , Yanna Zhang , Zhaoyan Sun , Xuepeng Qiu","doi":"10.1016/j.polymer.2024.127787","DOIUrl":"10.1016/j.polymer.2024.127787","url":null,"abstract":"<div><div>In recent years, with the development of the flexible display field, there has been an increasing demand for colorless polyimide (CPI) that can be used for transparent displays. In this work, two <em>cis-</em> and <em>trans-</em>isomers of diamines 2,2'-((1r, 4r)-cyclohexane-1,4-diyl)bis (benzoxazol-5-amine) (<em>trans</em>-CHDB) and 2,2'-((1s, 4s)-cyclohexane-1,4-diyl)bis (benzoxazol-5-amine) (<em>cis</em>-CHDB) containing benzoxazole and cyclohexane structures were synthesized, and two series of polyimides CPI were prepared with three commercial dianhydrides: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA) and cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA). Presence of bisbenzoxazole structure enhanced rigidity and linearity of CPI molecular chain. CPI <em>trans</em>-CHDB/CBDA exhibited excellent comprehensive performance with a high <em>T</em><sub>g</sub> of 404 °C, coefficient of thermal expansion of 27.4 ppm K<sup>−1</sup> Outstanding tensile modulus of 4.0 GPa. By introducing cyclohexane structure to suppress charge transfer interaction, optical transparency of CPI was increased. The transmittance of <em>trans</em>-CHDB/CBDA at 450 nm reached to 83.7 %, which was supposed to a promising application prospect for flexible display substrates.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127787"},"PeriodicalIF":4.1,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-06DOI: 10.1016/j.polymer.2024.127797
Zhaopeng Hu , Xin Jiang , Benteng Liu , Qiao Li , Hongda Meng , Yihu Song , Yongzhong Bao , Qiang Zheng
Co-vulcanization of natural rubber (NR) and high-moduli Eucommia ulmoides gum (EUG) is promising while the reduction in crystallinity of crosslinked EUG is adverse for developing high-performance materials. Proposed herein is a novel method to prepare high-strength and high-stretchability NR/EUG vulcanizates with rapid vulcanization of EUG into slightly crosslinked particles, followed by further vulcanization of NR to form crosslinked matrix network. Deep eutectic solvents (DESs) are employed to facilitate the vulcanization of EUG during its blending with NR. The two-step vulcanization results in vulcanizates exhibiting superior mechanical properties under shear, tensile, and compressive conditions, significantly exceeding those of vulcanizates prepared by traditional processing methods. The reinforcement mechanism is elucidated by controlling thermomechanical coupling conditions and is supported by comprehensive structural characterizations. It is suggested that the EUG crystalline regions, maintained through the special processing method, work in conjunction with the stress-induced crystallization of the matrix to enhance the vulcanizates, nearly doubling the deformation stress at 800 % strain. The crystalline regions can mediate the deformation stress during shear and compression and weaken nonlinear rheological behavior. The established structure-performance relationship is guidable for preparing high-performance NR/EUG blend vulcanizates.
