Pub Date : 2025-04-01DOI: 10.1016/j.progpolymsci.2025.101955
Heng Li , Weihong Zeng , Zhizhuang Li , Junpeng Zhao , Guangzhao Zhang
Hybrid block copolymers, comprising two or more polymer segments with distinct main-chain compositions and physicochemical properties, have garnered profound interests due to their often-fortified propensities for self-assembly and microphase separation. An ideal approach for synthesizing such a block copolymer comprises spontaneously sequential or simultaneous polymerizations of mixed monomers, bearing different polymerizable groups, from one initiator. However, major challenges are frequently posed by the stringent requirements for dual catalyst-monomer suitability and/or the compatibility of two mechanistically distinct polymerizations. Fortunately, recent years have witnessed rapid progress in organo-/metal-free catalytic polymerization techniques, cultivating a diversity of effective strategies for achieving sequence-selective copolymerization of mixed monomers and one-step controlled synthesis of hybrid block copolymers. We aim to summarize here the recent advances in one-step block copolymerization of heterocycles by organocatalysis, with also vinyl monomers involved in plenty of cases. We also provide a brief overview of the critical reaction mechanisms, address current limitations, and suggest future directions for one-step block copolymer synthesis.
{"title":"One-step hybrid block copolymerization by organocatalysis","authors":"Heng Li , Weihong Zeng , Zhizhuang Li , Junpeng Zhao , Guangzhao Zhang","doi":"10.1016/j.progpolymsci.2025.101955","DOIUrl":"10.1016/j.progpolymsci.2025.101955","url":null,"abstract":"<div><div>Hybrid block copolymers, comprising two or more polymer segments with distinct main-chain compositions and physicochemical properties, have garnered profound interests due to their often-fortified propensities for self-assembly and microphase separation. An ideal approach for synthesizing such a block copolymer comprises spontaneously sequential or simultaneous polymerizations of mixed monomers, bearing different polymerizable groups, from one initiator. However, major challenges are frequently posed by the stringent requirements for dual catalyst-monomer suitability and/or the compatibility of two mechanistically distinct polymerizations. Fortunately, recent years have witnessed rapid progress in organo-/metal-free catalytic polymerization techniques, cultivating a diversity of effective strategies for achieving sequence-selective copolymerization of mixed monomers and one-step controlled synthesis of hybrid block copolymers. We aim to summarize here the recent advances in one-step block copolymerization of heterocycles by organocatalysis, with also vinyl monomers involved in plenty of cases. We also provide a brief overview of the critical reaction mechanisms, address current limitations, and suggest future directions for one-step block copolymer synthesis.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"163 ","pages":"Article 101955"},"PeriodicalIF":26.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723497","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-01DOI: 10.1016/j.progpolymsci.2025.101944
Jinseok Park , Heewoon Shin , Wonho Lee , Sheng Li , Hyeong Jun Kim , Bumjoon J. Kim
Elastomeric polymer network electrolytes (EPNEs) are an emerging class of materials that combine the mechanical flexibility of elastomers with the ionic conductivity of electrolytes. Conventional liquid or gel-based polymer electrolytes suffer from solvent molecule-related leakage, evaporation, and flammability issues. Solid-state polymer electrolytes offer enhanced safety but tend to be rigid, brittle, and show poor adhesion with limited ionic conductivity. EPNEs offer solvent-free solid-state ionic conduction, enabled by the segmental motion of the flexible polymer chains. Their network structures also offer superior mechanical resilience and elasticity, making them highly promising for advanced electrochemical applications. In this review, we provide a comprehensive overview of EPNEs, comparing their characteristics to other electrolytes, and highlighting the various synthetic methods and design principles employed. Key performance metrics, including ionic conductivity, mechanical strength, and operational stabilities, are discussed in the context of their applications in energy applications, wearable electronics, and soft ionotronics. By addressing the potential of EPNEs and their development directions, this review highlights their critical role in advancing next-generation electrolytes, opening new opportunities for various fields of electrochemical devices.
