Pub Date : 2024-08-29DOI: 10.1038/s41428-024-00948-z
Takumi Yoshida, Toru Hoshi, Takao Aoyagi
In this study, polymers with different copolymerization composition ratios of α-chloro-ε-caprolactone (α-ClCL) and ε-caprolactone (ε-CL) were prepared using α-ClCL, which can polymerize on its own. The copolymers were prepared by using trimethylolpropane as the initiator, and acryloyl groups were added to the polymer ends to form macromonomers capable of cross-linking reactions. The functionalized macromonomers were confirmed to possess shape-memory properties when cross-flinked in film form by heat. The composition of the functional groups in the macromonomer could be adjusted by changing the ratio of α-ClCL to ε-CL used in the copolymerization. In addition, the chloro group introduced by α-ClCL was converted into an azide group. Both the cross-linked film with chloro groups and the film converted to azide groups prepared in this study exhibited shape-memory according to the softening point of the film. Through fluorescence microscopy, it was confirmed that the converted azide groups were modified with alkylated rhodamine B based on the click reaction. Furthermore, azide-assisted films are expected to add various functions through click reactions in the future. In this study, branched polymers with different copolymerization composition ratios of α-chloro-ε-caprolactone (α-ClCL) and ε-caprolactone (ε-CL) were prepared using α-ClCL and trimethylolpropane as the initiator. Furthermore, acryloyl groups were introduced at each chain ends of branched polymer to form macromonomers capable of cross-linking reactions. Films obtained by photo-crosslinking macromonomers with chloro groups showed shape-memory properties. In addition, the chloro group introduced by α-ClCL was converted into an azide group. This film is expected to be applied to various functional surfaces through the click reaction in the future.
{"title":"Molecular design of reactive polycaprolactone that can be induced into shape-memory materials promotes further functionalization","authors":"Takumi Yoshida, Toru Hoshi, Takao Aoyagi","doi":"10.1038/s41428-024-00948-z","DOIUrl":"10.1038/s41428-024-00948-z","url":null,"abstract":"In this study, polymers with different copolymerization composition ratios of α-chloro-ε-caprolactone (α-ClCL) and ε-caprolactone (ε-CL) were prepared using α-ClCL, which can polymerize on its own. The copolymers were prepared by using trimethylolpropane as the initiator, and acryloyl groups were added to the polymer ends to form macromonomers capable of cross-linking reactions. The functionalized macromonomers were confirmed to possess shape-memory properties when cross-flinked in film form by heat. The composition of the functional groups in the macromonomer could be adjusted by changing the ratio of α-ClCL to ε-CL used in the copolymerization. In addition, the chloro group introduced by α-ClCL was converted into an azide group. Both the cross-linked film with chloro groups and the film converted to azide groups prepared in this study exhibited shape-memory according to the softening point of the film. Through fluorescence microscopy, it was confirmed that the converted azide groups were modified with alkylated rhodamine B based on the click reaction. Furthermore, azide-assisted films are expected to add various functions through click reactions in the future. In this study, branched polymers with different copolymerization composition ratios of α-chloro-ε-caprolactone (α-ClCL) and ε-caprolactone (ε-CL) were prepared using α-ClCL and trimethylolpropane as the initiator. Furthermore, acryloyl groups were introduced at each chain ends of branched polymer to form macromonomers capable of cross-linking reactions. Films obtained by photo-crosslinking macromonomers with chloro groups showed shape-memory properties. In addition, the chloro group introduced by α-ClCL was converted into an azide group. This film is expected to be applied to various functional surfaces through the click reaction in the future.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 12","pages":"1177-1186"},"PeriodicalIF":2.3,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222757","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-29DOI: 10.1038/s41428-024-00950-5
A. B. M. Nazmul Islam, Nana Kayo, Yuki Motoishi, Ryo Hamano, Naoki Tanaka, Koichiro Kato, Tsuyohiko Fujigaya
The surface modification of carbon materials is an effective method for enhancing the properties of carbon-based functional materials; particularly, the use of a polymer coating is advantageous owing to its intactness and simplicity. Polybenzimidazole (PBI) has been used to modify carbon surfaces, yet its adsorption behavior has not been thoroughly examined. In this study, the adsorption kinetics and thermodynamics of PBI adsorption on various types of carbon black with different surface morphologies and chemical compositions were analyzed via isotherm measurements. To determine the effects of the polymer, its adsorption behavior was compared to that of the PBI monomer (1,3-bis(1H-benzo[d]imidazol-2-yl)benzene (referred to as the PBI-unit)). The surface adsorption of PBI was slower than that of the PBI-unit; however, PBI exhibited a greater adsorption capacity. The PBI adsorption is an entropy-driven process, whereas PBI-unit adsorption is enthalpy-driven. The adsorption of PBI was more thermodynamically favorable on carbon surfaces with higher crystallinity (lower oxygenation) owing to the easier detachment of solvent molecules from the carbon surface, leading to a higher adsorption constant. Physical modification of carbon materials using polymers is a useful technique for altering surface properties. The adsorption phenomenon of polybenzimidazole (PBI) in organic solvents onto different carbon materials with different surface morphologies and chemical compositions was examined to assess the key parameter controlling the adsorption phenomena. Adsorption isotherm measurements revealed that the adsorption of PBI was irreversible and thermodynamically favourable when interaction between solvent-carbon or PBI-solvent is low. PBI did not diffuse into micropore and the coverage ratio of the PBI onto mesopore and macropore surface was around 60%.