{"title":"Co-vulcanization of natural rubber and Eucommia ulmoides gum for mediation of the nonlinear rheology behaviors","authors":"Zhaopeng Hu , Xin Jiang , Benteng Liu , Qiao Li , Hongda Meng , Yihu Song , Yongzhong Bao , Qiang Zheng","doi":"10.1016/j.polymer.2024.127797","DOIUrl":"10.1016/j.polymer.2024.127797","url":null,"abstract":"<div><div>Co-vulcanization of natural rubber (NR) and high-moduli Eucommia ulmoides gum (EUG) is promising while the reduction in crystallinity of crosslinked EUG is adverse for developing high-performance materials. Proposed herein is a novel method to prepare high-strength and high-stretchability NR/EUG vulcanizates with rapid vulcanization of EUG into slightly crosslinked particles, followed by further vulcanization of NR to form crosslinked matrix network. Deep eutectic solvents (DESs) are employed to facilitate the vulcanization of EUG during its blending with NR. The two-step vulcanization results in vulcanizates exhibiting superior mechanical properties under shear, tensile, and compressive conditions, significantly exceeding those of vulcanizates prepared by traditional processing methods. The reinforcement mechanism is elucidated by controlling thermomechanical coupling conditions and is supported by comprehensive structural characterizations. It is suggested that the EUG crystalline regions, maintained through the special processing method, work in conjunction with the stress-induced crystallization of the matrix to enhance the vulcanizates, nearly doubling the deformation stress at 800 % strain. The crystalline regions can mediate the deformation stress during shear and compression and weaken nonlinear rheological behavior. The established structure-performance relationship is guidable for preparing high-performance NR/EUG blend vulcanizates.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127797"},"PeriodicalIF":4.1,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594257","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-05DOI: 10.1016/j.polymer.2024.127783
Li Lu , Jie Lin , Tingting Peng , Zhaowei Jia , Jincai Wu
Poly (α-hydroxy acids) (PAHAs) have garnered significant attention due to their pivotal role in various fields, including packaging, agriculture, and biomedical engineering, as biodegradable polyesters. Therefore, significant efforts have been dedicated to the development of methodologies that enable the facile preparation of PAHAs with controlled molecular weights and diverse pendant groups for versatile applications. However, the production of PAHAs through the ring-opening polymerization (ROP) of OCAs is highly challenging due to the strong side reaction of monomer racemization and the faster polymerization kinetics. To synthesize PAHAs with specific pendant groups and structure, researchers have developed a variety of ROP systems, each with its own unique advantages in recent years. Here, we have provided a summary of the fundamental characteristics and recent advancements of various methods, such as controlled/living ROP systems, topology-controlled ROP systems, stereoselective ROP systems of OCAs, and other copolymerization routes. Moreover, this article discusses the benefits and unresolved issues associated with different synthetic methods, providing readers with the necessary information to select rapid and manageable ROP systems for PAHAs synthesis.
{"title":"Recent advances in ring-opening (co)Polymerization of O-carboxyanhydrides","authors":"Li Lu , Jie Lin , Tingting Peng , Zhaowei Jia , Jincai Wu","doi":"10.1016/j.polymer.2024.127783","DOIUrl":"10.1016/j.polymer.2024.127783","url":null,"abstract":"<div><div>Poly (α-hydroxy acids) (PAHAs) have garnered significant attention due to their pivotal role in various fields, including packaging, agriculture, and biomedical engineering, as biodegradable polyesters. Therefore, significant efforts have been dedicated to the development of methodologies that enable the facile preparation of PAHAs with controlled molecular weights and diverse pendant groups for versatile applications. However, the production of PAHAs through the ring-opening polymerization (ROP) of OCAs is highly challenging due to the strong side reaction of monomer racemization and the faster polymerization kinetics. To synthesize PAHAs with specific pendant groups and structure, researchers have developed a variety of ROP systems, each with its own unique advantages in recent years. Here, we have provided a summary of the fundamental characteristics and recent advancements of various methods, such as controlled/living ROP systems, topology-controlled ROP systems, stereoselective ROP systems of OCAs, and other copolymerization routes. Moreover, this article discusses the benefits and unresolved issues associated with different synthetic methods, providing readers with the necessary information to select rapid and manageable ROP systems for PAHAs synthesis.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"314 ","pages":"Article 127783"},"PeriodicalIF":4.1,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-05DOI: 10.1016/j.polymer.2024.127785
Zhe Wang , Haodong Hu , Ruizheng Gao , Jingbo Zhou , Hongyu Zhu , Fei Xu , Jianwen Peng , Luchao Pei , Huaiyuan Wang , Di Bao , Yanji Zhu
The inherent low intrinsic thermal conductivity of epoxy resin severely restricts its potential application, making it difficult to meet the growing demand of energy, electrical and electronic technologies. The liquid crystal epoxy resin, which is wildly employed to improve the intrinsic thermal conductivity of epoxy resin, is constrained by its complex molecular structure design and synthesis procedures. In this work, the rigid group of 4,4′-dihydroxybiphenyl was introduced into the main chain of epoxy resin by ring-opening polymerization (ROP) to change the molecular structure of epoxy resin. The introduction of biphenyl groups enhances the orderliness of molecular structure and forms hydrogen bonds between molecules, which further enhances the transport of intramolecular phonons. The thermal conductivity of the graft modified epoxy resin (GMR) after DDM curing is 0.30 W m−1 K−1. After adding of organic crystal phenazine (PNE) to the GMR matrix, the inherent strong crystallization behaviors of PNE can accelerate the regularity arrangement of rigid groups in GMR, and promote the nucleation and crystallization process of GMR/PNE. The thermal conductivity of GMR/PNE after DDM curing can reach 0.33 W m−1 K−1. It is 165 % of the thermal conductivity of traditional epoxy resin, which is 0.2 W m−1 K−1. This study will provide a new method to improve the intrinsic thermal conductivity of polymer materials.
