Pub Date : 2024-10-10DOI: 10.1038/s41428-024-00977-8
Takayuki Hirai
Composite materials are widely used in many industrial products because they combine the properties of organic and inorganic materials. This review focuses on the property modification of composite materials where polymer blends are used as matrices to obtain functional composites. Polymer blends can be fabricated via the physical process of melt mixing; thus, they have good scalability. However, poor material design criteria compared with those of polymer synthesis are critical defects in polymer blending. To address this problem, we focused on the multiscale phase separation in polymer blends. Polymer blends can be divided into three categories according to their phase morphology: immiscible, miscible, and reactive. They exhibit characteristic behaviors that depend on their morphology. We propose a novel material design concept to combine polymers with different phase morphologies to obtain a combination of modification mechanisms. To provide specific examples, two previous studies on the modification of carbon- and glass-fiber-reinforced plastics were summarized. One study involves improving the hygrothermal resistance of carbon-fiber-reinforced polyamide by incorporating both miscible and immiscible components into the polyamide. The other study involves fabricating transparent glass-fiber-reinforced polyamides by investigating miscible and reactive blends. Our recent study on the property modification of composite materials where polymer blends are used as matrices were summarized. Polymer blends have good scalability; however, poor material design criteria is a critical defect in polymer blending. To address this problem, we focused on the multiscale phase separation in polymer blends. We propose a novel material design concept to combine polymers with different phase morphologies to obtain a combination of modification mechanisms, and hygrothermal resistant CFRP and transparent GFRP using polymer blends as matrix were obtained.
{"title":"Modification of fiber-reinforced composites using polymer blends as matrices","authors":"Takayuki Hirai","doi":"10.1038/s41428-024-00977-8","DOIUrl":"10.1038/s41428-024-00977-8","url":null,"abstract":"Composite materials are widely used in many industrial products because they combine the properties of organic and inorganic materials. This review focuses on the property modification of composite materials where polymer blends are used as matrices to obtain functional composites. Polymer blends can be fabricated via the physical process of melt mixing; thus, they have good scalability. However, poor material design criteria compared with those of polymer synthesis are critical defects in polymer blending. To address this problem, we focused on the multiscale phase separation in polymer blends. Polymer blends can be divided into three categories according to their phase morphology: immiscible, miscible, and reactive. They exhibit characteristic behaviors that depend on their morphology. We propose a novel material design concept to combine polymers with different phase morphologies to obtain a combination of modification mechanisms. To provide specific examples, two previous studies on the modification of carbon- and glass-fiber-reinforced plastics were summarized. One study involves improving the hygrothermal resistance of carbon-fiber-reinforced polyamide by incorporating both miscible and immiscible components into the polyamide. The other study involves fabricating transparent glass-fiber-reinforced polyamides by investigating miscible and reactive blends. Our recent study on the property modification of composite materials where polymer blends are used as matrices were summarized. Polymer blends have good scalability; however, poor material design criteria is a critical defect in polymer blending. To address this problem, we focused on the multiscale phase separation in polymer blends. We propose a novel material design concept to combine polymers with different phase morphologies to obtain a combination of modification mechanisms, and hygrothermal resistant CFRP and transparent GFRP using polymer blends as matrix were obtained.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 1","pages":"79-86"},"PeriodicalIF":2.3,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925796","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 : 2024-10-10DOI: 10.1038/s41428-024-00973-y
Naoya Abe, Keiji Numata
Plant mitochondria are essential for energy production and male sterility. The genetic transformation of plant mitochondria has attracted attention due to its potential to improve the mitochondrial function and agricultural productivity of energy crops. However, mitochondrial genome editing has been challenging because the delivery of the macromolecules needed for genome engineering to mitochondria has not been established until now. In addition, the genome editing efficiency in mitochondria needs to be improved as much as possible due to the lack of a selection marker for mitochondria. To achieve mitochondrial modification, the proteins and/or DNA/RNA needed for genome editing should be delivered to mitochondria precisely and efficiently. Peptides have been utilized to improve delivery efficiency to plant mitochondria. Thus, we herein review advances in delivery technologies related to plant mitochondrial genome engineering using various functional peptides. There are many barriers to gene and protein delivery to plant mitochondria, such as cell walls, cell membranes, and cytosolic localization. Functional peptides have been used to overcome these barriers. Peptides have a characteristic function depending on their sequence and high-order structure. The cytotoxicity of these peptides is also low. Therefore, functional peptides have attracted attention for their ability to improve gene and protein delivery efficiency to plant mitochondria.
