Polymer Chemistry最新文献

{"title":"Emerging trends in the chemistry of polymeric resists for extreme ultraviolet lithography","authors":"Jie Cen ,&nbsp;Zhengyu Deng ,&nbsp;Shiyong Liu","doi":"10.1039/d4py00957f","DOIUrl":"10.1039/d4py00957f","url":null,"abstract":"<div><div>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 the 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. In addition, advancements have been made in developing single-component chemically amplified resists (CARs) with covalently attached photoacid generators (PAGs), as well as 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.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 45","pages":"Pages 4599-4614"},"PeriodicalIF":4.1,"publicationDate":"2024-11-04","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}

{"title":"[Ru]-Catalyzed Olefin Metathesis and Ethenolysis for the Synthesis and Recycling of Bio-Based Polycarbonates and Polycyanurates","authors":"Dana M. Pinson, Francesca D. Eckstrom, Gregory S. Ostrom, K. Randall McClain, Lawrence Baldwin, Benjamin Grant Harvey","doi":"10.1039/d4py00940a","DOIUrl":"https://doi.org/10.1039/d4py00940a","url":null,"abstract":"Eugenol, an abundant, naturally occurring phenolic compound, was converted into a thermoplastic polycarbonate by olefin metathesis followed by interfacial polymerization with triphosghene. This resulted in polymers with Mn ranging from 5300 – 12700 g mol-1 and an average glass transition temperature (Tg) of 82 °C. The polycarbonates were depolymerized via ethenolysis reactions under modest ethylene pressures (150 – 240 psi) in the presence of [Ru]-metathesis catalysts to yield a discrete monomer [bis(4-allyl-2-methoxyphenol) carbonate, compound 2]. 2 was then polymerized with a second generation Grubbs catalyst (M204) to produce a recycled polymer with Mn = 7500 g mol-1 and a Tg of 114 °C. The 32 °C increase in Tg was due to the isomerization of the allyl group to internal positions, which then allowed for the formation of stilbene and 3-carbon unsaturated linkages between aromatic groups. To expand the ethenolysis recycling approach to cross-linked networks, eugenol was converted into a cyanate ester (3), which was then thermally cyclotrimerized to generate 2,4,6-tris(4-allyl-2-methoxyphenoxy)-1,3,5-triazine (4), a monomer with a triazine core and three pendent aromatic rings with methoxy and allyl substituents. 4 was cross-linked via olefin metathesis (M204 catalyst) to generate a network with Mn = 8600 g mol-1 and a Tg of 180 °C. Similar to the polycarbonate, the polycyanurate was efficiently depolymerized in the presence of ethylene to regenerate 4. Compound 4 was then polymerized and depolymerized two additional times, demonstrating full circularity for the triazine monomer/network. The recycled networks exhibited similar Tgs (167–184 °C) and thermal stability compared to the virgin polymer. Overall, this work demonstrates that both thermoplastic and cross-linked networks can be readily prepared from eugenol and catalytically recycled under standard ethenolysis conditions. Unlike many conventional approaches, the recycled polymers described in this work exhibited no significant degradation in thermomechanical properties. This type of approach supports a circular bioeconomy and may help to reduce plastic waste and the accumulation of micro/nanoplastic particles in the environment.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"65 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574350","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}

{"title":"Enhanced mechanical properties of acrylate and 5-vinyl-2-norbornene-based ethylene terpolymers: rational design and synthesis using remotely modulated phosphine–sulfonate palladium complexes†","authors":"Yong-Qing Li ,&nbsp;Gui-Ping Cao ,&nbsp;Yu-Cai Cao","doi":"10.1039/d4py00722k","DOIUrl":"10.1039/d4py00722k","url":null,"abstract":"<div><div>From a practical perspective, it is important to maintain or increase the mechanical properties of functional ethylene copolymers to those of nonpolar polyethylene (PE). In this contribution, we report the enhanced mechanical properties of acrylate- and 5-vinyl-2-norbornene (VNB)-based ethylene terpolymers. Originally, phosphine-sulfonate and with methyl and phenyl installed <em>para</em> to the sulfonic group were synthesized and characterized. Subsequently, long-chain (but more challenging) polar monomers in which the polar groups combined linearly with double bonds (butyl acrylate (BA) and ethylene glycol monomethyl ether acrylate (EGMA)) were chosen to obtain more flexible chain structures. Crosslinkable and cyclic VNB were used, targeting at rapid crosslinking and enhanced material properties. Ethylene copolymerization and terpolymerization could be efficiently achieved using this strategy, and polymers exhibited improved surface and similar or enhanced mechanical properties compared with those of PE. High activity (2.9 × 10⁷ g (mol h)⁻¹) and high molecular weight (3.8 × 10⁵) were simultaneously observed in ethylene homopolymerization. E-BA(0.64) and E-EGMA(0.87) had a strain-at-break as high as 1016% and 974%, respectively, and stress-at-break up to 45 MPa compared with those of ethylene homopolymer. VNB-based terpolymers E-BA(0.68)–VNB(0.94) and E-EGMA(0.73)–VNB(1) displayed better tensile elongations (723% and 714%) than those of ENB- and DCPD-based terpolymers. Furthermore, though similar thermoplastic properties to PE (strain recovery (SR) = 10%) were observed, enhanced mechanical properties of teropolymers were obtained after sulfur vulcanization, with SR = 19–23% and Δ<em>σ</em> (stress differences) = 3.3–10.3 MPa.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 45","pages":"Pages 4662-4672"},"PeriodicalIF":4.1,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142488541","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}