{"title":"Synergy between biphenyl mesomorphic structure and organic crystal phenazine for improving the intrinsic thermal conductivity of epoxy","authors":"Zhe Wang , Haodong Hu , Ruizheng Gao , Jingbo Zhou , Hongyu Zhu , Fei Xu , Jianwen Peng , Luchao Pei , Huaiyuan Wang , Di Bao , Yanji Zhu","doi":"10.1016/j.polymer.2024.127785","DOIUrl":"10.1016/j.polymer.2024.127785","url":null,"abstract":"<div><div>The inherent low intrinsic thermal conductivity of epoxy resin severely restricts its potential application, making it difficult to meet the growing demand of energy, electrical and electronic technologies. The liquid crystal epoxy resin, which is wildly employed to improve the intrinsic thermal conductivity of epoxy resin, is constrained by its complex molecular structure design and synthesis procedures. In this work, the rigid group of 4,4′-dihydroxybiphenyl was introduced into the main chain of epoxy resin by ring-opening polymerization (ROP) to change the molecular structure of epoxy resin. The introduction of biphenyl groups enhances the orderliness of molecular structure and forms hydrogen bonds between molecules, which further enhances the transport of intramolecular phonons. The thermal conductivity of the graft modified epoxy resin (GMR) after DDM curing is 0.30 W m<sup>−1</sup> K<sup>−1</sup>. After adding of organic crystal phenazine (PNE) to the GMR matrix, the inherent strong crystallization behaviors of PNE can accelerate the regularity arrangement of rigid groups in GMR, and promote the nucleation and crystallization process of GMR/PNE. The thermal conductivity of GMR/PNE after DDM curing can reach 0.33 W m<sup>−1</sup> K<sup>−1</sup>. It is 165 % of the thermal conductivity of traditional epoxy resin, which is 0.2 W m<sup>−1</sup> K<sup>−1</sup>. This study will provide a new method to improve the intrinsic thermal conductivity of polymer materials.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"314 ","pages":"Article 127785"},"PeriodicalIF":4.1,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142579905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-04DOI: 10.1016/j.polymer.2024.127781
Jinmei Ma , Shiyan Zhou , Yaqi Wang , Rong Chen , Shuai Wang , Fenghua Zhang , Yu-Peng He
Silicone-modified waterborne polyacrylate resins were created using semi-continuous emulsion polymerization. Vinyltriethoxysilane (A151) was used as a modified monomer. Two-component waterborne coatings were then prepared by adding poly (hexamethylene diisocyanate) (PHDI) as a curing agent to the A151-modified polyacrylate resins for the first time. The reaction mechanism of the acrylate copolymer and the curing mechanism of the coating were demonstrated using Fourier transform infrared spectroscopy (FTIR). The modification significantly improved the hydrophobicity and thermal stability of the coating, as confirmed by increased contact angle measurement and thermogravimetric (TG) analysis. Water absorption was reduced from 35 % to 10 % while maintaining optimal adhesion levels. Additionally, the low glass transition temperature of the acrylate resin emulsion film was investigated by differential scanning calorimetry (DSC), indicating excellent coating film properties for the two-component waterborne resin. The modification with PHDI not only significantly increased the water resistance time of the polymer coating but also improved the coating hardness while maintaining excellent adhesion of the silicon-containing resin to the substrate. This study introduces a new method for synthesizing low-cost, high-performance waterborne acrylate resins.