{"title":"Peptide-mediated gene and protein delivery systems to plant mitochondria for modifying mitochondrial functions","authors":"Naoya Abe, Keiji Numata","doi":"10.1038/s41428-024-00973-y","DOIUrl":"10.1038/s41428-024-00973-y","url":null,"abstract":"Plant mitochondria are essential for energy production and male sterility. The genetic transformation of plant mitochondria has attracted attention due to its potential to improve the mitochondrial function and agricultural productivity of energy crops. However, mitochondrial genome editing has been challenging because the delivery of the macromolecules needed for genome engineering to mitochondria has not been established until now. In addition, the genome editing efficiency in mitochondria needs to be improved as much as possible due to the lack of a selection marker for mitochondria. To achieve mitochondrial modification, the proteins and/or DNA/RNA needed for genome editing should be delivered to mitochondria precisely and efficiently. Peptides have been utilized to improve delivery efficiency to plant mitochondria. Thus, we herein review advances in delivery technologies related to plant mitochondrial genome engineering using various functional peptides. There are many barriers to gene and protein delivery to plant mitochondria, such as cell walls, cell membranes, and cytosolic localization. Functional peptides have been used to overcome these barriers. Peptides have a characteristic function depending on their sequence and high-order structure. The cytotoxicity of these peptides is also low. Therefore, functional peptides have attracted attention for their ability to improve gene and protein delivery efficiency to plant mitochondria.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 1","pages":"57-68"},"PeriodicalIF":2.3,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00973-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925794","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 : 2024-10-10DOI: 10.1038/s41428-024-00954-1
Eiji Ihara
Recent results from the author’s research group on the development of polymer syntheses using diazocarbonyl compounds as monomers are described. A series of new Pd-based initiating systems for C1 polymerization of diazoacetate have been developed, each of which possesses characteristic initiating ability with respect to high-molecular-weight polymer synthesis, tacticity control, and chain end functionalization. The use of functional ester substituents has led to polymers with unique properties and functionalities in comparison to their vinyl polymer counterparts [poly(alkyl acrylate)] with the same ester substituent. Polycondensations using bis(diazocarbonyl) compounds as monomers are also described. By utilizing a variety of reactivities of a diazocarbonyl group, a series of three-, two-, and single-component polycondensations have been realized, affording new polymers whose chemical structures cannot be attained by any existing method for polymer syntheses. Polymer syntheses utilizing diazocarbonyl compounds as monomers are described. Pd-based initiators active for the C1 polymerization of diazoacetates have been developed; the presence of η3-type anionic ligand on the Pd center has been proved to be essential for the initiator to be highly active for the polymerization. Pd complexes bearing naphthoquinone or its derivatives as a ligand were effective for the initiator generation in conjunction with NaBPh4. By using a series of bis(diazocarbonyl) compounds as monomers, three-, two-, and single-component polycondensations have been newly developed, affording unprecedented polymer structures.