{"title":"Elastomeric polymer network electrolyte: Synthesis, properties, and applications","authors":"Jinseok Park , Heewoon Shin , Wonho Lee , Sheng Li , Hyeong Jun Kim , Bumjoon J. Kim","doi":"10.1016/j.progpolymsci.2025.101944","DOIUrl":"10.1016/j.progpolymsci.2025.101944","url":null,"abstract":"<div><div>Elastomeric polymer network electrolytes (EPNEs) are an emerging class of materials that combine the mechanical flexibility of elastomers with the ionic conductivity of electrolytes. Conventional liquid or gel-based polymer electrolytes suffer from solvent molecule-related leakage, evaporation, and flammability issues. Solid-state polymer electrolytes offer enhanced safety but tend to be rigid, brittle, and show poor adhesion with limited ionic conductivity. EPNEs offer solvent-free solid-state ionic conduction, enabled by the segmental motion of the flexible polymer chains. Their network structures also offer superior mechanical resilience and elasticity, making them highly promising for advanced electrochemical applications. In this review, we provide a comprehensive overview of EPNEs, comparing their characteristics to other electrolytes, and highlighting the various synthetic methods and design principles employed. Key performance metrics, including ionic conductivity, mechanical strength, and operational stabilities, are discussed in the context of their applications in energy applications, wearable electronics, and soft ionotronics. By addressing the potential of EPNEs and their development directions, this review highlights their critical role in advancing next-generation electrolytes, opening new opportunities for various fields of electrochemical devices.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"163 ","pages":"Article 101944"},"PeriodicalIF":26.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143631438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-01DOI: 10.1016/j.progpolymsci.2025.101956
Iván Zapata-González , Enrique Saldívar-Guerra , Robin A. Hutchinson
Microstructure and copolymer composition are characteristics important for both commodity and tailor-made materials synthesized by Free Radical Copolymerization (FRCoP) and other polymerization chemistries. The Mayo-Lewis equation (MLE), published in 1944, revolutionized copolymerization practice and theory by providing a straightforward relationship between comonomer and copolymer composition in terms of two parameters, the reactivity ratios (RR). Since that time, various forms of this non-linear equation, all based upon the terminal model (TM) of copolymerization, have been developed to facilitate estimation of RR values through fitting of experimentally measured copolymer compositions as a function of comonomer composition and/or monomer conversion. Early transformations introduced to allow linear regression methodologies have been replaced by powerful nonlinear numerical methods that provide statistically valid estimations of the reactivity ratios. In this review, the fundamentals of the linear and nonlinear numerical methodologies are described, with an emphasis on the recommended non-linear strategies for the determination of the RR using copolymer/monomer composition data at both low and moderate/high conversions. The shape and calculation of the Joint Confidence Regions (JCRs) associated with the RR values is also reviewed, and the optimal design of experiments for the determination of RR values is described.
While remarkably robust, the MLE does not provide an adequate description of copolymer composition for some systems. An examination of the assumptions associated with the derivation provides context for these exceptions. Systematic extensions of the MLE to capture the influence of penultimate unit effects, depropagation, and system (e.g., solvent, concentration, pH) dependencies are outlined. Additionally, discrepancies reported in the copolymer composition between the free-radical copolymerization and reversible deactivation radical copolymerization are analyzed in terms of kinetic fundamentals. While deviations from classic behavior are the exception rather than the rule, they demonstrate the need to carefully investigate any new system to validate the applicability of the MLE.