{"title":"Preparation and properties of vinyltriethoxysilane-modified waterborne acrylate resins","authors":"Jinmei Ma , Shiyan Zhou , Yaqi Wang , Rong Chen , Shuai Wang , Fenghua Zhang , Yu-Peng He","doi":"10.1016/j.polymer.2024.127781","DOIUrl":"10.1016/j.polymer.2024.127781","url":null,"abstract":"<div><div>Silicone-modified waterborne polyacrylate resins were created using semi-continuous emulsion polymerization. Vinyltriethoxysilane (A151) was used as a modified monomer. Two-component waterborne coatings were then prepared by adding poly (hexamethylene diisocyanate) (PHDI) as a curing agent to the A151-modified polyacrylate resins for the first time. The reaction mechanism of the acrylate copolymer and the curing mechanism of the coating were demonstrated using Fourier transform infrared spectroscopy (FTIR). The modification significantly improved the hydrophobicity and thermal stability of the coating, as confirmed by increased contact angle measurement and thermogravimetric (TG) analysis. Water absorption was reduced from 35 % to 10 % while maintaining optimal adhesion levels. Additionally, the low glass transition temperature of the acrylate resin emulsion film was investigated by differential scanning calorimetry (DSC), indicating excellent coating film properties for the two-component waterborne resin. The modification with PHDI not only significantly increased the water resistance time of the polymer coating but also improved the coating hardness while maintaining excellent adhesion of the silicon-containing resin to the substrate. This study introduces a new method for synthesizing low-cost, high-performance waterborne acrylate resins.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"314 ","pages":"Article 127781"},"PeriodicalIF":4.1,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574670","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-04DOI: 10.1016/j.polymer.2024.127779
Xiaodong Yang , Hui Sun , Tian Gao , Yining Sun , Jing Li , Sailing Lei , Bin Yu
The removal of oil from water surfaces is crucial for protecting the environment and living organisms from the hazards posed by industrial oily wastewater and offshore oil spills. However, achieving enhanced mechanical robustness, corrosion resistance, and durability in oil-water separation membranes presents a significant challenge. In this study, poly(ethylene chlorotrifluoroethylene) (ECTFE) resin, a novel semicrystalline polymer material composed of alternating ethylene and chlorotrifluoroethylene molecules, was fabricated into melt-blown fabric (MB) by melt-blowing technology. By optimizing the side wind temperature, collector distance, roller speed, and hot air pressure, ECTFE MB with superior mechanical properties was established. Additionally, the obtained ECTFE MB exhibited excellent hydrophobicity with a water contact angle reaching 127.8°. The separation efficiency for various oil-water mixtures (oil phase including carbon tetrachloride, petroleum ether, dichloromethane, n-hexane, and isooctane) exceeded 99 %. Furthermore, after 90 cycles of oil-water separation, ECTFE MB maintained high flux (72183.16 L m−2 h−1) and separation efficiency of 99.40 % when carbon tetrachloride was used as oil phase. Notably, ECTFE MB demonstrated exceptional resistance to harsh environments, including strong acids, bases, and mild high temperature. The investigation of failure modes of ECTFE MB revealed that the primary failure mode of ECTFE MB was the disruption of the oil-water interface. The maximum water height that the ECTFE MB could withstand was 1376 mm. Consequently, ECTFE MB exhibit excellent mechanical properties, chemical stability, and cycling stability, indicating the potential application in the field of oil-water separation.