{"title":"Kinetics and thermodynamics analysis of the polybenzimidazole adsorption onto carbon materials using adsorption isotherm measurements","authors":"A. B. M. Nazmul Islam, Nana Kayo, Yuki Motoishi, Ryo Hamano, Naoki Tanaka, Koichiro Kato, Tsuyohiko Fujigaya","doi":"10.1038/s41428-024-00950-5","DOIUrl":"10.1038/s41428-024-00950-5","url":null,"abstract":"The surface modification of carbon materials is an effective method for enhancing the properties of carbon-based functional materials; particularly, the use of a polymer coating is advantageous owing to its intactness and simplicity. Polybenzimidazole (PBI) has been used to modify carbon surfaces, yet its adsorption behavior has not been thoroughly examined. In this study, the adsorption kinetics and thermodynamics of PBI adsorption on various types of carbon black with different surface morphologies and chemical compositions were analyzed via isotherm measurements. To determine the effects of the polymer, its adsorption behavior was compared to that of the PBI monomer (1,3-bis(1H-benzo[d]imidazol-2-yl)benzene (referred to as the PBI-unit)). The surface adsorption of PBI was slower than that of the PBI-unit; however, PBI exhibited a greater adsorption capacity. The PBI adsorption is an entropy-driven process, whereas PBI-unit adsorption is enthalpy-driven. The adsorption of PBI was more thermodynamically favorable on carbon surfaces with higher crystallinity (lower oxygenation) owing to the easier detachment of solvent molecules from the carbon surface, leading to a higher adsorption constant. Physical modification of carbon materials using polymers is a useful technique for altering surface properties. The adsorption phenomenon of polybenzimidazole (PBI) in organic solvents onto different carbon materials with different surface morphologies and chemical compositions was examined to assess the key parameter controlling the adsorption phenomena. Adsorption isotherm measurements revealed that the adsorption of PBI was irreversible and thermodynamically favourable when interaction between solvent-carbon or PBI-solvent is low. PBI did not diffuse into micropore and the coverage ratio of the PBI onto mesopore and macropore surface was around 60%.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 12","pages":"1153-1163"},"PeriodicalIF":2.3,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00950-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222759","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lignin is the most abundant aromatic material in the Earth’s terrestrial ecosystems. However, very few studies have been conducted on the potential application of lignin derivatives as fillers for electrolytes in lithium batteries to determine cell performance. Herein, a novel electrochemically stable composite polymer electrolyte (CPE) containing a lignin derivative and dilignol was exploited for battery application for the first time. The lignin derivatives improved both the ionic conductivity and mechanical performance of the polymer-based electrolytes. The resulting alterations in the coordination number led to enhanced Li+ mobility and consequently, increased conductivity. Notably, the LiFePO4/Li cell had good stability and recovery capacity, and the Coulombic efficiency was approximately 100%, with a capacity of more than 150 mAh g−1. A novel electrochemically stable composite polymer electrolyte (CPE) containing a lignin derivative and dilignol was exploited for battery application for the first time. The lignin derivatives improved both the ionic conductivity and mechanical performance of the polymer-based electrolytes. Notably, the LiFePO4/Li cell had improved stability and recovery capacity, and the Coulombic efficiency was approximately 100%, with a capacity of more than 150 mAh g−1. The resulting alterations in the coordination number led to enhanced Li+ mobility and consequently, increased conductivity and cell capacity.