{"title":"80 years of the Mayo Lewis equation. A comprehensive review on the numerical estimation techniques for the reactivity ratios in typical and emerging copolymerizations","authors":"Iván Zapata-González , Enrique Saldívar-Guerra , Robin A. Hutchinson","doi":"10.1016/j.progpolymsci.2025.101956","DOIUrl":"10.1016/j.progpolymsci.2025.101956","url":null,"abstract":"<div><div>Microstructure and copolymer composition are characteristics important for both commodity and tailor-made materials synthesized by Free Radical Copolymerization (FRCoP) and other polymerization chemistries. The Mayo-Lewis equation (MLE), published in 1944, revolutionized copolymerization practice and theory by providing a straightforward relationship between comonomer and copolymer composition in terms of two parameters, the reactivity ratios (RR). Since that time, various forms of this non-linear equation, all based upon the terminal model (TM) of copolymerization, have been developed to facilitate estimation of RR values through fitting of experimentally measured copolymer compositions as a function of comonomer composition and/or monomer conversion. Early transformations introduced to allow linear regression methodologies have been replaced by powerful nonlinear numerical methods that provide statistically valid estimations of the reactivity ratios. In this review, the fundamentals of the linear and nonlinear numerical methodologies are described, with an emphasis on the recommended non-linear strategies for the determination of the RR using copolymer/monomer composition data at both low and moderate/high conversions. The shape and calculation of the Joint Confidence Regions (JCRs) associated with the RR values is also reviewed, and the optimal design of experiments for the determination of RR values is described.</div><div>While remarkably robust, the MLE does not provide an adequate description of copolymer composition for some systems. An examination of the assumptions associated with the derivation provides context for these exceptions. Systematic extensions of the MLE to capture the influence of penultimate unit effects, depropagation, and system (e.g., solvent, concentration, pH) dependencies are outlined. Additionally, discrepancies reported in the copolymer composition between the free-radical copolymerization and reversible deactivation radical copolymerization are analyzed in terms of kinetic fundamentals. While deviations from classic behavior are the exception rather than the rule, they demonstrate the need to carefully investigate any new system to validate the applicability of the MLE.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"163 ","pages":"Article 101956"},"PeriodicalIF":26.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798225","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-15DOI: 10.1016/j.progpolymsci.2025.101945
Jing Lyu , Lishan Li , Xuetong Zhang
Aramid, a prominent member within the polymer family, is a quintessential high-performance material. It presents extensive application in numerous crucial fields ranging from aerospace and armament to individual protection, vehicle industries, and leisure sports. Nanoporous aramid aerogels, a remarkable derivative of aramid polymers, not only inherit aramid's numerous excellent properties but also boast extensive porosity and a large specific surface area, opening up a wide spectrum of emerging applications. However, there are lamentably few reviews that comprehensively encapsulate the most recent progress of aramid aerogels, even though they stand at the vanguard of scientific research. Herein, the aramid colloidal aerogels fabricated via the “colloidal approach” from aramid nanofibers (ANFs) are defined in terms of processing. The ANF colloidal dispersion is thoroughly overviewed with respect to preparation methods, rheological behaviors and the corresponding regulating factors. The sol-gel transition of ANF colloidal dispersion triggered by the destabilizing strategy is unveiled from thermodynamics and kinetics perspectives. Next, the fabrication strategies for aramid colloidal aerogels in various configurations and their confining functionalization are systematically summarized and analyzed. Furthermore, a wide array of captivating properties of aramid colloidal aerogels, including thermal, mechanical, permselective, sorptive, and electrochemical properties are introduced. With these fascinating properties, a multitude of emerging applications such as thermal management, shielding, purification, hemostasis, sensing, energy storage and conversion, are touched upon, inspiring more cutting-edge researches in materials science, environmental engineering, bioengineering, and multidisciplinary fields. Finally, the possible challenges and opportunities in the development of nanoporous aramid colloidal aerogels are identified, and a perspective on the future directions is proposed.