{"title":"Development of polymer syntheses using diazocarbonyl compounds as monomers","authors":"Eiji Ihara","doi":"10.1038/s41428-024-00954-1","DOIUrl":"10.1038/s41428-024-00954-1","url":null,"abstract":"Recent results from the author’s research group on the development of polymer syntheses using diazocarbonyl compounds as monomers are described. A series of new Pd-based initiating systems for C1 polymerization of diazoacetate have been developed, each of which possesses characteristic initiating ability with respect to high-molecular-weight polymer synthesis, tacticity control, and chain end functionalization. The use of functional ester substituents has led to polymers with unique properties and functionalities in comparison to their vinyl polymer counterparts [poly(alkyl acrylate)] with the same ester substituent. Polycondensations using bis(diazocarbonyl) compounds as monomers are also described. By utilizing a variety of reactivities of a diazocarbonyl group, a series of three-, two-, and single-component polycondensations have been realized, affording new polymers whose chemical structures cannot be attained by any existing method for polymer syntheses. Polymer syntheses utilizing diazocarbonyl compounds as monomers are described. Pd-based initiators active for the C1 polymerization of diazoacetates have been developed; the presence of η3-type anionic ligand on the Pd center has been proved to be essential for the initiator to be highly active for the polymerization. Pd complexes bearing naphthoquinone or its derivatives as a ligand were effective for the initiator generation in conjunction with NaBPh4. By using a series of bis(diazocarbonyl) compounds as monomers, three-, two-, and single-component polycondensations have been newly developed, affording unprecedented polymer structures.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 1","pages":"1-23"},"PeriodicalIF":2.3,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925786","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 : 2024-10-03DOI: 10.1038/s41428-024-00969-8
Ryota Tamate
Owing to the digital revolution and growing emphasis on sustainability, the demand for innovative electrochemical devices, such as flexible and wearable sensors, energy-harvesting devices, and high-capacity secondary batteries, has been increasing. Alongside this, various high-performance gel electrolytes with excellent mechanical and electrochemical properties have been developed. This focus review presents our recent research on enhancing the mechanical properties of gel electrolytes and their application in lithium secondary batteries. It discusses the efforts made to achieve self-healing ion gels, which utilize ionic liquids as the electrolyte solutions. Additionally, the review covers the application of functional gel electrolytes in next-generation lithium secondary batteries. It focuses particularly on improving the cycling performance of lithium metal anodes, which are considered the very promising anode material. Moreover, the future prospects of functional polymer gel electrolytes have been discussed in this review. This focus review presents our recent research on enhancing the mechanical properties of gel electrolytes and their application in lithium secondary batteries. It discusses the efforts made to achieve self-healing ion gels, which utilize ionic liquids as the electrolyte solutions. Additionally, the review covers the application of functional gel electrolytes in next-generation lithium secondary batteries. It focuses particularly on improving the cycling performance of lithium metal anodes, which are considered the very promising anode material.
{"title":"Development of functional polymer gel electrolytes and their application in next-generation lithium secondary batteries","authors":"Ryota Tamate","doi":"10.1038/s41428-024-00969-8","DOIUrl":"10.1038/s41428-024-00969-8","url":null,"abstract":"Owing to the digital revolution and growing emphasis on sustainability, the demand for innovative electrochemical devices, such as flexible and wearable sensors, energy-harvesting devices, and high-capacity secondary batteries, has been increasing. Alongside this, various high-performance gel electrolytes with excellent mechanical and electrochemical properties have been developed. This focus review presents our recent research on enhancing the mechanical properties of gel electrolytes and their application in lithium secondary batteries. It discusses the efforts made to achieve self-healing ion gels, which utilize ionic liquids as the electrolyte solutions. Additionally, the review covers the application of functional gel electrolytes in next-generation lithium secondary batteries. It focuses particularly on improving the cycling performance of lithium metal anodes, which are considered the very promising anode material. Moreover, the future prospects of functional polymer gel electrolytes have been discussed in this review. This focus review presents our recent research on enhancing the mechanical properties of gel electrolytes and their application in lithium secondary batteries. It discusses the efforts made to achieve self-healing ion gels, which utilize ionic liquids as the electrolyte solutions. Additionally, the review covers the application of functional gel electrolytes in next-generation lithium secondary batteries. It focuses particularly on improving the cycling performance of lithium metal anodes, which are considered the very promising anode material.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 1","pages":"43-55"},"PeriodicalIF":2.3,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00969-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925787","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 : 2024-10-03DOI: 10.1038/s41428-024-00966-x
Takuya Uto
Crystalline polysaccharides are abundant in nature and can be transformed into highly functional materials. However, the molecular basis for the formation of higher-order structures remains unclear. Computer simulation is an advanced tool for modeling macromolecular structures, and the atomistic simulations provide valuable information on the crystalline polysaccharides. Fiber deformation, crystalline transition, and novel nanostructures of cellulose were characterized through molecular dynamics simulations and density functional theory calculations of models of molecular chain sheets extracted from the crystal structure of the cellulose polymorphs. Extended ensemble molecular dynamics simulations were applied to analyze the artificial crystal structure of non-natural amylose analog polysaccharides, revealing the hexagonal packing of double helices through the self-assembly of molecular chains dispersed in aqueous solution. Dissolution simulations of the cellulose and chitin crystalline fibers revealed that the anions of ionic liquids, with their solvation power, played a key role in the cleavage of intermolecular hydrogen bonds in the crystal structure, whereas the cations contributed to irreversible molecular chain dispersion. The good correlation between the actual solubility of polysaccharides and the predicted number of intermolecular hydrogen bonds prompted the development of a platform that combined simulations and machine learning for high-throughput screening of solvents for cellulose and chitin. Crystalline polysaccharides, which are abundant in nature, can be transformed into highly functional materials. However, the molecular basis for the formation of higher-order structures remains incompletely understood. Computer simulation is an advanced tool for modeling macromolecular structures, with atomistic simulations providing valuable information on crystalline polysaccharides. This focus review covers theoretical and computational studies, including atomistic simulations, performed by our research group on the crystallographic properties and novel nanostructures of cellulose, crystal structure of amylose analog polysaccharides, and dissolution mechanism of cellulose and chitin crystalline fibers.