木质素是地球陆地生态系统中最丰富的芳香物质。然而，关于木质素衍生物作为锂电池电解质填料以确定电池性能的潜在应用研究却寥寥无几。在此，我们首次将含有木质素衍生物和二木酚的新型电化学稳定复合聚合物电解质（CPE）应用于电池。木质素衍生物改善了聚合物电解质的离子传导性和机械性能。配位数的改变增强了 Li+ 的迁移率，从而提高了电导率。值得注意的是，LiFePO4/Li 电池具有良好的稳定性和恢复能力，库仑效率约为 100%，容量超过 150 mAh g-1。
{"title":"Ion-conductive properties and lithium battery performance of composite polymer electrolytes filled with lignin derivatives","authors":"Zitong Liu, Takumi Karasawa, Wei Tan, Hikaru Minegishi, Yasuyuki Matsushita, Kazuhiro Shikinaka, Yuichiro Otsuka, Yoichi Tominaga","doi":"10.1038/s41428-024-00941-6","DOIUrl":"10.1038/s41428-024-00941-6","url":null,"abstract":"Lignin is the most abundant aromatic material in the Earth’s terrestrial ecosystems. However, very few studies have been conducted on the potential application of lignin derivatives as fillers for electrolytes in lithium batteries to determine cell performance. Herein, a novel electrochemically stable composite polymer electrolyte (CPE) containing a lignin derivative and dilignol was exploited for battery application for the first time. The lignin derivatives improved both the ionic conductivity and mechanical performance of the polymer-based electrolytes. The resulting alterations in the coordination number led to enhanced Li+ mobility and consequently, increased conductivity. Notably, the LiFePO4/Li cell had good stability and recovery capacity, and the Coulombic efficiency was approximately 100%, with a capacity of more than 150 mAh g−1. A novel electrochemically stable composite polymer electrolyte (CPE) containing a lignin derivative and dilignol was exploited for battery application for the first time. The lignin derivatives improved both the ionic conductivity and mechanical performance of the polymer-based electrolytes. Notably, the LiFePO4/Li cell had improved stability and recovery capacity, and the Coulombic efficiency was approximately 100%, with a capacity of more than 150 mAh g−1. The resulting alterations in the coordination number led to enhanced Li+ mobility and consequently, increased conductivity and cell capacity.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 12","pages":"1165-1175"},"PeriodicalIF":2.3,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222760","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polymer alloy films were prepared by blending a polyfunctional benzoxazine monomer (OP-p), which was derived from an oligonuclear phenolic compound with a 4,4ʹ-dimethylenebiphenyl group as the phenol linker, and 4,4′-bismaleimidodiphenylmethane (BMI; 10–90 wt.%), followed by thermal curing up to 240 °C. The polymerization behavior was investigated via differential scanning calorimetry and Fourier transform infrared analyses; the results indicated that the obtained polymer alloys consisted of an AB crosslinked network structure formed through the ether linkage between the hydroxyl group of polybenzoxazine and the double bond of BMI. The obtained polymer alloy films were self-standing, homogeneous, and transparent. Based on the dynamic mechanical analysis of the films, the glass transition temperature (Tg) increased to 228 °C and 329 °C for the polymer alloy films with BMI contents of 60 wt.% and 75 wt.%, respectively, which were higher than those of the POP-p or PBMI homopolymer. Despite the improvement in the Tg, the alloy films exhibited sufficient toughness as evidenced via the tensile test. Moreover, thermogravimetric analysis of the polymer alloys revealed that the thermal stability increased with increasing BMI content. High performance polymer alloy films with high Tg, heat resistance, and sufficient toughness were prepared by blending a polyfunctional benzoxazine monomer (OP-p) and 4,4′-bismaleimidodiphenylmethane (BMI; 10–90 wt.%), followed by thermal curing up to 240 °C. The Tg increased to 228 °C and 329 °C for the polymer alloy films with BMI contents of 60 wt.% and 75 wt.%, respectively, which were higher than those of the POP-p or PBMI homopolymer. Despite the improvement in the Tg, the alloy films exhibited sufficient toughness as evidenced via the tensile test.
