Herein, we introduce a sustainable method for latex production via surfactant-free emulsion polymerization (SFEP) carrying out a photoinitiated polymerization (photo-SFEP) under both artificial light and sunlight. We discuss the use of sodium phenyl-2,4,6-trimethylbenzoylphosphinate (TPO-Na) as a water-soluble photoinitiator to in-situ prepare polymeric nanoparticles under mild conditions, eliminating the need of conventional surfactants. The methodology exploits the rapid photolysis of TPO-Na, which generates anionic radical species that initiate the polymerization of glycidyl methacrylate (GlyMA), selected as a model monomer. Photo-SFEP was optimized to ensure colloidal stability over several months, even under varying environmental ionic strengths. The structural and colloidal properties of the nanoparticles were thoroughly characterized using dynamic light scattering (DLS), transmission electron microscopy (TEM), and zeta potential measurements, confirming the reproducibility and robustness of the latex dispersions. Our methodology shows promise as a scalable, efficient alternative to conventional emulsion polymerization techniques. Additionally, its versatility was affirmed by extending its application to various vinylic monomers, showcasing its broad potential.
{"title":"Shedding Light on Surfactant-Free Emulsion Polymerization","authors":"Erika Paola Fonseca Parra, Jean-Luc Six, Khalid Ferji","doi":"10.1039/d4py01076k","DOIUrl":"https://doi.org/10.1039/d4py01076k","url":null,"abstract":"Herein, we introduce a sustainable method for latex production via surfactant-free emulsion polymerization (SFEP) carrying out a photoinitiated polymerization (photo-SFEP) under both artificial light and sunlight. We discuss the use of sodium phenyl-2,4,6-trimethylbenzoylphosphinate (TPO-Na) as a water-soluble photoinitiator to in-situ prepare polymeric nanoparticles under mild conditions, eliminating the need of conventional surfactants. The methodology exploits the rapid photolysis of TPO-Na, which generates anionic radical species that initiate the polymerization of glycidyl methacrylate (GlyMA), selected as a model monomer. Photo-SFEP was optimized to ensure colloidal stability over several months, even under varying environmental ionic strengths. The structural and colloidal properties of the nanoparticles were thoroughly characterized using dynamic light scattering (DLS), transmission electron microscopy (TEM), and zeta potential measurements, confirming the reproducibility and robustness of the latex dispersions. Our methodology shows promise as a scalable, efficient alternative to conventional emulsion polymerization techniques. Additionally, its versatility was affirmed by extending its application to various vinylic monomers, showcasing its broad potential.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"9 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992594","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jenny Stephan, Merlin R. Stühler, Christoph Fornacon-Wood, Mathias Dimde, Kai Ludwig, Heinz Sturm, Jorge Olmedo, Alejandro Muller, Alex Johannes Plajer
Sulfur-containing polymers can coordinate transition metals via sulfur-centered, chemically soft lone pairs, although this typically occurs in a spatially uncontrolled manner. In this study, we employed the controlled ring-opening copolymerization of oxetane with sulfur-containing comonomers to construct a series of amphiphilic block copolymers featuring thioester and thiocarbonate functionalities. These copolymers self-assemble in aqueous solution into aggregates with a sulfur-rich core capable of coordinating transition metals. This behavior could be resolved by employing cryo-transmission electron tomography and then extended to complexes incorporating functional coligands. Our study demonstrates how selective catalysis can be harnessed to produce functional polymers with tunable metal coordination properties, paving the way for an emerging class of sulfur-containing copolymers.