{"title":"Atomistic simulations of polysaccharide materials for insights into their crystal structure, nanostructure, and dissolution mechanism","authors":"Takuya Uto","doi":"10.1038/s41428-024-00966-x","DOIUrl":"10.1038/s41428-024-00966-x","url":null,"abstract":"Crystalline polysaccharides are abundant in nature and can be transformed into highly functional materials. However, the molecular basis for the formation of higher-order structures remains unclear. Computer simulation is an advanced tool for modeling macromolecular structures, and the atomistic simulations provide valuable information on the crystalline polysaccharides. Fiber deformation, crystalline transition, and novel nanostructures of cellulose were characterized through molecular dynamics simulations and density functional theory calculations of models of molecular chain sheets extracted from the crystal structure of the cellulose polymorphs. Extended ensemble molecular dynamics simulations were applied to analyze the artificial crystal structure of non-natural amylose analog polysaccharides, revealing the hexagonal packing of double helices through the self-assembly of molecular chains dispersed in aqueous solution. Dissolution simulations of the cellulose and chitin crystalline fibers revealed that the anions of ionic liquids, with their solvation power, played a key role in the cleavage of intermolecular hydrogen bonds in the crystal structure, whereas the cations contributed to irreversible molecular chain dispersion. The good correlation between the actual solubility of polysaccharides and the predicted number of intermolecular hydrogen bonds prompted the development of a platform that combined simulations and machine learning for high-throughput screening of solvents for cellulose and chitin. Crystalline polysaccharides, which are abundant in nature, can be transformed into highly functional materials. However, the molecular basis for the formation of higher-order structures remains incompletely understood. Computer simulation is an advanced tool for modeling macromolecular structures, with atomistic simulations providing valuable information on crystalline polysaccharides. This focus review covers theoretical and computational studies, including atomistic simulations, performed by our research group on the crystallographic properties and novel nanostructures of cellulose, crystal structure of amylose analog polysaccharides, and dissolution mechanism of cellulose and chitin crystalline fibers.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 1","pages":"33-41"},"PeriodicalIF":2.3,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00966-x.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925791","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}
Post-polymerization modification (PPM) via active ester chemistry is a valuable method for modulating side-chain structures without altering their main-chain topology. Herein, we synthesized a double-stranded vinyl polymer with an active ester by crosslinking radical polymerization within the nanochannels of a metal‒organic framework (MOF) with a pore diameter comparable to that of the duplex. The resulting double-stranded poly(1,1,1,3,3,3-hexafluoroisopropyl acrylate) (DPHFIPA) was readily converted into acrylates and acrylamides with side chains derived from the nucleophile used in the PPM. This approach offers a pathway for creating double-stranded vinyl polymers with repeating units that are otherwise difficult to synthesize, even when MOF-templated polymerization is used. Double-stranded polymers have attracted attention due to their elegant structures and potential properties arising from their topology. In this work, we performed cross-linking polymerization of an active ester acrylate monomer within the nanochannels of a metal‒organic framework (MOF). The spatial constraints in the MOF facilitated the formation of a polymer duplex. Subsequently, transformation of the side chains could be achieved without altering the double-stranded topology, providing a variety of functional vinyl polymer duplexes.