{"title":"Polymer alloys with high thermal properties consisting of polyfunctional benzoxazine derived from an oligonuclear phenolic compound and bismaleimide","authors":"Takumi Uramatsu, Sho Morinaga, Taichi Shibatsuka, Takehiro Kawauchi","doi":"10.1038/s41428-024-00947-0","DOIUrl":"10.1038/s41428-024-00947-0","url":null,"abstract":"Polymer alloy films were prepared by blending a polyfunctional benzoxazine monomer (OP-p), which was derived from an oligonuclear phenolic compound with a 4,4ʹ-dimethylenebiphenyl group as the phenol linker, and 4,4′-bismaleimidodiphenylmethane (BMI; 10–90 wt.%), followed by thermal curing up to 240 °C. The polymerization behavior was investigated via differential scanning calorimetry and Fourier transform infrared analyses; the results indicated that the obtained polymer alloys consisted of an AB crosslinked network structure formed through the ether linkage between the hydroxyl group of polybenzoxazine and the double bond of BMI. The obtained polymer alloy films were self-standing, homogeneous, and transparent. Based on the dynamic mechanical analysis of the films, the glass transition temperature (Tg) increased to 228 °C and 329 °C for the polymer alloy films with BMI contents of 60 wt.% and 75 wt.%, respectively, which were higher than those of the POP-p or PBMI homopolymer. Despite the improvement in the Tg, the alloy films exhibited sufficient toughness as evidenced via the tensile test. Moreover, thermogravimetric analysis of the polymer alloys revealed that the thermal stability increased with increasing BMI content. High performance polymer alloy films with high Tg, heat resistance, and sufficient toughness were prepared by blending a polyfunctional benzoxazine monomer (OP-p) and 4,4′-bismaleimidodiphenylmethane (BMI; 10–90 wt.%), followed by thermal curing up to 240 °C. The Tg increased to 228 °C and 329 °C for the polymer alloy films with BMI contents of 60 wt.% and 75 wt.%, respectively, which were higher than those of the POP-p or PBMI homopolymer. Despite the improvement in the Tg, the alloy films exhibited sufficient toughness as evidenced via the tensile test.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 12","pages":"1223-1230"},"PeriodicalIF":2.3,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00947-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222762","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-23DOI: 10.1038/s41428-024-00946-1
Yujin Kang, Donguk Kim, Wonho Lee, Changyeon Lee
The photoinduced solid‒liquid phase transition is a fascinating phenomenon that can be utilized for a range of applications, including debondable adhesives, photolithography, and soft actuators; however, developing polymers with this function is not trivial. In this work, we report an azobenzene (Azo)-containing polymer capable of rapid room-temperature photoliquefaction upon UV irradiation and elucidate the design principles for photoliquefying polymers that harness the photothermal effect. We prepare a series of Azo polymers by coupling diacrylate Azo with dithiol-functionalized flexible spacers of different lengths, such as ethylene glycol (EG), hexa(ethylene glycol) (HEG), and poly(ethylene glycol) (PEG). EG-Azo, with the shortest spacer, has a high melting temperature (Tm) of 78 °C due to the strong interactions among the liquid-crystalline Azo molecules. Owing to the high Tm, EG-Azo does not exhibit a photoinduced solid‒liquid phase transition, although it has the greatest photothermal effect among the polymers (temperature rise to 50 °C). The incorporation of the longer spacers effectively decreases the Tm of the Azo polymers. For example, PEG-Azo possesses a reduced Tm of 40 °C, thereby enabling photoliquefaction at room temperature after only 1 min of UV irradiation. PEG-Azo can be reversibly returned to a solid-state within 5 min after the UV light is turned off. This work shows that the length of flexible spacers in azobenzene (Azo)-based polymers is crucial for achieving room-temperature photoliquefaction (i.e., UV light-induced solid‒liquid phase transition). By adjusting the length of dithiol-functionalized flexible spacers, the melting temperature (Tm) of Azo polymers can be effectively modulated. Incorporating longer spacers decreases the Tm to a temperature achievable by the photothermal effect of Azo molecules, thus enabling photoliquefaction of Azo polymers at room temperature.
{"title":"Role of flexible spacers in achieving photoinduced phase transitions of azobenzene-based liquid-crystalline polymers at room temperature","authors":"Yujin Kang, Donguk Kim, Wonho Lee, Changyeon Lee","doi":"10.1038/s41428-024-00946-1","DOIUrl":"10.1038/s41428-024-00946-1","url":null,"abstract":"The photoinduced solid‒liquid phase transition is a fascinating phenomenon that can be utilized for a range of applications, including debondable adhesives, photolithography, and soft actuators; however, developing polymers with this function is not trivial. In this work, we report an azobenzene (Azo)-containing polymer capable of rapid room-temperature photoliquefaction upon UV irradiation and elucidate the design principles for photoliquefying polymers that harness the photothermal effect. We prepare a series of Azo polymers by coupling diacrylate Azo with dithiol-functionalized flexible spacers of different lengths, such as ethylene glycol (EG), hexa(ethylene glycol) (HEG), and poly(ethylene glycol) (PEG). EG-Azo, with the shortest spacer, has a high melting temperature (Tm) of 78 °C due to the strong interactions among the liquid-crystalline Azo molecules. Owing to the high Tm, EG-Azo does not exhibit a photoinduced solid‒liquid phase transition, although it has the greatest photothermal effect among the polymers (temperature rise to 50 °C). The incorporation of the longer spacers effectively decreases the Tm of the Azo polymers. For example, PEG-Azo possesses a reduced Tm of 40 °C, thereby enabling photoliquefaction at room temperature after only 1 min of UV irradiation. PEG-Azo can be reversibly returned to a solid-state within 5 min after the UV light is turned off. This work shows that the length of flexible spacers in azobenzene (Azo)-based polymers is crucial for achieving room-temperature photoliquefaction (i.e., UV light-induced solid‒liquid phase transition). By adjusting the length of dithiol-functionalized flexible spacers, the melting temperature (Tm) of Azo polymers can be effectively modulated. Incorporating longer spacers decreases the Tm to a temperature achievable by the photothermal effect of Azo molecules, thus enabling photoliquefaction of Azo polymers at room temperature.