{"title":"Nanoporous aramid colloidal aerogels: Design, fabrication, and performance","authors":"Jing Lyu , Lishan Li , Xuetong Zhang","doi":"10.1016/j.progpolymsci.2025.101945","DOIUrl":"10.1016/j.progpolymsci.2025.101945","url":null,"abstract":"<div><div>Aramid, a prominent member within the polymer family, is a quintessential high-performance material. It presents extensive application in numerous crucial fields ranging from aerospace and armament to individual protection, vehicle industries, and leisure sports. Nanoporous aramid aerogels, a remarkable derivative of aramid polymers, not only inherit aramid's numerous excellent properties but also boast extensive porosity and a large specific surface area, opening up a wide spectrum of emerging applications. However, there are lamentably few reviews that comprehensively encapsulate the most recent progress of aramid aerogels, even though they stand at the vanguard of scientific research. Herein, the aramid colloidal aerogels fabricated via the “colloidal approach” from aramid nanofibers (ANFs) are defined in terms of processing. The ANF colloidal dispersion is thoroughly overviewed with respect to preparation methods, rheological behaviors and the corresponding regulating factors. The sol-gel transition of ANF colloidal dispersion triggered by the destabilizing strategy is unveiled from thermodynamics and kinetics perspectives. Next, the fabrication strategies for aramid colloidal aerogels in various configurations and their confining functionalization are systematically summarized and analyzed. Furthermore, a wide array of captivating properties of aramid colloidal aerogels, including thermal, mechanical, permselective, sorptive, and electrochemical properties are introduced. With these fascinating properties, a multitude of emerging applications such as thermal management, shielding, purification, hemostasis, sensing, energy storage and conversion, are touched upon, inspiring more cutting-edge researches in materials science, environmental engineering, bioengineering, and multidisciplinary fields. Finally, the possible challenges and opportunities in the development of nanoporous aramid colloidal aerogels are identified, and a perspective on the future directions is proposed.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"163 ","pages":"Article 101945"},"PeriodicalIF":26.0,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143631435","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-01DOI: 10.1016/j.progpolymsci.2025.101934
R. Gonçalves , J. Serra , A. Reizabal , D.M. Correia , L.C. Fernandes , R. Brito-Pereira , E. Lizundia , C.M. Costa , S. Lanceros-Méndez
Rapid technological developments in biomedicine, sensors, actuators and energy areas are taken place in the context of the global digital transformation, supported by the “Industry 4.0″ and “Internet of Things” (IoT) concepts. Those developments must include circular economy considerations in the scope of the 2030 sustainable developments goals to ensure easy access to affordable, sustainable, reliable, and modern services for all. To fulfil these advances, materials with high-performance based on biopolymers with tailored dielectric, magnetic and conducting properties are needed for improving devices performance while reducing environmental impact. Within this scope, bio-based resources are considered as next-generation materials for a broader range of applications. In this context, we present on the molecular structure, organization, main physical-chemical and functional properties of the most promising biopolymers. Further, the various possible modifications and processing methods are discussed to reach specific morphological, structural and/or functional characteristics. Finally, bio polymers-based blends and composites are discussed, alongside with their main application areas, opportunities, and challenges.