{"title":"Sulfur-Containing Block Polymers from Ring-Opening Copolymerisation: Coordinative Encapsulants for Transition Metals","authors":"Jenny Stephan, Merlin R. Stühler, Christoph Fornacon-Wood, Mathias Dimde, Kai Ludwig, Heinz Sturm, Jorge Olmedo, Alejandro Muller, Alex Johannes Plajer","doi":"10.1039/d4py01415d","DOIUrl":"https://doi.org/10.1039/d4py01415d","url":null,"abstract":"Sulfur-containing polymers can coordinate transition metals via sulfur-centered, chemically soft lone pairs, although this typically occurs in a spatially uncontrolled manner. In this study, we employed the controlled ring-opening copolymerization of oxetane with sulfur-containing comonomers to construct a series of amphiphilic block copolymers featuring thioester and thiocarbonate functionalities. These copolymers self-assemble in aqueous solution into aggregates with a sulfur-rich core capable of coordinating transition metals. This behavior could be resolved by employing cryo-transmission electron tomography and then extended to complexes incorporating functional coligands. Our study demonstrates how selective catalysis can be harnessed to produce functional polymers with tunable metal coordination properties, paving the way for an emerging class of sulfur-containing copolymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"71 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990610","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hui Tian, Yifan Wang, Chunji Wu, Xiaohui Kang, Baoli Wang
Polar polyolefins are of fundamental interest and practical significance. The direct synthesis of polyethylene containing two kinds of heteroatoms by early transition catalysts is still rare due to the complicated poisoning action, but these novel copolymers may behave superposed and unexpected characteristic. Herein we report the production of polyethylene containing two distinct polar groups (such as O, S and F) by scandium complexes. Sc-2 with bulkier ligand can raise polar olefin incorporation. S and F atoms on comonomer 1g (2S/F-o) shows significantly positive effect during copolymerization with ethylene and results in high incorporation ratio (17.2 to 44.9 mol%), high activity (69.0 to 211 kg molSc–1 h–1 bar–1) and high molecular weight (Mn) up to 33.3 × 104 g mol–1. The polymerization mechanistic aspect of cooperative action between S and F atoms on 1g has been elucidated by DFT studies. We expect that our new findings could guide the synthesis of polyolefins containing multi-functional groups.
极性聚烯烃具有重要的现实意义。由于中毒作用复杂，用早过渡催化剂直接合成含两种杂原子的聚乙烯尚属罕见，但这些新型共聚物可能表现出叠加性和意想不到的特性。在这里，我们报道了用钪配合物生产含有两个不同极性基团（如O， S和F）的聚乙烯。配体较大的Sc-2能提高极性烯烃的结合。共聚单体1g （2S/F-o）上的S和F原子在乙烯共聚过程中表现出显著的正向作用，并获得了高掺入比（17.2 ~ 44.9 mol%）、高活性（69.0 ~ 211 kg molSc-1 h-1 bar-1）和高分子量（Mn） （33.3 × 104 g mol - 1）。通过DFT研究阐明了S和F原子在1g上协同作用的聚合机理。我们期望我们的新发现可以指导含多官能团聚烯烃的合成。
{"title":"Direct Synthesis of Polyethylene Containing Two Kinds of Heteroatoms by Scandium Complexes","authors":"Hui Tian, Yifan Wang, Chunji Wu, Xiaohui Kang, Baoli Wang","doi":"10.1039/d4py01393j","DOIUrl":"https://doi.org/10.1039/d4py01393j","url":null,"abstract":"Polar polyolefins are of fundamental interest and practical significance. The direct synthesis of polyethylene containing two kinds of heteroatoms by early transition catalysts is still rare due to the complicated poisoning action, but these novel copolymers may behave superposed and unexpected characteristic. Herein we report the production of polyethylene containing two distinct polar groups (such as O, S and F) by scandium complexes. <strong>Sc-2</strong> with bulkier ligand can raise polar olefin incorporation. S and F atoms on comonomer <strong>1g</strong> (<strong>2S/F-<em>o</em></strong>) shows significantly positive effect during copolymerization with ethylene and results in high incorporation ratio (17.2 to 44.9 mol%), high activity (69.0 to 211 kg mol<small><sub>Sc</sub></small><small><sup>–1</sup></small> h<small><sup>–1</sup></small> bar<small><sup>–1</sup></small>) and high molecular weight (Mn) up to 33.3 × 10<small><sup>4</sup></small> g mol<small><sup>–1</sup></small>. The polymerization mechanistic aspect of cooperative action between S and F atoms on <strong>1g</strong> has been elucidated by DFT studies. We expect that our new findings could guide the synthesis of polyolefins containing multi-functional groups.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"23 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989790","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Poly(styrene-co-maleic anhydride) (SMAnh) is a petroleum-based copolymer with desirable properties that afford utility in both industrial and academic fields. The reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization of the bioderived comonomers, indene and itaconic anhydride, was explored using three chain transfer agents with varying activity, and generally well-controlled (Đ < 1.40) polymerizations were observed.
