The nano-objects generated by scalable polymerization-induced self-assembly (PISA) process can serve as organic nanofillers, replacing the widely used inorganic nanofillers in composites. In this contribution, the polyisoprene (PI)-b-polystyrene (PS) (PI-b-PS) or PI-b-PS/PS nano-objects were prepared by living anionic polymerization-induced self-assembly (LAPISA) process or the derived process of living anionic polymerization-induced cooperative assembly (LAPICA) using nonpolar n-heptane as solvent, which facilitated the control over morphologies and sizes. After the living species in core region were in-situ crosslinked by divinylbenzene (DVB) monomer, the stabilized PDVB@(PI-b-PS) or PDVB@(PI-b-PS/PS) nano-objects were generated. After the hydroxylated or epoxidized nano-objects were obtained through thiol-ene or epoxidation reaction on double bonds of PI stabilizer, the miscibility between nano-objects and epoxy resin was improved, and the functionalized nano-objects could be introduced into epoxy resin. The differential scanning calorimetry (DSC), thermal gravimetric analyzer (TGA) and thermomechanical analyzer (TMA) results affirmed that the organic nano-objects could improve the thermal properties of composites, which were obviously superior to the commercial inorganic silica nano-objects. Especially, the composites with smaller spherical nano-objects had higher glass transition temperature (Tg) than those with the larger spherical ones or worm-like ones. The transmission electron microscopy (TEM) measurement supported the uniform distribution of organic nano-objects and the formation of sufficiently integrated interfaces between epoxy resin and nano-objects, thereby improving the thermal properties of composites.
{"title":"Functionalization of Nano-objects in Living Anionic Polymerization-Induced Self-assembly and their use for Improving Thermal Properties of Epoxy Resins","authors":"Guicun Guo, Jiali Wu, Jingwei Zhang, Peng Zhou, Ding Shen, Penghan Li, Guowei Wang","doi":"10.1039/d4py01008f","DOIUrl":"https://doi.org/10.1039/d4py01008f","url":null,"abstract":"The nano-objects generated by scalable polymerization-induced self-assembly (PISA) process can serve as organic nanofillers, replacing the widely used inorganic nanofillers in composites. In this contribution, the polyisoprene (PI)-b-polystyrene (PS) (PI-b-PS) or PI-b-PS/PS nano-objects were prepared by living anionic polymerization-induced self-assembly (LAPISA) process or the derived process of living anionic polymerization-induced cooperative assembly (LAPICA) using nonpolar n-heptane as solvent, which facilitated the control over morphologies and sizes. After the living species in core region were in-situ crosslinked by divinylbenzene (DVB) monomer, the stabilized PDVB@(PI-b-PS) or PDVB@(PI-b-PS/PS) nano-objects were generated. After the hydroxylated or epoxidized nano-objects were obtained through thiol-ene or epoxidation reaction on double bonds of PI stabilizer, the miscibility between nano-objects and epoxy resin was improved, and the functionalized nano-objects could be introduced into epoxy resin. The differential scanning calorimetry (DSC), thermal gravimetric analyzer (TGA) and thermomechanical analyzer (TMA) results affirmed that the organic nano-objects could improve the thermal properties of composites, which were obviously superior to the commercial inorganic silica nano-objects. Especially, the composites with smaller spherical nano-objects had higher glass transition temperature (Tg) than those with the larger spherical ones or worm-like ones. The transmission electron microscopy (TEM) measurement supported the uniform distribution of organic nano-objects and the formation of sufficiently integrated interfaces between epoxy resin and nano-objects, thereby improving the thermal properties of composites.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486256","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}
Noushin Rajabalinia, Fatemeh Salarhosseini, Robin A. Hutchinson
The properties of waterborne polymer dispersions synthesized by emulsion radical polymerization are influenced by reactions in both the aqueous medium and the growing particles. Mathematical models representing the process often do not consider the difference in the propagation rate coefficient (kp) of monomers in the two phases, despite the body of evidence demonstrating that solvent polarity influences monomer-monomer and monomer-solvent hydrogen-bonding that affects both kp homopropagation values and copolymerization reactivity ratios. Therefore, it is vital to develop experimental approaches to systematically measure the influence of solvent on the copolymerization kinetics of hydrophobic monomers under conditions that are similar to emulsion systems. In this work, we study the copolymerization of methyl acrylate (MA) with di(ethylene glycol) methyl ether methacrylate (DEGMEMA) as models for the common emulsion monomers butyl acrylate and methyl methacrylate. As well as varying solvent choice and monomer concentration, MA/DEGMEMA copolymerization kinetics are compared to those of MA with methacrylic acid (MAA) to determine the influence of monomer functionality on its relative reactivity. The findings suggest that the copolymer composition of all methacrylate-acrylate systems – whether involving functional or non-functional monomers – converge to a single curve in protic polar aqueous solution.