{"title":"Biobased polymers for advanced applications: Towards a sustainable future","authors":"R. Gonçalves , J. Serra , A. Reizabal , D.M. Correia , L.C. Fernandes , R. Brito-Pereira , E. Lizundia , C.M. Costa , S. Lanceros-Méndez","doi":"10.1016/j.progpolymsci.2025.101934","DOIUrl":"10.1016/j.progpolymsci.2025.101934","url":null,"abstract":"<div><div>Rapid technological developments in biomedicine, sensors, actuators and energy areas are taken place in the context of the global digital transformation, supported by the “Industry 4.0″ and “Internet of Things” (IoT) concepts. Those developments must include circular economy considerations in the scope of the 2030 sustainable developments goals to ensure easy access to affordable, sustainable, reliable, and modern services for all. To fulfil these advances, materials with high-performance based on biopolymers with tailored dielectric, magnetic and conducting properties are needed for improving devices performance while reducing environmental impact. Within this scope, bio-based resources are considered as next-generation materials for a broader range of applications. In this context, we present on the molecular structure, organization, main physical-chemical and functional properties of the most promising biopolymers. Further, the various possible modifications and processing methods are discussed to reach specific morphological, structural and/or functional characteristics. Finally, bio polymers-based blends and composites are discussed, alongside with their main application areas, opportunities, and challenges.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"162 ","pages":"Article 101934"},"PeriodicalIF":26.0,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462444","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-01DOI: 10.1016/j.progpolymsci.2025.101932
F. Baffie, L. Sinniger, M. Lansalot, V. Monteil, F. D'Agosto
The present paper reviews advancements in reversible-deactivation radical polymerization (RDRP) of ethylene. Polyethylene, one of the most produced polymers, is traditionally made using high-pressure radical polymerization (RP) or catalytic coordination-insertion methods. However, the harsh conditions required for RP and ethylene low reactivity have limited laboratory-scale innovations. Efforts to develop milder polymerization conditions (< 100 °C, < 500 bar) have facilitated the exploration of RDRP techniques applied to ethylene. RDRP based on reversible termination or degenerative transfer have been investigated. Among them, those based on degenerative transfer such as reversible addition-fragmentation chain transfer (RAFT), organotellurium mediated radical polymerization (TeRP) or iodine transfer polymerization (ITP) proved more successful, enabling not only controlled homopolymerization of ethylene but also the synthesis of well-defined (block) copolymers based on ethylene.
{"title":"From radical to reversible-deactivation radical polymerization of ethylene","authors":"F. Baffie, L. Sinniger, M. Lansalot, V. Monteil, F. D'Agosto","doi":"10.1016/j.progpolymsci.2025.101932","DOIUrl":"10.1016/j.progpolymsci.2025.101932","url":null,"abstract":"<div><div>The present paper reviews advancements in reversible-deactivation radical polymerization (RDRP) of ethylene. Polyethylene, one of the most produced polymers, is traditionally made using high-pressure radical polymerization (RP) or catalytic coordination-insertion methods. However, the harsh conditions required for RP and ethylene low reactivity have limited laboratory-scale innovations. Efforts to develop milder polymerization conditions (< 100 °C, < 500 bar) have facilitated the exploration of RDRP techniques applied to ethylene. RDRP based on reversible termination or degenerative transfer have been investigated. Among them, those based on degenerative transfer such as reversible addition-fragmentation chain transfer (RAFT), organotellurium mediated radical polymerization (TeRP) or iodine transfer polymerization (ITP) proved more successful, enabling not only controlled homopolymerization of ethylene but also the synthesis of well-defined (block) copolymers based on ethylene.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"162 ","pages":"Article 101932"},"PeriodicalIF":26.0,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418044","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-01DOI: 10.1016/j.progpolymsci.2025.101935
Yong Guo , Qingshan Yang , Siqi Huo , Juan Li , Pooya Jafari , Zhengping Fang , Pingan Song , Hao Wang
Thermosets play a critical role in aerospace, automotive, electronics, and construction industries due to their mechanical strength, thermal stability, and chemical resistance. Advanced thermoset materials, such as epoxy resins, phenolic resins and unsaturated polyester resins, have significantly contributed to industrial innovation. However, these traditional thermosets heavily rely on petroleum-based resources and suffer non-recyclability and even high flammability. Last years have witnessed the use of many renewable chemicals for developing advanced bio-based thermosets with tunable physical properties, such as recyclability and reprocessability enabled by dynamic covalent chemistries, fire retardancy, mechanical and thermal properties. This review aims to summarize recent advances in recyclable, flame-retardant, bio-based thermosets, and highlights their molecular structures and design strategies for achieving high performances. We also discuss intrinsic flame-retardant modes of action, and degradation/recycling mechanisms based on dynamic covalent chemistry. Following discussions on their applications, some key challenges and opportunities are also proposed for the development of next-generation advanced thermosets. This work is expected to expedite the creation of high-performance recyclable thermosets and to advance the sustainability transition of traditional thermosets.