{"title":"Bioderived copolymer alternatives to poly(styrene-co-maleic anhydride) via RAFT-mediated copolymerization","authors":"Lauren Elaine Ball, Michael-Phillip Smith, Bert Klumperman","doi":"10.1039/d4py01227e","DOIUrl":"https://doi.org/10.1039/d4py01227e","url":null,"abstract":"Poly(styrene-<em>co</em>-maleic anhydride) (SMAnh) is a petroleum-based copolymer with desirable properties that afford utility in both industrial and academic fields. The reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization of the bioderived comonomers, indene and itaconic anhydride, was explored using three chain transfer agents with varying activity, and generally well-controlled (<em>Đ</em> < 1.40) polymerizations were observed.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987258","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Arthur Werner, Connor A. Sanders, Sandra Smeltzer, Sean R. George, Andreas Gernandt, Bernd Reck, Michael F. Cunningham
Block-Random Copolymers (BRCs) incorporating acrylics were synthesised using nitroxide-mediated polymerisation (NMP) to form macro-stabilisers for the preparation ofpolymer latexes. These hybrids of block copolymers and random copolymers are traditionally composed of a polystyrene hydrophobic block coupled with a hydrophilic random block of styrene and acrylic acid. Their aqueous dispersions exhibit unique behaviour compared to conventional block copolymers, including being responsible for a unique nucleation mechanism in emulsion polymerisation. However, all previous work has only used styrene as the hydrophobic monomer, and only styrene emulsion polymerizations have been conducted. To explore the versatility of BRCs for the polymerisation of monomers other than styrenics (e.g. acrylates, methacrylates), the BRC library was explored with the introduction of methyl methacrylate (MMA) and n-butyl acrylate (n-BuA) units as the hydrophobic monomers. With blocks composed of one or multiple monomers, all the BRCs were successfully dispersed in water at high concentrations (>100 g.L-1), with similar behaviour compared to previously reported for styrene-based BRCs. Semi-batch emulsion polymerisation of styrene or acrylates latexes was also performed. A hydrophobic block consisting of a n-BuA and styrene copolymer was found to be of the most interest, showing promising stability over the range of latexes polymerised
{"title":"Amphiphilic Block-Random Copolymer Stabilisers: Extension to Other Monomer Types","authors":"Arthur Werner, Connor A. Sanders, Sandra Smeltzer, Sean R. George, Andreas Gernandt, Bernd Reck, Michael F. Cunningham","doi":"10.1039/d4py01321b","DOIUrl":"https://doi.org/10.1039/d4py01321b","url":null,"abstract":"Block-Random Copolymers (BRCs) incorporating acrylics were synthesised using nitroxide-mediated polymerisation (NMP) to form macro-stabilisers for the preparation ofpolymer latexes. These hybrids of block copolymers and random copolymers are traditionally composed of a polystyrene hydrophobic block coupled with a hydrophilic random block of styrene and acrylic acid. Their aqueous dispersions exhibit unique behaviour compared to conventional block copolymers, including being responsible for a unique nucleation mechanism in emulsion polymerisation. However, all previous work has only used styrene as the hydrophobic monomer, and only styrene emulsion polymerizations have been conducted. To explore the versatility of BRCs for the polymerisation of monomers other than styrenics (e.g. acrylates, methacrylates), the BRC library was explored with the introduction of methyl methacrylate (MMA) and n-butyl acrylate (n-BuA) units as the hydrophobic monomers. With blocks composed of one or multiple monomers, all the BRCs were successfully dispersed in water at high concentrations (>100 g.L-1), with similar behaviour compared to previously reported for styrene-based BRCs. Semi-batch emulsion polymerisation of styrene or acrylates latexes was also performed. A hydrophobic block consisting of a n-BuA and styrene copolymer was found to be of the most interest, showing promising stability over the range of latexes polymerised","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"49 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986049","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Developing new chemically recyclable polymers is highly demanded for a circular plastic economy. Herein, we implemented a sulfur-substitution approach to improve the chemical recyclability and material performance of polycaprolactone (PCL). This thiocaprolactone (tCL) displayed excellent reactivity towards ring-opening polymerization, affording P(tCL) products with high thermal stability (Td = 330 °C), high air stability, high crystallinity, and outstanding mechanical and transport property (σB = ~20 MPa, ɛB = ~600%, PO2 = 0.38 Barrer) comparable to commercial low-density polyethylene. Impressively, chemical recycling of P(tCL) to its monomer could be accomplished with excellent yield and purity, thus establishing its circular life cycle