通过乳液自由基聚合法合成的水性聚合物分散体的特性受到水介质和生长颗粒中反应的影响。尽管大量证据表明，溶剂极性会影响单体与单体之间以及单体与溶剂之间的氢键作用，从而影响 kp 的同向扩散值和共聚反应率，但表示该过程的数学模型通常不会考虑单体在两相中传播速率系数 (kp) 的差异。因此，必须开发实验方法，在与乳液体系类似的条件下系统测量溶剂对疏水性单体共聚动力学的影响。在这项工作中，我们以常见的乳液单体丙烯酸丁酯和甲基丙烯酸甲酯为模型，研究了丙烯酸甲酯（MA）与甲基丙烯酸二（乙二醇）甲醚（DEGMEMA）的共聚。除了改变溶剂选择和单体浓度外，还将 MA/DEGMEMA 共聚动力学与 MA 与甲基丙烯酸（MAA）的共聚动力学进行了比较，以确定单体官能度对其相对反应性的影响。研究结果表明，在原生极性水溶液中，所有甲基丙烯酸酯-丙烯酸酯体系的共聚物组成--无论是涉及功能性单体还是非功能性单体--都会趋同于一条曲线。
{"title":"Acrylate-Methacrylate Radical Copolymerization Kinetics of Sparingly Water-Soluble Monomers in Polar and Nonpolar Solvents","authors":"Noushin Rajabalinia, Fatemeh Salarhosseini, Robin A. Hutchinson","doi":"10.1039/d4py01015a","DOIUrl":"https://doi.org/10.1039/d4py01015a","url":null,"abstract":"The properties of waterborne polymer dispersions synthesized by emulsion radical polymerization are influenced by reactions in both the aqueous medium and the growing particles. Mathematical models representing the process often do not consider the difference in the propagation rate coefficient (<em>k</em><small><sub>p</sub></small>) of monomers in the two phases, despite the body of evidence demonstrating that solvent polarity influences monomer-monomer and monomer-solvent hydrogen-bonding that affects both <em>k</em><small><sub>p</sub></small> homopropagation values and copolymerization reactivity ratios. Therefore, it is vital to develop experimental approaches to systematically measure the influence of solvent on the copolymerization kinetics of hydrophobic monomers under conditions that are similar to emulsion systems. In this work, we study the copolymerization of methyl acrylate (MA) with di(ethylene glycol) methyl ether methacrylate (DEGMEMA) as models for the common emulsion monomers butyl acrylate and methyl methacrylate. As well as varying solvent choice and monomer concentration, MA/DEGMEMA copolymerization kinetics are compared to those of MA with methacrylic acid (MAA) to determine the influence of monomer functionality on its relative reactivity. The findings suggest that the copolymer composition of all methacrylate-acrylate systems – whether involving functional or non-functional monomers – converge to a single curve in protic polar aqueous solution.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486255","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}
Kim Jiayi Wu, John M. Tobin, Anli Ji, Yang Shi, Chunchun Ye, Gary S. Nichol, Alessio Fuoco, Mariagiulia Longo, Johannes C. Jansen, Neil B. McKeown
The readily prepared CF3TMS adduct of anthraquinone is shown to be an efficient monomer for superacid-catalysed step-growth polymerisations, as exemplified by its reaction with diphenyl ether. The resulting polymer (BTFMA-DPE) is produced rapidly, with high molecular mass, and shows promise as a gas separation membrane material.