{"title":"Development of a novel ECTFE melt-blown nonwoven materials and its application in oil-water separation","authors":"Xiaodong Yang , Hui Sun , Tian Gao , Yining Sun , Jing Li , Sailing Lei , Bin Yu","doi":"10.1016/j.polymer.2024.127779","DOIUrl":"10.1016/j.polymer.2024.127779","url":null,"abstract":"<div><div>The removal of oil from water surfaces is crucial for protecting the environment and living organisms from the hazards posed by industrial oily wastewater and offshore oil spills. However, achieving enhanced mechanical robustness, corrosion resistance, and durability in oil-water separation membranes presents a significant challenge. In this study, poly(ethylene chlorotrifluoroethylene) (ECTFE) resin, a novel semicrystalline polymer material composed of alternating ethylene and chlorotrifluoroethylene molecules, was fabricated into melt-blown fabric (MB) by melt-blowing technology. By optimizing the side wind temperature, collector distance, roller speed, and hot air pressure, ECTFE MB with superior mechanical properties was established. Additionally, the obtained ECTFE MB exhibited excellent hydrophobicity with a water contact angle reaching 127.8°. The separation efficiency for various oil-water mixtures (oil phase including carbon tetrachloride, petroleum ether, dichloromethane, n-hexane, and isooctane) exceeded 99 %. Furthermore, after 90 cycles of oil-water separation, ECTFE MB maintained high flux (72183.16 L m<sup>−2</sup> h<sup>−1</sup>) and separation efficiency of 99.40 % when carbon tetrachloride was used as oil phase. Notably, ECTFE MB demonstrated exceptional resistance to harsh environments, including strong acids, bases, and mild high temperature. The investigation of failure modes of ECTFE MB revealed that the primary failure mode of ECTFE MB was the disruption of the oil-water interface. The maximum water height that the ECTFE MB could withstand was 1376 mm. Consequently, ECTFE MB exhibit excellent mechanical properties, chemical stability, and cycling stability, indicating the potential application in the field of oil-water separation.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127779"},"PeriodicalIF":4.1,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-03DOI: 10.1016/j.polymer.2024.127777
Xinye Sun, Xinyue Deng, Shengwei Tang, Li Lv, Wenxiang Tang, Tao Zhang
The electrolyte is a crucial component that significantly affects the electrochemical performance of supercapacitors. The hydroxypropyl methylcellulose (HPMC)-based gel polymer electrolyte (GPE) with high operating voltage was synthesized via an innovative “one-pot” method in this study, and the impacts of organic solvent/water ratio and LiNO3 concentration on gelation and conductivity of the GPE were investigated systematically. Under the optimal condition with a DMF/water ratio of 10:0 and the incorporation of 7 % LiNO3, the ionic conductivity reached 1.06 S m−1. Integrated into symmetric supercapacitors, the HPMC-based GPE demonstrated an expanded electrochemical window of 2.7 V. It also possessed a specific capacitance of 115.8 F g−1 at 1.0 A g−1, an energy density of 29.31 Wh kg−1, and outstanding cyclic stability, retaining 86 % of its initial capacitance after 2000 cycles. Through cyclic stability tests under pressure conditions, the assembled flexible supercapacitors were able to maintain capacitance retention of 60 % and coulombic efficiency of 97 %. This work offers a streamlined synthesis for HPMC-based GPE with superior electrochemical properties, which exhibits its potential in advancing supercapacitor technology for flexible electronics.