{"title":"Implementing Sulfur-Substitution Approach Toward a High-Performance Recyclable Polythioester","authors":"Si-Qi Wang, Long-Hai Liu, Kun Li, Wei Xiong, Hua-Zhong Fan, Qing Cao, Zhongzheng Cai, Jian-Bo Zhu","doi":"10.1039/d4py01425a","DOIUrl":"https://doi.org/10.1039/d4py01425a","url":null,"abstract":"Developing new chemically recyclable polymers is highly demanded for a circular plastic economy. Herein, we implemented a sulfur-substitution approach to improve the chemical recyclability and material performance of polycaprolactone (PCL). This thiocaprolactone (tCL) displayed excellent reactivity towards ring-opening polymerization, affording P(tCL) products with high thermal stability (Td = 330 °C), high air stability, high crystallinity, and outstanding mechanical and transport property (σB = ~20 MPa, ɛB = ~600%, PO2 = 0.38 Barrer) comparable to commercial low-density polyethylene. Impressively, chemical recycling of P(tCL) to its monomer could be accomplished with excellent yield and purity, thus establishing its circular life cycle","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"2 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986051","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Developing new sulfur-containing polymers with chemical recyclability is highly demanded as next-generation high-performance sustainable polymeric materials. Herein, we prepared two seven-membered thiolactone monomers (M1 and M2) with sulfur-incorporated at different positions. Both monomers displayed excellent reactivity towards ring-opening polymerization with >90% monomer conversion at room temperature. The resulting poly(thioether-thioester) products P(M)s exhibited high thermal stability and comparable mechanical properties (σB = ~30 MPa, ɛB = ~660%) to commercial low-density polyethylene. Chemical recycling of P(M1) to its monomer M1 could be accomplished with excellent yield and purity. Intriguingly, P(M1) could be applied for selective absorption and recovery of Au3+ with >99% efficiency by the exploit of chemical recyclability of P(M1).
{"title":"Chemically Recyclable Poly(thioether-thioester)s via Ring-Opening Polymerization of Seven-Membered Thiolactones","authors":"Long-Hai Liu, Si-Qi Wang, Hua-Zhong Fan, Qing Cao, Zhongzheng Cai, Jian-Bo Zhu","doi":"10.1039/d4py01442a","DOIUrl":"https://doi.org/10.1039/d4py01442a","url":null,"abstract":"Developing new sulfur-containing polymers with chemical recyclability is highly demanded as next-generation high-performance sustainable polymeric materials. Herein, we prepared two seven-membered thiolactone monomers (M1 and M2) with sulfur-incorporated at different positions. Both monomers displayed excellent reactivity towards ring-opening polymerization with >90% monomer conversion at room temperature. The resulting poly(thioether-thioester) products P(M)s exhibited high thermal stability and comparable mechanical properties (σB = ~30 MPa, ɛB = ~660%) to commercial low-density polyethylene. Chemical recycling of P(M1) to its monomer M1 could be accomplished with excellent yield and purity. Intriguingly, P(M1) could be applied for selective absorption and recovery of Au3+ with >99% efficiency by the exploit of chemical recyclability of P(M1).","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"43 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jie Liu, Pengcheng Miao, Xuefei Leng, Yidi Li, Wei Wang, Yang Li
Polyhydroxyurethanes (PHUs) are considered a sustainable and safer alternative to traditional toxic isocyanate-based polyurethanes (PUs). There are two important characteristics of PHUs, which are their mechanical and self-healing properties. However, these two features are contradictory properties difficult to optimize simultaneously. In this work, a strong and rapid self-healing bio-based PHU network was prepared based on carbonated daidzein (DZ-BCC) and amines. The self-healing properties are tailored by using aminopropyl-terminated polydimethylsiloxane (H2N-PDMS-NH2) as a soft segment, increasing the chain mobility. The high crosslinking density of networks and the benzopyran ring structure in daidzein give the resulting PHUs a strength of up to 28.3 MPa. Despite their excellent mechanical properties, these materials show rapid self-healing capability, chemical recyclability, and remarkable reprocessing efficiency. Notably, 94% of the original tensile strength can be recovered after self-healing for 30 min at 150 °C. In addition, the prepared materials have the potential to be used as adhesives in wood and glass bonding, achieving lap shear strengths of up to 6.4 MPa and 3.4 MPa, respectively. Moreover, bonded glasses with PHUs exhibit excellent high-temperature resistance, maintaining stability up to 150 °C. This study presents bio-based PHUs derived from daidzein with good mechanical and dynamic performance simultaneously, and broadens their applications in high temperature-resistant adhesives.