{"title":"The CF3TMS adduct of anthraquinone as a monomer for making polymers with potential as separation membranes","authors":"Kim Jiayi Wu, John M. Tobin, Anli Ji, Yang Shi, Chunchun Ye, Gary S. Nichol, Alessio Fuoco, Mariagiulia Longo, Johannes C. Jansen, Neil B. McKeown","doi":"10.1039/d4py01002g","DOIUrl":"https://doi.org/10.1039/d4py01002g","url":null,"abstract":"The readily prepared CF<small><sub>3</sub></small>TMS adduct of anthraquinone is shown to be an efficient monomer for superacid-catalysed step-growth polymerisations, as exemplified by its reaction with diphenyl ether. The resulting polymer (<strong>BTFMA-DPE</strong>) is produced rapidly, with high molecular mass, and shows promise as a gas separation membrane material.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452354","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}
Andrew J. King, Ryan P. Sherrier, Jeffrey Aubé, Aleksandr V Zhukhovitskiy
The properties, applications, and end-of-life considerations of plastics are fundamentally linked to the structure of the polymer backbones at the core of these materials. With that in mind, editing the polymer backbone composition offers exciting opportunities to transform the plastics economy; yet, few examples of such transformations utilize commodity plastics as starting materials. In this work, we describe the development of a tandem C–H oxidation/hydroxyalkyl azide mediated rearrangement strategy that converts polyethylene into “polyethylene-like” materials with iminium ethers, esters, amides, and other pendant chemical functionality. Control over formation of esters or amides is achieved by variation of the hydroxyalkyl azide reagent, as well as processing conditions. By targeting specific functionalities, a variety of thermal and mechanical properties can be accessed. For example, incorporation of iminium ethers decreases the Young’s modulus of post-consumer PE from 196 MPa to 69–83 MPa, but conversion of the iminium ethers to esters and amides produces materials with moduli of 212–287 MPa—values higher than the original material. Thus, the demonstration of a modular backbone editing methodology for polyethylene showcases the broader value of this emerging strategy for polymer modification.
{"title":"Backbone Editing of Oxidized Polyethylene: Insertion of Oxygen and Nitrogen Atoms via Hydroxyalkyl Azide-Mediated Rearrangements","authors":"Andrew J. King, Ryan P. Sherrier, Jeffrey Aubé, Aleksandr V Zhukhovitskiy","doi":"10.1039/d4py00973h","DOIUrl":"https://doi.org/10.1039/d4py00973h","url":null,"abstract":"The properties, applications, and end-of-life considerations of plastics are fundamentally linked to the structure of the polymer backbones at the core of these materials. With that in mind, editing the polymer backbone composition offers exciting opportunities to transform the plastics economy; yet, few examples of such transformations utilize commodity plastics as starting materials. In this work, we describe the development of a tandem C–H oxidation/hydroxyalkyl azide mediated rearrangement strategy that converts polyethylene into “polyethylene-like” materials with iminium ethers, esters, amides, and other pendant chemical functionality. Control over formation of esters or amides is achieved by variation of the hydroxyalkyl azide reagent, as well as processing conditions. By targeting specific functionalities, a variety of thermal and mechanical properties can be accessed. For example, incorporation of iminium ethers decreases the Young’s modulus of post-consumer PE from 196 MPa to 69–83 MPa, but conversion of the iminium ethers to esters and amides produces materials with moduli of 212–287 MPa—values higher than the original material. Thus, the demonstration of a modular backbone editing methodology for polyethylene showcases the broader value of this emerging strategy for polymer modification.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452353","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}
Thermosetting polymer materials have been widely used in many fields due to their excellent properties. Due to the restriction of the crosslinking network, traditional thermosetting polymer materials exhibit insolubility and immiscibility. Therefore, reprocessing of thermosetting polymer materials is a great challenge. With the depletion of petroleum-based resources, the utilization of natural resources for the preparation of bio-based thermosetting polymer materials is a major trend. In this study, eugenol-based covalent adaptable thermosets were prepared by UV curing and thermal curing according to thiol click chemistry. The mechanical properties of the eugenol-based covalent adaptable thermosets could be regulated according to the components, which were better than those of the control sample. The eugenol-based covalent adaptable thermosets exhibited excellent transparency and UV shielding properties. The introduction of dynamic covalent boronic ester (BSH) promoted the formation of residual char and enhanced the fire safety of eugenol-based covalent adaptable thermosets. Because of the dynamic borate ester bonds in the cross-linked network, the eugenol-based covalent adaptable thermosets exhibited significant stress relaxation behavior, excellent shape memory function and self-healing properties. The samples could be reprocessed at 100 °C several times. After three cycles of pulverizing and hot pressing, the recovery ratio of the tensile strength for the reprocessed samples remained above 85%. This study provides a novel strategy for preparing self-healable, reprocessable and anti-flammable covalent adaptable thermosets with tunable mechanical properties.