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 11","pages":"1061-1067"},"PeriodicalIF":2.3,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00946-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222761","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study prepared dual thermoresponsive diblock copolymers (E95Nn; n = 93 and 291) comprising poly(ethylene glycol) ethyl ether acrylate (PeDEGA; E) and poly(N-isopropylacrylamide) (PNIPAM; N) blocks with different lower critical solution temperatures (LCSTs). E95Nn was prepared via organotellurium-mediated living radical polymerization through a one-pot synthesis method. Energy-dispersive X-ray spectroscopy revealed that tellurium residue at the polymer chain end was removed during purification via dialysis. The LCST of the PeDEGA was lower than that of PNIPAM. At temperatures below the LCST of PeDEGA, E95Nn dissolved as a single polymer chain (the unimer state). When an aqueous solution of E95Nn was heated, polymer micelles with a PeDEGA core and PNIPAM shells formed above the LCST of the PeDEGA. In pure water, 7–10 polymer micelles formed intermicellar aggregates. The polymer micelles encapsulated hydrophobic guest molecules into the hydrophobic core formed from the PeDEGA chains. Large intermicellar aggregates formed above the LCST of PNIPAM owing to hydrophobic interactions between the PNIPAM shells. It is expected that E95Nn polymer micelles can be applied as drug carriers for thermoresponsive controlled drug release. Dual thermoresponsive diblock copolymers comprising poly(di(ethylene glycol) ethyl ether acrylate) (PeDEGA) and poly(N-isopropylacrylamide) (PNIPAM) blocks with different lower critical solution temperatures (LCSTA and LCSTB) were prepared via organotellurium-mediated living radical polymerization. The LCSTA of the PeDEGA was lower than the LCSTB of PNIPAM. At T < LCSTA, the diblock copolymers dissolve in a unimer state. When the LCSTA ≤ T < LCSTB, polymer micelles with a PeDEGA core and PNIPAM shells formed. Above the LCSTB, intermicellar aggregates formed owing to hydrophobic interactions between the PNIPAM shells.
{"title":"Thermoresponsive behavior of dual hydrophilic diblock copolymers prepared via organotellurium-mediated living radical polymerization","authors":"Misato Hayashi, Rintaro Takahashi, Thi Ngan Vu, Kazuaki Matsumura, Shigeru Yamago, Shin-ichi Yusa","doi":"10.1038/s41428-024-00952-3","DOIUrl":"10.1038/s41428-024-00952-3","url":null,"abstract":"This study prepared dual thermoresponsive diblock copolymers (E95Nn; n = 93 and 291) comprising poly(ethylene glycol) ethyl ether acrylate (PeDEGA; E) and poly(N-isopropylacrylamide) (PNIPAM; N) blocks with different lower critical solution temperatures (LCSTs). E95Nn was prepared via organotellurium-mediated living radical polymerization through a one-pot synthesis method. Energy-dispersive X-ray spectroscopy revealed that tellurium residue at the polymer chain end was removed during purification via dialysis. The LCST of the PeDEGA was lower than that of PNIPAM. At temperatures below the LCST of PeDEGA, E95Nn dissolved as a single polymer chain (the unimer state). When an aqueous solution of E95Nn was heated, polymer micelles with a PeDEGA core and PNIPAM shells formed above the LCST of the PeDEGA. In pure water, 7–10 polymer micelles formed intermicellar aggregates. The polymer micelles encapsulated hydrophobic guest molecules into the hydrophobic core formed from the PeDEGA chains. Large intermicellar aggregates formed above the LCST of PNIPAM owing to hydrophobic interactions between the PNIPAM shells. It is expected that E95Nn polymer micelles can be applied as drug carriers for thermoresponsive controlled drug release. Dual thermoresponsive diblock copolymers comprising poly(di(ethylene glycol) ethyl ether acrylate) (PeDEGA) and poly(N-isopropylacrylamide) (PNIPAM) blocks with different lower critical solution temperatures (LCSTA and LCSTB) were prepared via organotellurium-mediated living radical polymerization. The LCSTA of the PeDEGA was lower than the LCSTB of PNIPAM. At T < LCSTA, the diblock copolymers dissolve in a unimer state. When the LCSTA ≤ T < LCSTB, polymer micelles with a PeDEGA core and PNIPAM shells formed. Above the LCSTB, intermicellar aggregates formed owing to hydrophobic interactions between the PNIPAM shells.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 12","pages":"1129-1141"},"PeriodicalIF":2.3,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222763","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-13DOI: 10.1038/s41428-024-00944-3
Kuiyong Jia, Zhe Chen, Zhujun Huang, Xiangcheng Pan
The synthesis of optically active polymers from monomers with chiral central centers is a well-established method, but reports on the synthesis of optically active polymers using axially chiral monomers are limited. In this study, we present the controlled radical polymerization of axially chiral monomers derived from the commercially available 1,1′-bi-2-naphthol (BINOL) structure. A series of optically active polymers based on the axially chiral structures were successfully polymerized using cumyl dithiobenzoate (CDB) as a chain transfer agent (CTA) for the reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymerization process resulted in polymers with high conversions and yield controlled molecular weights. The differences observed in the specific optical rotation and the circular dichroism (CD) signal intensity between the polymers and the monomers confirmed the synthesis of optically active polymers with specific structures. Owing to their unique molecular scaffold, these chiral polymers have promising applications in areas such as chiral separation and catalysis. The graphical abstract shows the controlled radical polymerization of axially chiral monomers bearing a 1,1′-bi-2-naphthol (BINOL) skeleton. The evident increase in magnitude and opposite deflection direction of the specific optical rotation between the synthesized polymer and the monomer confirms the synthesis of the chiral polymers with specific structures.