{"title":"High strength and rapid self-healing daidzein-based polyhydroxyurethanes for high temperature-resistant adhesives","authors":"Jie Liu, Pengcheng Miao, Xuefei Leng, Yidi Li, Wei Wang, Yang Li","doi":"10.1039/d4py01396d","DOIUrl":"https://doi.org/10.1039/d4py01396d","url":null,"abstract":"Polyhydroxyurethanes (PHUs) are considered a sustainable and safer alternative to traditional toxic isocyanate-based polyurethanes (PUs). There are two important characteristics of PHUs, which are their mechanical and self-healing properties. However, these two features are contradictory properties difficult to optimize simultaneously. In this work, a strong and rapid self-healing bio-based PHU network was prepared based on carbonated daidzein (DZ-BCC) and amines. The self-healing properties are tailored by using aminopropyl-terminated polydimethylsiloxane (H<small><sub>2</sub></small>N-PDMS-NH<small><sub>2</sub></small>) as a soft segment, increasing the chain mobility. The high crosslinking density of networks and the benzopyran ring structure in daidzein give the resulting PHUs a strength of up to 28.3 MPa. Despite their excellent mechanical properties, these materials show rapid self-healing capability, chemical recyclability, and remarkable reprocessing efficiency. Notably, 94% of the original tensile strength can be recovered after self-healing for 30 min at 150 °C. In addition, the prepared materials have the potential to be used as adhesives in wood and glass bonding, achieving lap shear strengths of up to 6.4 MPa and 3.4 MPa, respectively. Moreover, bonded glasses with PHUs exhibit excellent high-temperature resistance, maintaining stability up to 150 °C. This study presents bio-based PHUs derived from daidzein with good mechanical and dynamic performance simultaneously, and broadens their applications in high temperature-resistant adhesives.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"91 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975278","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhenyu Yang, Xiaoting Ji, Xinlong Sha, Jincheng Ding, Lin Cheng, Guangfeng Li
With the increasing global attention on energy and environmental issues, there is a growing push towards the eco-friendly transformation of adhesive materials. However, designing and developing eco-friendly adhesive materials with ultra-strong adhesion has always been a significant challenge in the field of adhesion. Herein, we present an eco-friendly adhesive (CBA) derived from bio-based thioctic acid (TA) that combines synergistic covalent and dynamic covalent polymeric segments, demonstrating strong adhesive strength and closed-loop recyclability. Specifically, leveraging the synergistic effects of dynamic covalent and covalent chain segments within the polymer network, the adhesive CBA exhibits ultra-strong adhesive strength (16.1 MPa), exceptional antifreeze performance (11.6 MPa at −196 °C), high reusability with 12.1 MPa retained after ten cycles, and resistance to common organic solvents. Importantly, the main chains of disulfide bonds formed through solid-phase thermal-induced ring-opening polymerization of TA, combined with robust reversible amide bonds to crosslink into a network, enables closed-loop recyclability. This approach of using bio-based materials with synergistic dynamic covalent and covalent bonds effectively balances adhesive strength with environmental sustainability, offering an excellent solution for designing and developing new adhesive materials.