热固性聚合物材料以其优异的性能被广泛应用于许多领域。由于交联网络的限制，传统的热固性聚合物材料表现出不溶性和不粘性。因此，热固性聚合物材料的再加工是一项巨大的挑战。随着石油资源的枯竭，利用自然资源制备生物基热固性聚合物材料是大势所趋。本研究采用硫醇点击化学法，通过紫外固化和热固化制备了丁香酚基共价适应性热固性塑料。丁香酚基共价适应性热固性塑料的力学性能可根据组分进行调节，其力学性能优于对照样品。丁香酚基共价适应性热固性塑料具有优异的透明度和紫外线屏蔽性能。动态共价硼酸酯（BSH）的引入促进了残炭的形成，提高了丁香酚基共价适应性热固性塑料的防火安全性。由于交联网络中的动态硼酸酯键，丁香酚基共价适应性热固性塑料表现出显著的应力松弛行为、优异的形状记忆功能和自愈合性能。样品可在 100 °C 下多次重复加工。经过三次粉碎和热压循环后，再加工样品的拉伸强度恢复率保持在 85% 以上。这项研究为制备具有可调机械性能的自愈合、可再加工和抗燃共价适应性热固性塑料提供了一种新的策略。
{"title":"Self-healable, reprocessable and anti-flammable eugenol-derived covalent adaptable thermosets based on dynamic covalent boronic esters and thiol-ene click chemistry","authors":"Haoxin Niu, Yu Li, Ping Zhang, Wenwen Guo, Xin Wang, Yuan Hu","doi":"10.1039/d4py00684d","DOIUrl":"https://doi.org/10.1039/d4py00684d","url":null,"abstract":"Thermosetting polymer materials have been widely used in many fields due to their excellent properties. Due to the restriction of the crosslinking network, traditional thermosetting polymer materials exhibit insolubility and immiscibility. Therefore, reprocessing of thermosetting polymer materials is a great challenge. With the depletion of petroleum-based resources, the utilization of natural resources for the preparation of bio-based thermosetting polymer materials is a major trend. In this study, eugenol-based covalent adaptable thermosets were prepared by UV curing and thermal curing according to thiol click chemistry. The mechanical properties of the eugenol-based covalent adaptable thermosets could be regulated according to the components, which were better than those of the control sample. The eugenol-based covalent adaptable thermosets exhibited excellent transparency and UV shielding properties. The introduction of dynamic covalent boronic ester (BSH) promoted the formation of residual char and enhanced the fire safety of eugenol-based covalent adaptable thermosets. Because of the dynamic borate ester bonds in the cross-linked network, the eugenol-based covalent adaptable thermosets exhibited significant stress relaxation behavior, excellent shape memory function and self-healing properties. The samples could be reprocessed at 100 °C several times. After three cycles of pulverizing and hot pressing, the recovery ratio of the tensile strength for the reprocessed samples remained above 85%. This study provides a novel strategy for preparing self-healable, reprocessable and anti-flammable covalent adaptable thermosets with tunable mechanical properties.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142443937","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}
With the demand for increasingly smaller feature sizes, extreme ultraviolet (EUV) lithography has become the cutting-edge technology for fabricating highly miniaturized integrated circuits. However, the limited brightness of EUV light source, the distinct exposure mechanism, and the high resolution required for patterns pose significant challenges for resist materials—particularly for conventional polymeric resists, which often suffer from low EUV absorption, high molecular weight, and nonhomogeneous composition. In this Review, we focus on polymer resists for EUV lithography and offer our perspectives on recent exciting advances in the polymer chemistry of these resists. For example, in recent years, there has been significant progress in incorporating high EUV-absorbing moieties and photosensitizers into resists to enhance EUV absorbance and quantum efficiency. Additionally, advancements have been made in developing single-component chemically amplified resists (CARs) with covalently attached photoacid generators (PAGs), as well as in main-chain scission-type resists. Furthermore, the creation of precision oligomeric resists with precisely defined primary sequences and discrete molecular weights has opened new possibilities for EUV resist design. Lastly, we provide a critical outlook on the future opportunities and challenges in the development of EUV resists.