{"title":"Recyclable fire-retardant bio-based thermosets: From molecular engineering to performances and applications","authors":"Yong Guo , Qingshan Yang , Siqi Huo , Juan Li , Pooya Jafari , Zhengping Fang , Pingan Song , Hao Wang","doi":"10.1016/j.progpolymsci.2025.101935","DOIUrl":"10.1016/j.progpolymsci.2025.101935","url":null,"abstract":"<div><div>Thermosets play a critical role in aerospace, automotive, electronics, and construction industries due to their mechanical strength, thermal stability, and chemical resistance. Advanced thermoset materials, such as epoxy resins, phenolic resins and unsaturated polyester resins, have significantly contributed to industrial innovation. However, these traditional thermosets heavily rely on petroleum-based resources and suffer non-recyclability and even high flammability. Last years have witnessed the use of many renewable chemicals for developing advanced bio-based thermosets with tunable physical properties, such as recyclability and reprocessability enabled by dynamic covalent chemistries, fire retardancy, mechanical and thermal properties. This review aims to summarize recent advances in recyclable, flame-retardant, bio-based thermosets, and highlights their molecular structures and design strategies for achieving high performances. We also discuss intrinsic flame-retardant modes of action, and degradation/recycling mechanisms based on dynamic covalent chemistry. Following discussions on their applications, some key challenges and opportunities are also proposed for the development of next-generation advanced thermosets. This work is expected to expedite the creation of high-performance recyclable thermosets and to advance the sustainability transition of traditional thermosets.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"162 ","pages":"Article 101935"},"PeriodicalIF":26.0,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546674","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-19DOI: 10.1016/j.progpolymsci.2025.101933
Mehran Ghasemlou , Callum Stewart , Shima Jafarzadeh , Mina Dokouhaki , Motilal Mathesh , Minoo Naebe , Colin J. Barrow
Surfaces with broader resistance to liquids and solids elicited increased interest in both fundamental research and practical applications. With the technological development and breakthroughs on graft polymerization, flexible polymer chains with extremely low glass transition temperatures (around −100 °C) can be easily affixed on a smooth substrate to make self-lubricated omniphobic covalently attached liquids (SOCALs). SOCALs are emerging surfaces displaying interfacial mobility of molecular-level polymer chains through bending and rotational motions. They have shown unprecedented dynamic fluidity in sliding multiple liquids irrespective of their surface tensions. Their exceptional slipperiness has positioned them at the forefront of fields such as surface science, materials science, and biology. Understanding the underlying principles of SOCALs is crucial for harnessing their features to improve the performance of engineering systems. This review aims to comprehensively overview state-of-the-art developments of SOCALs, dissecting fundamental principles that govern surface de-wetting on these materials. It then examines the design configuration of SOCALs and how the physical characteristics of chains such as surface density, molecular weight, and structure influence their interface mobility and dynamic liquid-like quality. Finally, it highlights representative applications of SOCAL-coated materials in real-world scenarios, emphasizing the exploration of SOCAL materials as a conduit for radical advancements in materials and structural design, bridging the gap between material and interface innovation.