{"title":"An Eco-Friendly Adhesive with Ultra-Strong Adhesive Performance","authors":"Zhenyu Yang, Xiaoting Ji, Xinlong Sha, Jincheng Ding, Lin Cheng, Guangfeng Li","doi":"10.1039/d4py01398k","DOIUrl":"https://doi.org/10.1039/d4py01398k","url":null,"abstract":"With the increasing global attention on energy and environmental issues, there is a growing push towards the eco-friendly transformation of adhesive materials. However, designing and developing eco-friendly adhesive materials with ultra-strong adhesion has always been a significant challenge in the field of adhesion. Herein, we present an eco-friendly adhesive (CBA) derived from bio-based thioctic acid (TA) that combines synergistic covalent and dynamic covalent polymeric segments, demonstrating strong adhesive strength and closed-loop recyclability. Specifically, leveraging the synergistic effects of dynamic covalent and covalent chain segments within the polymer network, the adhesive CBA exhibits ultra-strong adhesive strength (16.1 MPa), exceptional antifreeze performance (11.6 MPa at −196 °C), high reusability with 12.1 MPa retained after ten cycles, and resistance to common organic solvents. Importantly, the main chains of disulfide bonds formed through solid-phase thermal-induced ring-opening polymerization of TA, combined with robust reversible amide bonds to crosslink into a network, enables closed-loop recyclability. This approach of using bio-based materials with synergistic dynamic covalent and covalent bonds effectively balances adhesive strength with environmental sustainability, offering an excellent solution for designing and developing new adhesive materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"36 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975281","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chirality and chiral materials demonstrate ever-growing importance. Non-spherical chiral polymer particles have witnessed an increasing interest in recent years, owing to their fascinating physicochemical properties as well as wide-ranging applications. There is a trend to develop new technologies based on existing technical principles, and the design and synthesis of polymer particles will play a vital role in the further development of chiral applications. In this review, the state-of-the-art research progress of non-spherical chiral polymer particles in the past ten years is summarized. First, the preparation strategies of non-spherical chiral polymer particles are detailed from multiple perspectives, including emulsion polymerization, precipitation polymerization and suspension polymerization, as well as special processes such as spray drying, microfluidics, photolithography, and self-assembly. In addition, this review adds to the development from spherical to non-spherical particle morphology. Then, the applications of the resulting beguiling particles in chiral separation, asymmetric catalysis, drug release, and circularly polarized luminescence are illustrated. Finally, the challenges and opportunities that exist in the field are pointed out. This review aims to offer important guidance and stimulate more research attention to this rapidly developing field.
{"title":"Evolution and Recent Progress of Non-spherical Chiral Micro- and Nanoparticles: Preparation, Design, and Advanced Applications","authors":"Pengpeng Li, Jiahao Zhang, Xinlong Liu, Xin Zhang, Jinsong Ma, Guohua Sun, Lianlong Hou, Saleem Raza","doi":"10.1039/d4py01057d","DOIUrl":"https://doi.org/10.1039/d4py01057d","url":null,"abstract":"Chirality and chiral materials demonstrate ever-growing importance. Non-spherical chiral polymer particles have witnessed an increasing interest in recent years, owing to their fascinating physicochemical properties as well as wide-ranging applications. There is a trend to develop new technologies based on existing technical principles, and the design and synthesis of polymer particles will play a vital role in the further development of chiral applications. In this review, the state-of-the-art research progress of non-spherical chiral polymer particles in the past ten years is summarized. First, the preparation strategies of non-spherical chiral polymer particles are detailed from multiple perspectives, including emulsion polymerization, precipitation polymerization and suspension polymerization, as well as special processes such as spray drying, microfluidics, photolithography, and self-assembly. In addition, this review adds to the development from spherical to non-spherical particle morphology. Then, the applications of the resulting beguiling particles in chiral separation, asymmetric catalysis, drug release, and circularly polarized luminescence are illustrated. Finally, the challenges and opportunities that exist in the field are pointed out. This review aims to offer important guidance and stimulate more research attention to this rapidly developing field.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"21 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975279","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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