{"title":"Synthesis and controlled radical polymerization of axially chiral monomers with a binaphthyl skeleton","authors":"Kuiyong Jia, Zhe Chen, Zhujun Huang, Xiangcheng Pan","doi":"10.1038/s41428-024-00944-3","DOIUrl":"10.1038/s41428-024-00944-3","url":null,"abstract":"The synthesis of optically active polymers from monomers with chiral central centers is a well-established method, but reports on the synthesis of optically active polymers using axially chiral monomers are limited. In this study, we present the controlled radical polymerization of axially chiral monomers derived from the commercially available 1,1′-bi-2-naphthol (BINOL) structure. A series of optically active polymers based on the axially chiral structures were successfully polymerized using cumyl dithiobenzoate (CDB) as a chain transfer agent (CTA) for the reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymerization process resulted in polymers with high conversions and yield controlled molecular weights. The differences observed in the specific optical rotation and the circular dichroism (CD) signal intensity between the polymers and the monomers confirmed the synthesis of optically active polymers with specific structures. Owing to their unique molecular scaffold, these chiral polymers have promising applications in areas such as chiral separation and catalysis. The graphical abstract shows the controlled radical polymerization of axially chiral monomers bearing a 1,1′-bi-2-naphthol (BINOL) skeleton. The evident increase in magnitude and opposite deflection direction of the specific optical rotation between the synthesized polymer and the monomer confirms the synthesis of the chiral polymers with specific structures.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 11","pages":"987-995"},"PeriodicalIF":2.3,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00944-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222764","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An ionic electroactive polymer actuator (IEPA) was fabricated in this study using a blend of regioregular-poly(3-hexylthiophene) (RR-P3HT) nanofibers, regiorandom-P3HT (RRa-P3HT), and polybutadiene rubber (PBR). The RR-P3HT nanofiber mat, which was reinforced with RRa-P3HT as tie chains and PBR as a flexible matrix, exhibited a large surface area where the nanofibers contacted the electrolyte. Therefore, efficient actuation is expected to synergize with the superior carrier mobility inherent in the nanofibrous architecture. The blended actuator, which preserved the RR-P3HT nanofiber structure, exhibited a substantial bending angle exceeding 80° following the redox reaction while sustaining reversible actuation for more than 30 cycles. An optimal scan rate below 100 mV s−1 was required to obtain substantial actuation. Therefore, the RR-P3HT nanofibers blended with RRa-P3HT and PBR demonstrated remarkable functionality as an IEPA, which was characterized by a significant bending angle and enduring cyclic actuation capabilities. An ionic electroactive polymer actuator (IEPA) was fabricated using regioregular-poly(3-hexylthiophene) (RR-P3HT) nanofibers. The RR-P3HT nanofiber mat was reinforced with regiorandom-P3HT (RRa-P3HT) as the tie chains and polybutadiene rubber (PBR) as a flexible matrix. The blended actuator, which preserved the RR-P3HT nanofiber structure, exhibited a substantial bending angle exceeding 80° after the redox reaction while sustaining reversible actuation for more than 30 cycles. The RR-P3HT nanofibers that were blended with RRa-P3HT and PBR demonstrated remarkable functionality as an IEPA, characterized by a significant bending angle and enduring cyclic actuation capabilities.