{"title":"Self-lubricated, liquid-like omniphobic polymer brushes: Advances and strategies for enhanced fluid and solid control","authors":"Mehran Ghasemlou , Callum Stewart , Shima Jafarzadeh , Mina Dokouhaki , Motilal Mathesh , Minoo Naebe , Colin J. Barrow","doi":"10.1016/j.progpolymsci.2025.101933","DOIUrl":"10.1016/j.progpolymsci.2025.101933","url":null,"abstract":"<div><div>Surfaces with broader resistance to liquids and solids elicited increased interest in both fundamental research and practical applications. With the technological development and breakthroughs on graft polymerization, flexible polymer chains with extremely low glass transition temperatures (around −100 °C) can be easily affixed on a smooth substrate to make self-lubricated omniphobic covalently attached liquids (SOCALs). SOCALs are emerging surfaces displaying interfacial mobility of molecular-level polymer chains through bending and rotational motions. They have shown unprecedented dynamic fluidity in sliding multiple liquids irrespective of their surface tensions. Their exceptional slipperiness has positioned them at the forefront of fields such as surface science, materials science, and biology. Understanding the underlying principles of SOCALs is crucial for harnessing their features to improve the performance of engineering systems. This review aims to comprehensively overview state-of-the-art developments of SOCALs, dissecting fundamental principles that govern surface de-wetting on these materials. It then examines the design configuration of SOCALs and how the physical characteristics of chains such as surface density, molecular weight, and structure influence their interface mobility and dynamic liquid-like quality. Finally, it highlights representative applications of SOCAL-coated materials in real-world scenarios, emphasizing the exploration of SOCAL materials as a conduit for radical advancements in materials and structural design, bridging the gap between material and interface innovation.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"162 ","pages":"Article 101933"},"PeriodicalIF":26.0,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.progpolymsci.2025.101930
Magdalena Zdanowicz , Sandra Paszkiewicz , Miroslawa El Fray
Thermoplastic polyesters constitute an important class of materials in today's world due to their unique combination of properties, versatility, recyclability, sustainability, and other advantages. A wide range of monomers used in polyesters synthesis lead to their usage in various industries, such as packaging, automotive, or electronics. Poly(ethylene terephthalate) (PET) and other thermoplastic polyesters have been around for decades, however, nowadays, with growing problems such as microplastic migration, growth of landfills, and decreasing sources of fossil fuels, the lack of their biodegradability or the high cost of biodegradable ones make it necessary to search for greener solutions. A novel group of media: deep eutectic solvents (DESs) that have found applications in many areas of science, can also be applied in polyester technology. This review is a holistic approach presenting polyesters in every step of their technology. DESs as easy-to-prepare, green, and cheap alternatives to the organic solvents, metal salts, and ionic liquids employed as reaction media or catalysts. In polyester synthesis, DESs serve as monomer sources, reaction media, and catalysts, i.e. monomeric DESs facilitate solvent-free, autocatalyzed polymerization and production of safe and biodegradable materials that can be applied, for example, in pharmaceutical or medicine engineering. Some DESs cannot depolymerize polyesters, but can render their surfaces more hydrophilic without affecting crystallinity and thus hold promise as functional additives (interfacial/active agents, plasticizers and compatibilizers) for polyesters and their blends. DESs have been widely used in the depolymerization of polyesters (mainly PET but also poly(lactic acid) and poly(ethylene 2,5-furanoate)) as cheaper or greener catalysts or reaction media (or both) with conversion up to 100% and high yield of monomer. In this paper, we consider polyesters and DES issue from the “cradle-to-grave” or even "cradle-to-grave-to-cradle" viewpoint emphasizing the importance of solvolysis as a chemical recycling method. Finally, we present the future perspectives and possibilities of DES usage in polyester technology.