{"title":"Double-stranded vinyl polymer with transformable side chains synthesized in a metal‒organic framework","authors":"Yuki Kametani, Masahiro Abe, Tomohito Mori, Takashi Uemura","doi":"10.1038/s41428-024-00970-1","DOIUrl":"10.1038/s41428-024-00970-1","url":null,"abstract":"Post-polymerization modification (PPM) via active ester chemistry is a valuable method for modulating side-chain structures without altering their main-chain topology. Herein, we synthesized a double-stranded vinyl polymer with an active ester by crosslinking radical polymerization within the nanochannels of a metal‒organic framework (MOF) with a pore diameter comparable to that of the duplex. The resulting double-stranded poly(1,1,1,3,3,3-hexafluoroisopropyl acrylate) (DPHFIPA) was readily converted into acrylates and acrylamides with side chains derived from the nucleophile used in the PPM. This approach offers a pathway for creating double-stranded vinyl polymers with repeating units that are otherwise difficult to synthesize, even when MOF-templated polymerization is used. Double-stranded polymers have attracted attention due to their elegant structures and potential properties arising from their topology. In this work, we performed cross-linking polymerization of an active ester acrylate monomer within the nanochannels of a metal‒organic framework (MOF). The spatial constraints in the MOF facilitated the formation of a polymer duplex. Subsequently, transformation of the side chains could be achieved without altering the double-stranded topology, providing a variety of functional vinyl polymer duplexes.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 1","pages":"129-135"},"PeriodicalIF":2.3,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00970-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925795","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}
Poly(dialkyl fumarate)s (PDRFs), which are produced by the radical polymerization of dialkyl fumarates, are highly transparent amorphous polymer materials with excellent heat resistance, mechanical, and optical properties. The physical properties of PDRFs with a rigid poly(substituted methylene) structure discontinuously change at their β transition temperature (Tβ) because of restricted local molecular motion, including the rotation of substituents in the side chain. In this study, we performed a radical polymerization of symmetric and asymmetric dialkyl fumarates, including 4-tert-butylcyclohexyl esters with a fixed cycloalkyl conformation, to clarify the thermal and optical properties of the produced PDRFs. The Tβ value, refractive index, and density of the PDRFs increased with the introduction of the 4-tert-butylcyclohexyl group. Based on the wide-angle X-ray scattering (WAXS) measurement results, we analyzed the spontaneous aggregation of the PDRF chains in the solid state to discuss their density and optical properties in detail. Poly(dialkyl fumarate)s (PDRFs) with a rigid poly(substituted methylene) structure are highly transparent amorphous polymer materials with excellent heat resistance, mechanical, and optical properties. In this study, we performed a radical polymerization of symmetric and asymmetric dialkyl fumarates, including 4-tert-butylcyclohexyl esters with a fixed cycloalkyl conformation, and found that the β transition temperatures, refractive indices, and densities of the PDRFs increased with the introduction of the 4-tert-butylcyclohexyl group. The density, optical properties, and spontaneous aggregation structures of the PDRF in the solid state were discussed.
{"title":"Synthesis of polyfumarates containing a 4-tert-butylcyclohexyl group and unique solid-state properties based on the orientation of rigid poly(substituted methylene) chains","authors":"Ryotaro Ishimaru, Yasuhito Suzuki, Akikazu Matsumoto","doi":"10.1038/s41428-024-00967-w","DOIUrl":"10.1038/s41428-024-00967-w","url":null,"abstract":"Poly(dialkyl fumarate)s (PDRFs), which are produced by the radical polymerization of dialkyl fumarates, are highly transparent amorphous polymer materials with excellent heat resistance, mechanical, and optical properties. The physical properties of PDRFs with a rigid poly(substituted methylene) structure discontinuously change at their β transition temperature (Tβ) because of restricted local molecular motion, including the rotation of substituents in the side chain. In this study, we performed a radical polymerization of symmetric and asymmetric dialkyl fumarates, including 4-tert-butylcyclohexyl esters with a fixed cycloalkyl conformation, to clarify the thermal and optical properties of the produced PDRFs. The Tβ value, refractive index, and density of the PDRFs increased with the introduction of the 4-tert-butylcyclohexyl group. Based on the wide-angle X-ray scattering (WAXS) measurement results, we analyzed the spontaneous aggregation of the PDRF chains in the solid state to discuss their density and optical properties in detail. Poly(dialkyl fumarate)s (PDRFs) with a rigid poly(substituted methylene) structure are highly transparent amorphous polymer materials with excellent heat resistance, mechanical, and optical properties. In this study, we performed a radical polymerization of symmetric and asymmetric dialkyl fumarates, including 4-tert-butylcyclohexyl esters with a fixed cycloalkyl conformation, and found that the β transition temperatures, refractive indices, and densities of the PDRFs increased with the introduction of the 4-tert-butylcyclohexyl group. The density, optical properties, and spontaneous aggregation structures of the PDRF in the solid state were discussed.