{"title":"Emerging trends in the chemistry of polymeric resists for extreme ultraviolet lithography","authors":"Jie Cen, Zhengyu Deng, Shiyong Liu","doi":"10.1039/d4py00957f","DOIUrl":"https://doi.org/10.1039/d4py00957f","url":null,"abstract":"With the demand for increasingly smaller feature sizes, extreme ultraviolet (EUV) lithography has become the cutting-edge technology for fabricating highly miniaturized integrated circuits. However, the limited brightness of EUV light source, the distinct exposure mechanism, and the high resolution required for patterns pose significant challenges for resist materials—particularly for conventional polymeric resists, which often suffer from low EUV absorption, high molecular weight, and nonhomogeneous composition. In this Review, we focus on polymer resists for EUV lithography and offer our perspectives on recent exciting advances in the polymer chemistry of these resists. For example, in recent years, there has been significant progress in incorporating high EUV-absorbing moieties and photosensitizers into resists to enhance EUV absorbance and quantum efficiency. Additionally, advancements have been made in developing single-component chemically amplified resists (CARs) with covalently attached photoacid generators (PAGs), as well as in main-chain scission-type resists. Furthermore, the creation of precision oligomeric resists with precisely defined primary sequences and discrete molecular weights has opened new possibilities for EUV resist design. Lastly, we provide a critical outlook on the future opportunities and challenges in the development of EUV resists.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436336","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}
Jessica Lalonde, Ghanshyam Pilania, Babetta L Marrone
Conventional plastics pose significant environmental and health risks across their life cycle, driving intense interest in sustainable alternatives. Among these, polyhydroxyalkanoates (PHAs) stand out for their biocompatibility, degradation characteristics, and diverse applications. Yet, challenges like production cost, scalability, and limited chemical variety hinder their widespread adoption, impacting material selection and design. This review examines PHA research through the lens of the classical materials tetrahedron, exploring property-structure-processing-performance (PSPP) relationships. By analyzing recent literature and addressing current limitations, we gain valuable insights into PHA development. Despite challenges, we remain optimistic about the role of PHAs in transitioning towards a circular plastic economy, emphasizing the need for further research to unlock their full potential.
{"title":"Materials Designed to Degrade: Structure, Properties, Processing, and Performance Relationships in Polyhydroxyalkanoate Biopolymers","authors":"Jessica Lalonde, Ghanshyam Pilania, Babetta L Marrone","doi":"10.1039/d4py00623b","DOIUrl":"https://doi.org/10.1039/d4py00623b","url":null,"abstract":"Conventional plastics pose significant environmental and health risks across their life cycle, driving intense interest in sustainable alternatives. Among these, polyhydroxyalkanoates (PHAs) stand out for their biocompatibility, degradation characteristics, and diverse applications. Yet, challenges like production cost, scalability, and limited chemical variety hinder their widespread adoption, impacting material selection and design. This review examines PHA research through the lens of the classical materials tetrahedron, exploring property-structure-processing-performance (PSPP) relationships. By analyzing recent literature and addressing current limitations, we gain valuable insights into PHA development. Despite challenges, we remain optimistic about the role of PHAs in transitioning towards a circular plastic economy, emphasizing the need for further research to unlock their full potential.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142439635","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}
Gavin Irvine, Stuart Herron, Daniel W. Lester, Efrosyni Themistou
Biocompatible, acid-labile cross-linked star polymer model networks (CSPMNs) have a great potential for use in drug delivery. However, a primary complication of this research stems from the prevalence for their synthesis to take place in organic solvents. Herein, to minimize CSPMN potential cytotoxicity, aqueous reversible addition-fragmentation chain transfer polymerization is employed for their synthesis. Initially, “arm-first” star polymers were synthesized in water using poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) homopolymer and, non-degradable ethylene glycol dimethacrylate or acid-labile diacetal-based bis[(2-methacryloyloxy)ethoxymethyl] ether cross-linker. Subsequently, OEGMA addition resulted in preparation of “in-out” star polymers (with higher molecular weights) followed by cross-linker addition to form CSPMNs. Rhodamine B dye encapsulation was performed during CSPMN synthesis and its release was observed in biologically relevant conditions. Having shown the effective breakdown of the diacetal-based CSPMNs, their potential for use in drug delivery in low pH environments (i.e. cancerous tumors) is expected to be high.