{"title":"Polyesters and deep eutectic solvents: From synthesis through modification to depolymerization","authors":"Magdalena Zdanowicz , Sandra Paszkiewicz , Miroslawa El Fray","doi":"10.1016/j.progpolymsci.2025.101930","DOIUrl":"10.1016/j.progpolymsci.2025.101930","url":null,"abstract":"<div><div>Thermoplastic polyesters constitute an important class of materials in today's world due to their unique combination of properties, versatility, recyclability, sustainability, and other advantages. A wide range of monomers used in polyesters synthesis lead to their usage in various industries, such as packaging, automotive, or electronics. Poly(ethylene terephthalate) (PET) and other thermoplastic polyesters have been around for decades, however, nowadays, with growing problems such as microplastic migration, growth of landfills, and decreasing sources of fossil fuels, the lack of their biodegradability or the high cost of biodegradable ones make it necessary to search for greener solutions. A novel group of media: deep eutectic solvents (DESs) that have found applications in many areas of science, can also be applied in polyester technology. This review is a holistic approach presenting polyesters in every step of their technology. DESs as easy-to-prepare, green, and cheap alternatives to the organic solvents, metal salts, and ionic liquids employed as reaction media or catalysts. In polyester synthesis, DESs serve as monomer sources, reaction media, and catalysts, i.e. monomeric DESs facilitate solvent-free, autocatalyzed polymerization and production of safe and biodegradable materials that can be applied, for example, in pharmaceutical or medicine engineering. Some DESs cannot depolymerize polyesters, but can render their surfaces more hydrophilic without affecting crystallinity and thus hold promise as functional additives (interfacial/active agents, plasticizers and compatibilizers) for polyesters and their blends. DESs have been widely used in the depolymerization of polyesters (mainly PET but also poly(lactic acid) and poly(ethylene 2,5-furanoate)) as cheaper or greener catalysts or reaction media (or both) with conversion up to 100% and high yield of monomer. In this paper, we consider polyesters and DES issue from the “cradle-to-grave” or even \"cradle-to-grave-to-cradle\" viewpoint emphasizing the importance of solvolysis as a chemical recycling method. Finally, we present the future perspectives and possibilities of DES usage in polyester technology.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"161 ","pages":"Article 101930"},"PeriodicalIF":26.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418039","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-01DOI: 10.1016/j.progpolymsci.2025.101929
Yitian Teng , Jiayu Chi , Jinjian Huang , Ze Li , Sicheng Li , Xiuwen Wu , Linyong Zhu , Jianan Ren
Hydrogels have attracted significant interest as promising biomedical materials due to their tunable physiochemical features, tailorable microstructures, high water content, and adjustable mechanical properties Despite their intrinsic advantages, the mismatch in mechanical performance between traditional hydrogels and tissues has severely restricted their utility in practical settings, generating an urgent need for developing tough hydrogels that can be used in continuous load-bearing scenarios without sacrificing other equally important mechanical features. This review summarises the evolving synthesis rationale and strategies to develop tough hydrogels, including recent considerations of biomimetic designs, which enables diverse applications of hydrogels in tissue engineering, adhesives, and drug delivery system Although challenges remain in this field, the translational applications of hydrogels are rapidly progressing, broadening the scope of material science and biomedicine.
{"title":"Hydrogel toughening resets biomedical application boundaries","authors":"Yitian Teng , Jiayu Chi , Jinjian Huang , Ze Li , Sicheng Li , Xiuwen Wu , Linyong Zhu , Jianan Ren","doi":"10.1016/j.progpolymsci.2025.101929","DOIUrl":"10.1016/j.progpolymsci.2025.101929","url":null,"abstract":"<div><div>Hydrogels have attracted significant interest as promising biomedical materials due to their tunable physiochemical features, tailorable microstructures, high water content, and adjustable mechanical properties Despite their intrinsic advantages, the mismatch in mechanical performance between traditional hydrogels and tissues has severely restricted their utility in practical settings, generating an urgent need for developing tough hydrogels that can be used in continuous load-bearing scenarios without sacrificing other equally important mechanical features. This review summarises the evolving synthesis rationale and strategies to develop tough hydrogels, including recent considerations of biomimetic designs, which enables diverse applications of hydrogels in tissue engineering, adhesives, and drug delivery system Although challenges remain in this field, the translational applications of hydrogels are rapidly progressing, broadening the scope of material science and biomedicine.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"161 ","pages":"Article 101929"},"PeriodicalIF":26.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143071982","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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