{"title":"Soft electroactive polymer actuators based on regioregular/regiorandom-poly(3-hexylthiophene) blends with a nanofiber structure","authors":"Yoshihiro Murasawa, Tomoya Yoshii, Takumi Suzuki, Takeshi Shimomura","doi":"10.1038/s41428-024-00949-y","DOIUrl":"10.1038/s41428-024-00949-y","url":null,"abstract":"An ionic electroactive polymer actuator (IEPA) was fabricated in this study using a blend of regioregular-poly(3-hexylthiophene) (RR-P3HT) nanofibers, regiorandom-P3HT (RRa-P3HT), and polybutadiene rubber (PBR). The RR-P3HT nanofiber mat, which was reinforced with RRa-P3HT as tie chains and PBR as a flexible matrix, exhibited a large surface area where the nanofibers contacted the electrolyte. Therefore, efficient actuation is expected to synergize with the superior carrier mobility inherent in the nanofibrous architecture. The blended actuator, which preserved the RR-P3HT nanofiber structure, exhibited a substantial bending angle exceeding 80° following the redox reaction while sustaining reversible actuation for more than 30 cycles. An optimal scan rate below 100 mV s−1 was required to obtain substantial actuation. Therefore, the RR-P3HT nanofibers blended with RRa-P3HT and PBR demonstrated remarkable functionality as an IEPA, which was characterized by a significant bending angle and enduring cyclic actuation capabilities. An ionic electroactive polymer actuator (IEPA) was fabricated using regioregular-poly(3-hexylthiophene) (RR-P3HT) nanofibers. The RR-P3HT nanofiber mat was reinforced with regiorandom-P3HT (RRa-P3HT) as the tie chains and polybutadiene rubber (PBR) as a flexible matrix. The blended actuator, which preserved the RR-P3HT nanofiber structure, exhibited a substantial bending angle exceeding 80° after the redox reaction while sustaining reversible actuation for more than 30 cycles. The RR-P3HT nanofibers that were blended with RRa-P3HT and PBR demonstrated remarkable functionality as an IEPA, characterized by a significant bending angle and enduring cyclic actuation capabilities.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 12","pages":"1187-1195"},"PeriodicalIF":2.3,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142222765","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Although vinyl ketones (VKs) exhibit excellent reactivity toward radicals and nucleophiles, their application in polymer chemistry has been limited compared with that of acrylates. One of the reasons is the difficulty of the synthesis, particularly that of multivalent VKs. Herein, we report the facile synthesis of divalent VKs via Friedel‒Crafts acylation of fluorene and subsequent elimination reactions. For example, via this approach, 2,7-diacryloyl-9,9-dimethylfluorene was obtained at high yields (78%). Because the monomer was obtained at high purity through recrystallization and washing, the procedure is suitable for industrial applications. The addition of dithiols and diamines via thia- and aza-Michael addition afforded the corresponding polythioesters and polyamines, respectively. In addition, the divalent VKs exhibited high reactivity in the Morita‒Baylis‒Hillman reaction with formaldehyde, affording a diol monomer. The polycondensation of the diol monomer and isophthaloyl dichloride yielded a poly(conjugated-ketone ester). Consequently, the divalent VKs described herein are attractive monomers and monomer precursors with ready accessibility and sufficient electrophilicity. A series of divalent vinyl ketones containing fluorene backbone were synthesized via Friedel-Crafts acylation and subsequent elimination reactions. The divalent vinyl ketones underwent polyaddition with dithiols to yield the corresponding polysulfide via thiol–ene click chemistry. They also exhibited high reactivity in the Baylis-Hillman reaction with formaldehyde to afford a diol monomer, and the polycondensation with isophthaloyl dichloride yielded a poly(conjugated-ketone ester).