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 1","pages":"95-107"},"PeriodicalIF":2.3,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41428-024-00967-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925782","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 : 2024-09-25DOI: 10.1038/s41428-024-00962-1
Seigo Suzuki
Advanced communication technology using millimeter waves (mmWaves) requires new polymeric materials with low dielectric properties to minimize signal transmission losses. The dielectric polarization of polymers, including electronic, vibrational, orientational, ionic, and interfacial contributions, as well as the water molecules absorbed within them, is strongly related to their dielectric properties in the mmWave region. This has led to the emergence of liquid crystal polymers (LCPs) and fluoropolymers as candidate materials for mmWave communication. However, their poor secondary processability and adhesion to copper wiring often limit their practical application. This focus review describes two types of thermoplastic films developed via formulation design technology for mmWave communication. A crystalline polyaryletherketone-based film, compounded with a plate-like, low-polarity filler and blended with miscible noncrystalline polymers to control the crystallization behavior, exhibits a low transmission loss capability comparable to that of LCPs. Additionally, this film offers solder reflow heat resistance, a low coefficient of thermal expansion (CTE), and excellent multilayer processing capabilities at low temperatures, making it suitable for use in multilayer substrates for mmWave communication applications. A polyolefin-based film demonstrates ultralow dielectric properties comparable to those of fluoropolymers and strong adhesion to copper foil. Furthermore, this film offers customizable functionalities, including laser processability, transparency, a low CTE, and flame retardancy, enabling its application in flat, flexible cables and transparent antennas. Owing to their unique characteristics, these films are promising candidates for mmWave communication materials. This focus review describes two types of thermoplastic films developed via formulation design technology for mmWave communication. The first type is a crystalline polyaryletherketone (PAEK)-based film, which is improved with plate-like fillers and miscible noncrystalline polymers. This film exhibits low dielectric properties, heat resistance, low thermal expansion, and excellent multilayer processing capabilities. The second type is a specialized polyolefin resin-based film, which achieves ultralow dielectric properties comparable to those of PTFE and combines excellent copper adhesion with customizable functionalities such as laser processability, transparency, and flame retardancy.
{"title":"Development of thermoplastic films via formulation design technology for millimeter-wave communication applications","authors":"Seigo Suzuki","doi":"10.1038/s41428-024-00962-1","DOIUrl":"10.1038/s41428-024-00962-1","url":null,"abstract":"Advanced communication technology using millimeter waves (mmWaves) requires new polymeric materials with low dielectric properties to minimize signal transmission losses. The dielectric polarization of polymers, including electronic, vibrational, orientational, ionic, and interfacial contributions, as well as the water molecules absorbed within them, is strongly related to their dielectric properties in the mmWave region. This has led to the emergence of liquid crystal polymers (LCPs) and fluoropolymers as candidate materials for mmWave communication. However, their poor secondary processability and adhesion to copper wiring often limit their practical application. This focus review describes two types of thermoplastic films developed via formulation design technology for mmWave communication. A crystalline polyaryletherketone-based film, compounded with a plate-like, low-polarity filler and blended with miscible noncrystalline polymers to control the crystallization behavior, exhibits a low transmission loss capability comparable to that of LCPs. Additionally, this film offers solder reflow heat resistance, a low coefficient of thermal expansion (CTE), and excellent multilayer processing capabilities at low temperatures, making it suitable for use in multilayer substrates for mmWave communication