{"title":"Acid-labile and non-degradable cross-linked star polymer model networks by aqueous polymerization for in situ encapsulation and release","authors":"Gavin Irvine, Stuart Herron, Daniel W. Lester, Efrosyni Themistou","doi":"10.1039/d3py00677h","DOIUrl":"https://doi.org/10.1039/d3py00677h","url":null,"abstract":"Biocompatible, acid-labile cross-linked star polymer model networks (CSPMNs) have a great potential for use in drug delivery. However, a primary complication of this research stems from the prevalence for their synthesis to take place in organic solvents. Herein, to minimize CSPMN potential cytotoxicity, aqueous reversible addition-fragmentation chain transfer polymerization is employed for their synthesis. Initially, “arm-first” star polymers were synthesized in water using poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA) homopolymer and, non-degradable ethylene glycol dimethacrylate or acid-labile diacetal-based bis[(2-methacryloyloxy)ethoxymethyl] ether cross-linker. Subsequently, OEGMA addition resulted in preparation of “in-out” star polymers (with higher molecular weights) followed by cross-linker addition to form CSPMNs. Rhodamine B dye encapsulation was performed during CSPMN synthesis and its release was observed in biologically relevant conditions. Having shown the effective breakdown of the diacetal-based CSPMNs, their potential for use in drug delivery in low pH environments (i.e. cancerous tumors) is expected to be high.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431620","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}
To decrease the proteins, bacteria, and cells adhesive and increase the usage duration of implants, minimizing biofouling is crucial in medical industries. Traditionally, antifouling coatings are covalently bonded to substrates, a process that can be time-consuming or substrate-dependent. In this study, we synthesized both block and random copolymers using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and methacryloxyethyltrimethyl ammonium chloride (METAC) through reversible addition-fragmentation chain transfer (RAFT) polymerization. These copolymers can be adsorbed onto metal-phenolic network (MPN)-modified substrates based on cation-π interactions, rapidly forming antifouling coatings in about 6 min. Due to the wide surface modification ability of MPN, the antifouling coatings could form on various substrates. The antifouling coatings can effectively resist against the adhesion of protein, cell, and bacterial. Moreover, block copolymers exhibited superior antifouling abilities compared to random copolymers. Notably, the antifouling performance of copolymers can be promoted by increasing the amount of PEGMA and METAC. The advantage of the reported method is rapid preparation of antifouling coatings on various substrates. In addition, the study provides an insight into the factors influencing the strength of cation-π interaction.