电解质是显著影响超级电容器电化学性能的关键成分。本研究采用创新的 "一锅法 "合成了具有高工作电压的羟丙基甲基纤维素（HPMC）基凝胶聚合物电解质（GPE），并系统研究了有机溶剂/水比例和LiNO3浓度对GPE凝胶化和电导率的影响。在DMF/水比为10:0、掺入7%的LiNO3的最佳条件下，离子电导率达到了1.06 S m-1。在 1.0 A g-1 时，其比电容为 115.8 F g-1，能量密度为 29.31 Wh kg-1，并且具有出色的循环稳定性，在循环 2000 次后仍能保持 86% 的初始电容。通过压力条件下的循环稳定性测试，组装后的柔性超级电容器能够保持 60% 的电容保持率和 97% 的库仑效率。这项研究提供了一种具有优异电化学特性的基于 HPMC 的 GPE 的简化合成方法，展示了其在推动柔性电子产品超级电容器技术发展方面的潜力。
{"title":"One-pot synthesis of hydroxypropyl methylcellulose-based gel polymer electrolytes for high-performance supercapacitors","authors":"Xinye Sun, Xinyue Deng, Shengwei Tang, Li Lv, Wenxiang Tang, Tao Zhang","doi":"10.1016/j.polymer.2024.127777","DOIUrl":"10.1016/j.polymer.2024.127777","url":null,"abstract":"<div><div>The electrolyte is a crucial component that significantly affects the electrochemical performance of supercapacitors. The hydroxypropyl methylcellulose (HPMC)-based gel polymer electrolyte (GPE) with high operating voltage was synthesized via an innovative “one-pot” method in this study, and the impacts of organic solvent/water ratio and LiNO<sub>3</sub> concentration on gelation and conductivity of the GPE were investigated systematically. Under the optimal condition with a DMF/water ratio of 10:0 and the incorporation of 7 % LiNO<sub>3</sub>, the ionic conductivity reached 1.06 S m<sup>−1</sup>. Integrated into symmetric supercapacitors, the HPMC-based GPE demonstrated an expanded electrochemical window of 2.7 V. It also possessed a specific capacitance of 115.8 F g<sup>−1</sup> at 1.0 A g<sup>−1</sup>, an energy density of 29.31 Wh kg<sup>−1</sup>, and outstanding cyclic stability, retaining 86 % of its initial capacitance after 2000 cycles. Through cyclic stability tests under pressure conditions, the assembled flexible supercapacitors were able to maintain capacitance retention of 60 % and coulombic efficiency of 97 %. This work offers a streamlined synthesis for HPMC-based GPE with superior electrochemical properties, which exhibits its potential in advancing supercapacitor technology for flexible electronics.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"314 ","pages":"Article 127777"},"PeriodicalIF":4.1,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142566093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-03DOI: 10.1016/j.polymer.2024.127780
Qian Wang , Jiawei Guan , Haichuan Du , Xinpeng Yang , Futing Shi , Daoxian Li , Pengzhi Guo , Yangjun Xia
Unveiling the corresponding relationship between the molecular architecture of organic semiconductor materials and the morphology within the active layer of the organic solar cells (OSCs) is essential for the innovation of novel optical materials and the refinement of device optimization strategies to overcome the bottlenecks in efficiency. In this work, three dithieno[3,2-b]benzo[1,2-b;4,5-b’]dithiophene(DTBDT)-alt-benzothiadiazole (BT) based polymer donors (PDTBDT-F-BT, PDTBDT-F-FBT, and PDTBDT-F-2FBT) with varying fluorine atom content within their acceptor segments were designed and synthesized, and the photovoltaic performances of these polymers when blended with Y6 were meticulously investigated. Incorporating fluorine atoms into the BT segment was observed to not only incrementally increase the optical bandgap, lower the HOMO energy level, and bolster the self-aggregation of the polymer, but also effectively reduce the surface energy of the resulting polymer, thereby altering the donor-acceptor (D-A) interfacial spacing and the phase separation in the blend films as illustrated by molecular dynamic simulations and morphology characterization. As a result, the OSCs fabricated using PDTBDT-F-FBT, which incorporates a single fluorine substitution in the BT unit, demonstrated the highest power conversion efficiency (PCE) of 9.92 %. More importantly, this blend film's morphology is likely to be more conducive to the incorporation of the radical polymer additive, GDTA. This has resulted in a notable reduction in voltage loss, ultimately achieving a higher PCE of 11.55 % for the PDTBDT-F-FBT:Y6 based OSCs. This research uncovered a synergistic impact of backbone fluorination and the incorporation of radical polymer additives, which contributed to reducing the energy loss and enhancing the efficiency of OSCs from DTBDT-based polymer donors.