applications. A polyolefin-based film demonstrates ultralow dielectric properties comparable to those of fluoropolymers and strong adhesion to copper foil. Furthermore, this film offers customizable functionalities, including laser processability, transparency, a low CTE, and flame retardancy, enabling its application in flat, flexible cables and transparent antennas. Owing to their unique characteristics, these films are promising candidates for mmWave communication materials. This focus review describes two types of thermoplastic films developed via formulation design technology for mmWave communication. The first type is a crystalline polyaryletherketone (PAEK)-based film, which is improved with plate-like fillers and miscible noncrystalline polymers. This film exhibits low dielectric properties, heat resistance, low thermal expansion, and excellent multilayer processing capabilities. The second type is a specialized polyolefin resin-based film, which achieves ultralow dielectric properties comparable to those of PTFE and combines excellent copper adhesion with customizable functionalities such as laser processability, transparency, and flame retardancy.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 1","pages":"69-77"},"PeriodicalIF":2.3,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925784","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 : 2024-09-25DOI: 10.1038/s41428-024-00963-0
Hiroya Shiba, Akikazu Matsumoto, Chie Kojima
Stimuli-sensitive polymers are useful smart materials. Dendrimers are synthetic polymers with well-defined structures, and various functional dendrimers have been produced by modifying compounds at their termini. We previously reported that polyamidoamine (PAMAM) dendrimers modified with cis-1,2-cyclohexane dicarboxylic acid (CHex) and phenylalanine (Phe), named PAMAM-CHex-Phe, exhibit upper critical solution temperature (UCST)-type thermosensitivity at acidic pH. In this study, we synthesized PAMAM dendrimers with CHex and various numbers of bound Phe residues and examined their pH and temperature sensitivities. Interestingly, PAMAM-CHex-Phe, with fewer than 32 Phe residues, showed lower critical solution temperature (LCST)-type thermosensitivity at pH 5 but not UCST-type thermosensitivity. PAMAM-CHex-Phe40 and PAMAM-CHex-Phe48 exhibited both LCST- and UCST-type thermosensitivity at pH values of 5 and 6, respectively. Fully Phe-modified PAMAM-CHex-Phe (PAMAM-CHex-Phe64) showed UCST-type but not LCST-type thermosensitivity. pH titration experiments suggested that the protonation behaviors of these dendrimers were different, likely resulting in different phase transitions. Therefore, the phase transition temperature and behavior could be regulated by varying the number of bound Phe residues in the PAMAM-CHex-Phe dendrimers and the solution pH. Polyamidoamine dendrimers modified with cis-1,2-cyclohexane dicarboxylic acid and phenylalanine, named PAMAM-CHex-Phe, with various numbers of Phe residues were synthesized as dual pH- and temperature-sensitive polymers. PAMAM-CHex-Phe, with fewer than 32 Phe residues, showed lower critical solution temperature (LCST)-type thermosensitivity at pH 5. PAMAM-CHex-Phe40 and PAMAM-CHex-Phe48 exhibited both LCST- and upper critical solution temperature (UCST)-type thermosensitivity at pH values of 5 and 6, respectively. PAMAM-CHex-Phe64 showed UCST-type thermosensitivity. Our results indicate that thermosensitivity can be regulated by changing the number of Phe residues in PAMAM-CHex-Phe and the solution pH.
{"title":"LCST/UCST-type thermosensitive properties of carboxy-terminal PAMAM dendrimers modified with different numbers of phenylalanine residues","authors":"Hiroya Shiba, Akikazu Matsumoto, Chie Kojima","doi":"10.1038/s41428-024-00963-0","DOIUrl":"10.1038/s41428-024-00963-0","url":null,"abstract":"Stimuli-sensitive polymers are useful smart materials. Dendrimers are synthetic polymers with well-defined structures, and various functional dendrimers have been produced by modifying compounds at their termini. We previously reported that polyamidoamine (PAMAM) dendrimers modified with cis-1,2-cyclohexane dicarboxylic acid (CHex) and phenylalanine (Phe), named PAMAM-CHex-Phe, exhibit upper critical solution temperature (UCST)-type thermosensitivity at acidic pH. In this study, we synthesized PAMAM dendrimers with CHex and various numbers of bound Phe residues and examined their pH and temperature sensitivities. Interestingly, PAMAM-CHex-Phe, with fewer than 32 Phe residues, showed lower critical solution temperature (LCST)-type thermosensitivity at pH 5 but not UCST-type thermosensitivity. PAMAM-CHex-Phe40 and PAMAM-CHex-Phe48 exhibited both LCST- and UCST-type thermosensitivity at pH values of 5 and 6, respectively. Fully Phe-modified PAMAM-CHex-Phe (PAMAM-CHex-Phe64) showed UCST-type but not LCST-type thermosensitivity. pH titration experiments suggested that the protonation behaviors of these dendrimers were different, likely resulting in different phase