{"title":"Rapid Formation of Antifouling Coatings via Cation-π Interactions","authors":"Zhicheng Huang, Kaijie Zhao, Shaoyin Wei, Yingxin Hao, Qina Yu, Jingcheng Hao, Jiwei Cui, Peiyu Zhang","doi":"10.1039/d4py00859f","DOIUrl":"https://doi.org/10.1039/d4py00859f","url":null,"abstract":"To decrease the proteins, bacteria, and cells adhesive and increase the usage duration of implants, minimizing biofouling is crucial in medical industries. Traditionally, antifouling coatings are covalently bonded to substrates, a process that can be time-consuming or substrate-dependent. In this study, we synthesized both block and random copolymers using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and methacryloxyethyltrimethyl ammonium chloride (METAC) through reversible addition-fragmentation chain transfer (RAFT) polymerization. These copolymers can be adsorbed onto metal-phenolic network (MPN)-modified substrates based on cation-π interactions, rapidly forming antifouling coatings in about 6 min. Due to the wide surface modification ability of MPN, the antifouling coatings could form on various substrates. The antifouling coatings can effectively resist against the adhesion of protein, cell, and bacterial. Moreover, block copolymers exhibited superior antifouling abilities compared to random copolymers. Notably, the antifouling performance of copolymers can be promoted by increasing the amount of PEGMA and METAC. The advantage of the reported method is rapid preparation of antifouling coatings on various substrates. In addition, the study provides an insight into the factors influencing the strength of cation-π interaction.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431621","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}
The development of catalytic systems is a central area of research in carbon dioxide (CO2) and epoxy copolymerization. A novel trinuclear cyclohexane-bridged tetradentate Schiff base chromium complex 1 was synthesized as a catalyst for the ring-opening copolymerization (ROCOP) of CO2 and cyclohexene oxide (CHO), resulting in the formation of poly (cyclohexene carbonate) (PCHC). The impact of polymerization temperature, CO2 pressure, reaction time, and catalyst loading on complex 1's polymerization activity was systematically investigated. It was observed that, with the addition of the co-catalyst PPNN3 (PPN= bis(triphenylphosphine)iminium), complex 1 exhibited enhanced catalytic activity for the ROCOP of CO2 and CHO under mild conditions. In contrast, the mononuclear tetradentate Schiff base chromium complex 2 system showed low activity under the same conditions. Compared to complex 2, complex 1 achieved a higher CHO conversion rate (70%) and 85% PCHC selectivity, with a turnover frequency (TOF) of 419 h-1, which is 5.3 times greater than that of complex 2. Additionally, the polymer produced by complex 1 had a molecular weight of 13790 g/mol, which is higher than that produced by complex 2 (8800 g/mol) and the commercial Salen CrCl catalyst (9610 g/mol). By varying the amounts of complex 1 and CHO, PCHC with different molecular weights (6000 g/mol to 14000 g/mol) and low dispersity can be easily obtained. Notably, the activation energy barrier for polycarbonate formation in the complex 1 system was 21.63 kJ/mol, compared to 32.88 kJ/mol in the complex 2 system.
{"title":"Catalytic Copolymerization of Carbon Dioxide and Cyclohexene Oxide by a Trinuclear Cyclohexane-bridged Tetradentate Schiff Base Chromium Complex","authors":"Jie Huang, Boxiong Shen","doi":"10.1039/d4py00956h","DOIUrl":"https://doi.org/10.1039/d4py00956h","url":null,"abstract":"The development of catalytic systems is a central area of research in carbon dioxide (CO2) and epoxy copolymerization. A novel trinuclear cyclohexane-bridged tetradentate Schiff base chromium complex 1 was synthesized as a catalyst for the ring-opening copolymerization (ROCOP) of CO2 and cyclohexene oxide (CHO), resulting in the formation of poly (cyclohexene carbonate) (PCHC). The impact of polymerization temperature, CO2 pressure, reaction time, and catalyst loading on complex 1's polymerization activity was systematically investigated. It was observed that, with the addition of the co-catalyst PPNN3 (PPN= bis(triphenylphosphine)iminium), complex 1 exhibited enhanced catalytic activity for the ROCOP of CO2 and CHO under mild conditions. In contrast, the mononuclear tetradentate Schiff base chromium complex 2 system showed low activity under the same conditions. Compared to complex 2, complex 1 achieved a higher CHO conversion rate (70%) and 85% PCHC selectivity, with a turnover frequency (TOF) of 419 h-1, which is 5.3 times greater than that of complex 2. Additionally, the polymer produced by complex 1 had a molecular weight of 13790 g/mol, which is higher than that produced by complex 2 (8800 g/mol) and the commercial Salen CrCl catalyst (9610 g/mol). By varying the amounts of complex 1 and CHO, PCHC with different molecular weights (6000 g/mol to 14000 g/mol) and low dispersity can be easily obtained. Notably, the activation energy barrier for polycarbonate formation in the complex 1 system was 21.63 kJ/mol, compared to 32.88 kJ/mol in the complex 2 system.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431623","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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