{"title":"Enhancing the photovoltaic performance of dithienobenzodithiophene based polymer donors through backbone fluorination and radical polymer additives","authors":"Qian Wang , Jiawei Guan , Haichuan Du , Xinpeng Yang , Futing Shi , Daoxian Li , Pengzhi Guo , Yangjun Xia","doi":"10.1016/j.polymer.2024.127780","DOIUrl":"10.1016/j.polymer.2024.127780","url":null,"abstract":"<div><div>Unveiling the corresponding relationship between the molecular architecture of organic semiconductor materials and the morphology within the active layer of the organic solar cells (OSCs) is essential for the innovation of novel optical materials and the refinement of device optimization strategies to overcome the bottlenecks in efficiency. In this work, three dithieno[3,2-<em>b</em>]benzo[1,2-<em>b</em>;4,5-<em>b’</em>]dithiophene(DTBDT)-<em>alt</em>-benzothiadiazole (BT) based polymer donors (PDTBDT-F-BT, PDTBDT-F-FBT, and PDTBDT-F-2FBT) with varying fluorine atom content within their acceptor segments were designed and synthesized, and the photovoltaic performances of these polymers when blended with Y6 were meticulously investigated. Incorporating fluorine atoms into the BT segment was observed to not only incrementally increase the optical bandgap, lower the HOMO energy level, and bolster the self-aggregation of the polymer, but also effectively reduce the surface energy of the resulting polymer, thereby altering the donor-acceptor (D-A) interfacial spacing and the phase separation in the blend films as illustrated by molecular dynamic simulations and morphology characterization. As a result, the OSCs fabricated using PDTBDT-F-FBT, which incorporates a single fluorine substitution in the BT unit, demonstrated the highest power conversion efficiency (PCE) of 9.92 %. More importantly, this blend film's morphology is likely to be more conducive to the incorporation of the radical polymer additive, GDTA. This has resulted in a notable reduction in voltage loss, ultimately achieving a higher PCE of 11.55 % for the PDTBDT-F-FBT:Y6 based OSCs. This research uncovered a synergistic impact of backbone fluorination and the incorporation of radical polymer additives, which contributed to reducing the energy loss and enhancing the efficiency of OSCs from DTBDT-based polymer donors.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"314 ","pages":"Article 127780"},"PeriodicalIF":4.1,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142566174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-02DOI: 10.1016/j.polymer.2024.127765
Cheng Qing , Kunhua Lin , Menglin Wang , Jia He , Rui Zhong , Kun Zhang , Kai Du , Yihan Wang , Qinjian Yin
Poly (3-hexylthiophene) (P3HT) is one of the promising organic magnetic materials due to its abundant spin properties and excellent solution processing ability. However, the dependence relationship of its magnetic properties on its electronic structure and solid-state order in thin film is unclear. Herein, the effect of molecular weight (Mw) on the ferromagnetism at room temperature of P3HT films was investigated by a comparative study on P3HT with Mw ranging from 19 to 84 kDa. The interference of magnetic impurities was carefully excluded. Structural analyses were performed to investigate the aggregates morphology and molecular features of P3HT thin films with different Mw. Differences in P3HT film ferromagnetism were observed and attributed to variation of solid-state order in mixed solvent. The saturation magnetization (Ms) increases first and then decreases with the increase of Mw, reaching a maximum value of 38.8 emu g−1 at 63 kDa, which was due to the largest molecular chain order and crystallinity of P3HT-63 kDa films. P3HT-84 kDa films had a higher proportion of disordered structural components and limited conjugation length, and yielding low crystallinity and magnetism (10.5 emu g−1).