transitions. Therefore, the phase transition temperature and behavior could be regulated by varying the number of bound Phe residues in the PAMAM-CHex-Phe dendrimers and the solution pH. Polyamidoamine dendrimers modified with cis-1,2-cyclohexane dicarboxylic acid and phenylalanine, named PAMAM-CHex-Phe, with various numbers of Phe residues were synthesized as dual pH- and temperature-sensitive polymers. PAMAM-CHex-Phe, with fewer than 32 Phe residues, showed lower critical solution temperature (LCST)-type thermosensitivity at pH 5. PAMAM-CHex-Phe40 and PAMAM-CHex-Phe48 exhibited both LCST- and upper critical solution temperature (UCST)-type thermosensitivity at pH values of 5 and 6, respectively. PAMAM-CHex-Phe64 showed UCST-type thermosensitivity. Our results indicate that thermosensitivity can be regulated by changing the number of Phe residues in PAMAM-CHex-Phe and the solution pH.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 1","pages":"137-142"},"PeriodicalIF":2.3,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925792","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}
The thermal curing reactions of p-tert-butylcalix[n]arenes (Cn) (n = 4, 6, and 8) with 1,3-phenylenebis(2-oxazoline) (PBO) were performed. The obtained thermosets were characterized to determine the relationships between the ring size of the calixarenes and the properties of their network polymers. The samples were cured by heating at 160 °C and 180 °C for 1 h each and then at 200 °C, 230 °C, and 250 °C for 2 h each without a solvent and catalyst. For comparison, a corresponding linear four-nucleus novolac (L4) was cured with PBO under the same conditions. Dynamic mechanical analyses of the thermosets revealed that the glass transition temperature (Tg) increased in the following order: L4/PBO < C4/PBO < C8/PBO < C6/PBO. Model reactions with a monofunctional oxazoline compound indicated that the final crosslinking degree of the network polymers increased with increasing ring size. Conversely, the cyclic structures became increasingly rigid as the ring size decreased. Because of its moderate reactivity and rigidity, the network polymer derived from C6 exhibited the highest Tg. Thermal curing reactions of p-tert-butylcalix[n]arenes (Cn: n = 4, 6, and 8) with 1,3-phenylenebis(2-oxazoline) (PBO) were conducted, and the obtained thermosets were characterized. The dynamic mechanical analyses of the thermosets revealed that the glass transition temperature (Tg) increased in the following order: C4/PBO < C8/PBO < C6/PBO. Meanwhile, model reactions indicated that the crosslinking degree increased as the ring size of the calixarene increased. The highest Tg of the C6/PBO thermoset was due to the moderate reactivity and rigidity of the cyclic structure of C6.
{"title":"Effect of the cyclic structures of p-tert-butylcalix[n]arenes on a bisoxazoline curing system","authors":"Morio Yonekawa, Hajime Kimura, Keiko Ohtsuka, Tomohiro Shimokawaji","doi":"10.1038/s41428-024-00964-z","DOIUrl":"10.1038/s41428-024-00964-z","url":null,"abstract":"The thermal curing reactions of p-tert-butylcalix[n]arenes (Cn) (n = 4, 6, and 8) with 1,3-phenylenebis(2-oxazoline) (PBO) were performed. The obtained thermosets were characterized to determine the relationships between the ring size of the calixarenes and the properties of their network polymers. The samples were cured by heating at 160 °C and 180 °C for 1 h each and then at 200 °C, 230 °C, and 250 °C for 2 h each without a solvent and catalyst. For comparison, a corresponding linear four-nucleus novolac (L4) was cured with PBO under the same conditions. Dynamic mechanical analyses of the thermosets revealed that the glass transition temperature (Tg) increased in the following order: L4/PBO < C4/PBO < C8/PBO < C6/PBO. Model reactions with a monofunctional oxazoline compound indicated that the final crosslinking degree of the network polymers increased with increasing ring size. Conversely, the cyclic structures became increasingly rigid as the ring size decreased. Because of its moderate reactivity and rigidity, the network polymer derived from C6 exhibited the highest Tg. Thermal curing reactions of p-tert-butylcalix[n]arenes (Cn: n = 4, 6, and 8) with 1,3-phenylenebis(2-oxazoline) (PBO) were conducted, and the obtained thermosets were characterized. The dynamic mechanical analyses of the thermosets revealed that the glass transition temperature (Tg) increased in the following order: C4/PBO < C8/PBO < C6/PBO. Meanwhile, model reactions indicated that the crosslinking degree increased as the ring size of the calixarene increased. The highest Tg of the C6/PBO thermoset was due to the moderate reactivity and rigidity of the cyclic structure of C6.","PeriodicalId":20302,"journal":{"name":"Polymer Journal","volume":"57 1","pages":"87-94"},"PeriodicalIF":2.3,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925785","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}
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