{"title":"Divalent vinyl ketones derived from fluorene: a facile synthesis of bifunctional acrylic monomers with high reactivity in thia-/aza-Michael addition and Morita-Baylis-Hillman reactions","authors":"Masatoshi Ohyama, Rie Yasuda, Shinsuke Miyauchi, Yasuhiro Kohsaka","doi":"10.1038/s41428-024-00939-0","DOIUrl":"10.1038/s41428-024-00939-0","url":null,"abstract":"Although vinyl ketones (VKs) exhibit excellent reactivity toward radicals and nucleophiles, their application in polymer chemistry has been limited compared with that of acrylates. One of the reasons is the difficulty of the synthesis, particularly that of multivalent VKs. Herein, we report the facile synthesis of divalent VKs via Friedel‒Crafts acylation of fluorene and subsequent elimination reactions. For example, via this approach, 2,7-diacryloyl-9,9-dimethylfluorene was obtained at high yields (78%). Because the monomer was obtained at high purity through recrystallization and washing, the procedure is suitable for industrial applications. The addition of dithiols and diamines via thia- and aza-Michael addition afforded the corresponding polythioesters and polyamines, respectively. In addition, the divalent VKs exhibited high reactivity in the Morita‒Baylis‒Hillman reaction with formaldehyde, affording a diol monomer. The polycondensation of the diol monomer and isophthaloyl dichloride yielded a poly(conjugated-ketone ester). Consequently, the divalent VKs described herein are attractive monomers and monomer precursors with ready accessibility and sufficient electrophilicity. A series of divalent vinyl ketones containing fluorene backbone were synthesized via Friedel-Crafts acylation and subsequent elimination reactions. The divalent vinyl ketones underwent polyaddition with dithiols to yield the corresponding polysulfide via thiol–ene click chemistry. They also exhibited high reactivity in the Baylis-Hillman reaction with formaldehyde to afford a diol monomer, and the polycondensation with isophthaloyl dichloride yielded a poly(conjugated-ketone ester).","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 12","pages":"1111-1116"},"PeriodicalIF":2.3,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00939-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141926087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-08DOI: 10.1038/s41428-024-00945-2
Islam M. A. Mekhemer, Yi-Chieh Chiu, Mohamed M. Elsenety, Ahmed M. Elewa, Dalia M. Dorrah, Khanh Do Gia Huynh, Dung Chau Kim Hoang, Chia-Chih Chang, Ho-Hsiu Chou
Organic conjugated polymer dots (Pdots) are considered promising photocatalysts for solar-driven hydrogen production. However, the impact of molecular weight on their photocatalytic activity remains unexplored. In this study, four thiophene-quinoxaline (PTQ)-based Pdots (D-A system) with tunable molecular weights were fabricated to elucidate the effects of molecular weight on Pdot photocatalytic activity. These Pdots serve as highly efficient and stable photocatalysts for visible-light-driven hydrogen generation in a solvent-free organic system, which was achieved for the first time. Low-molecular-weight Pdots exhibited minimal aggregation, small particle sizes, uniform morphology, enhanced charge transfer capability, and superior photocatalytic activity with remarkable photostability. Notably, L-PTQ10 and L-PTQ11 demonstrated exceptional hydrogen evolution rates of 15,807 and 10,411 μmol g−¹ h−¹, respectively, when coupled with a Pt cocatalyst. The findings from our DFT and molecular dynamics (MD) calculations strongly support our hypothesis, highlighting the use of low-molecular-weight PTQ-based Pdots as a promising strategy to develop efficient and stable photocatalysts for solar-driven hydrogen production. This study presents the synthesis of thiophene-quinoxaline (PTQ)-based polymer dots (Pdots) with tunable molecular weights (D-A system) for the first time. Remarkably, Low-molecular weight Pdots exhibit minimal aggregation, small size, and enhanced charge transfer, leading to superior photocatalytic activity and remarkable photostability.
{"title":"Solar-driven photocatalytic hydrogen production thiophene-quinoxaline-based polymer dots with tunable molecular weight","authors":"Islam M. A. Mekhemer, Yi-Chieh Chiu, Mohamed M. Elsenety, Ahmed M. Elewa, Dalia M. Dorrah, Khanh Do Gia Huynh, Dung Chau Kim Hoang, Chia-Chih Chang, Ho-Hsiu Chou","doi":"10.1038/s41428-024-00945-2","DOIUrl":"10.1038/s41428-024-00945-2","url":null,"abstract":"Organic conjugated polymer dots (Pdots) are considered promising photocatalysts for solar-driven hydrogen production. However, the impact of molecular weight on their photocatalytic activity remains unexplored. In this study, four thiophene-quinoxaline (PTQ)-based Pdots (D-A system) with tunable molecular weights were fabricated to elucidate the effects of molecular weight on Pdot photocatalytic activity. These Pdots serve as highly efficient and stable photocatalysts for visible-light-driven hydrogen generation in a solvent-free organic system, which was achieved for the first time. Low-molecular-weight Pdots exhibited minimal aggregation, small particle sizes, uniform morphology, enhanced charge transfer capability, and superior photocatalytic activity with remarkable photostability. Notably, L-PTQ10 and L-PTQ11 demonstrated exceptional hydrogen evolution rates of 15,807 and 10,411 μmol g−¹ h−¹, respectively, when coupled with a Pt cocatalyst. The findings from our DFT and molecular dynamics (MD) calculations strongly support our hypothesis, highlighting the use of low-molecular-weight PTQ-based Pdots as a promising strategy to develop efficient and stable photocatalysts for solar-driven hydrogen production. This study presents the synthesis of thiophene-quinoxaline (PTQ)-based polymer dots (Pdots) with tunable molecular weights (D-A system) for the first time. Remarkably, Low-molecular weight Pdots exhibit minimal aggregation, small size, and enhanced charge transfer, leading to superior photocatalytic activity and remarkable photostability.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"56 11","pages":"1079-1088"},"PeriodicalIF":2.3,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00945-2.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141929047","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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