{"title":"Molecular-weight dependence of ferromagnetism at room temperature of poly (3-hexylthiophene)","authors":"Cheng Qing , Kunhua Lin , Menglin Wang , Jia He , Rui Zhong , Kun Zhang , Kai Du , Yihan Wang , Qinjian Yin","doi":"10.1016/j.polymer.2024.127765","DOIUrl":"10.1016/j.polymer.2024.127765","url":null,"abstract":"<div><div>Poly (3-hexylthiophene) (P3HT) is one of the promising organic magnetic materials due to its abundant spin properties and excellent solution processing ability. However, the dependence relationship of its magnetic properties on its electronic structure and solid-state order in thin film is unclear. Herein, the effect of molecular weight (Mw) on the ferromagnetism at room temperature of P3HT films was investigated by a comparative study on P3HT with Mw ranging from 19 to 84 kDa. The interference of magnetic impurities was carefully excluded. Structural analyses were performed to investigate the aggregates morphology and molecular features of P3HT thin films with different Mw. Differences in P3HT film ferromagnetism were observed and attributed to variation of solid-state order in mixed solvent. The saturation magnetization (<em>M</em><sub>s</sub>) increases first and then decreases with the increase of Mw, reaching a maximum value of 38.8 emu g<sup>−1</sup> at 63 kDa, which was due to the largest molecular chain order and crystallinity of P3HT-63 kDa films. P3HT-84 kDa films had a higher proportion of disordered structural components and limited conjugation length, and yielding low crystallinity and magnetism (10.5 emu g<sup>−1</sup>).</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127765"},"PeriodicalIF":4.1,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142563188","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01DOI: 10.1016/j.polymer.2024.127750
Carolina Helena Franzon, Aurélien Roggero, Sébastien Pruvost, Jean-François Gérard
The molecular mobility of polyepoxy networks synthesized from diglycidyl ether of bisphenol-A (DGEBA) and cured with aliphatic diamines featuring varying polypropylene glycol (PPG) backbone lengths was investigated. The influence of ambient storage conditions, notably absorbed moisture, in conjunction with the network crosslink density on physical properties, was explored by using multiple techniques, including differential scanning calorimetry, dielectric and mechanical spectroscopies. In addition to known effects on glass transition and its dynamic manifestations, significant effects on secondary relaxation modes were observed, further highlighting the importance of controlling initial sample conditions when conducting molecular mobility studies. A bimodal -relaxation was observed in the presence of absorbed moisture as a result of an additional water-related mode, , ascribed to hydroxyether groups interacting with water.
我们研究了由双酚 A 的二缩水甘油醚（DGEBA）合成并用具有不同聚丙二醇（PPG）骨架长度的脂肪族二胺固化的聚环氧网络的分子流动性。研究采用了多种技术，包括差示扫描量热仪、介电光谱和机械光谱，探讨了环境储存条件（尤其是吸收的水分）以及网络交联密度对物理性质的影响。除了已知的对玻璃化转变及其动态表现的影响外，还观察到了对次级弛豫模式的显著影响，这进一步突出了在进行分子流动性研究时控制初始样品条件的重要性。在吸收水分的情况下，由于羟醚基团与水相互作用产生了一种与水相关的附加模式 β2β2，因此观察到了双模 β 松弛。
{"title":"Ambient moisture influence on the secondary relaxations of epoxy-amine networks with different crosslink densities","authors":"Carolina Helena Franzon, Aurélien Roggero, Sébastien Pruvost, Jean-François Gérard","doi":"10.1016/j.polymer.2024.127750","DOIUrl":"10.1016/j.polymer.2024.127750","url":null,"abstract":"<div><div>The molecular mobility of polyepoxy networks synthesized from diglycidyl ether of bisphenol-A (DGEBA) and cured with aliphatic diamines featuring varying polypropylene glycol (PPG) backbone lengths was investigated. The influence of ambient storage conditions, notably absorbed moisture, in conjunction with the network crosslink density on physical properties, was explored by using multiple techniques, including differential scanning calorimetry, dielectric and mechanical spectroscopies. In addition to known effects on glass transition and its dynamic manifestations, significant effects on secondary relaxation modes were observed, further highlighting the importance of controlling initial sample conditions when conducting molecular mobility studies. A bimodal <span><math><mi>β</mi></math></span>-relaxation was observed in the presence of absorbed moisture as a result of an additional water-related mode, <span><math><msub><mrow><mi>β</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span>, ascribed to hydroxyether groups interacting with water.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127750"},"PeriodicalIF":4.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562349","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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