{"title":"Control over membrane fluidity and biophysical properties of synthetic terpolymer stabilized complex coacervates†","authors":"Sebastian Novosedlik ,&nbsp;Alexander B. Cook ,&nbsp;Tim J. F. M. Voermans ,&nbsp;Henk M. Janssen ,&nbsp;Jan C. M. van Hest","doi":"10.1039/d4py00978a","DOIUrl":"10.1039/d4py00978a","url":null,"abstract":"<div><div>Cell membranes are vital barriers that regulate the composition of the intracellular environment and facilitate communication processes essential for cellular function and survival. In comparison to lipid membranes, artificial polymeric membranes generally offer enhanced stability due to their higher molecular weight and greater variability in the nature of the macromolecular building blocks, which provides access to a broad chemistry toolbox to regulate important features such as fluidity and permeability. We recently developed an artificial cell platform based on a complex coacervate, in which a terpolymer, composed of a hydrophilic poly(ethylene glycol) segment, a hydrophobic poly(caprolactone-<em>g</em>-trimethylene carbonate) domain and a polyglutamate anchor (PEG-<em>P</em>CL<em>g</em>TMC-PGA) was used for stabilization. These membranized structures showed excellent permeability, due to the high fluidity of the membrane. However, the polymer membrane proved to be unselective with regard to the molecular weight of guest molecules that were exchanged with the environment. To advance this platform, a series of terpolymers with distinctive features were synthesized to further refine their regulatory features of the polymer membrane. Through investigation of structural terpolymer variants, including those in which the hydrophobic domain was based on PCL<em>g</em>TMC, poly(<span>d</span>,<span>l</span>-lactic acid) or polystyrene, their influence on membrane permeability, fluidity, and sequestration of hydrophobic molecules, such as cholesterol, was determined. With this extended range of membrane-forming building blocks, this coacervate platform is equipped with tailored permeability through interactions with the coacervate lumen and facilitates sequestration of hydrophobic molecules into the membrane and controlled fluidity.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 45","pages":"Pages 4650-4661"},"PeriodicalIF":4.1,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/py/d4py00978a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142555766","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reversible aminolysis: a new concept for postpolymerization modification†","authors":"Koki Kasai ,&nbsp;Hideki Amii ,&nbsp;Ryohei Kakuchi","doi":"10.1039/d4py00827h","DOIUrl":"10.1039/d4py00827h","url":null,"abstract":"<div><div>Despite the powerful synthetic benefits of aminolysis postpolymerization modifications (PPMs), conventional aminolysis PPMs suffer from irreversibility owing to the difficulties in cleaving amide bonds formed from activated esters and amines. In this study, we propose a new aminolysis PPM system that enables reversible reactions by regenerating activated esters.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 45","pages":"Pages 4622-4626"},"PeriodicalIF":4.1,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574353","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}

{"title":"Long afterglow epoxidized soybean oil polymer composites with reversible dynamic cross-linking for intelligent coating†","authors":"Jiaman Hu, Zihao Wang, Minglin Yang, Chuansong Yu, Siyu Li, Yinggang Miao, Xiangqian Quan, Jize Liu and Shiyang Shao","doi":"10.1039/D4PY00857J","DOIUrl":"10.1039/D4PY00857J","url":null,"abstract":"<p >High-performance coatings with advanced functions such as long afterglow luminescence and self-healing have attracted great interest around the world, but the integration of these desirable multiple functions into a single composite system still remains a great challenge. Herein, an intelligent coating based on epoxidized soybean oil and modified long afterglow powders is presented for a self-healing intelligent coating. By constructing a dynamic hydrogen bonding network between natural polyphenols and epoxidized soybean oil, the obtained composites show desirable adhesive performances and self-healing ability: the shear strength of the obtained coating is able to reach 313.96 kPa while the self-healing efficiency was about 81.29% after a damage–healing process. Moreover, the introduction of SiO<small>₂</small>-modified SrAl<small>₂</small>O<small>₄</small>:Eu<small>²⁺</small>,Dy<small>³⁺</small> powders endows the intelligent coating with long afterglow ability, which greatly benefits the visualized monitoring of small cracks. Meanwhile, the obtained bio-sourced composites could be degraded under anaerobic composting conditions within 5 days, and after degradation the long afterglow powders could be separated and recycled with almost consistent performance (luminescent intensity remains 95.19%) in contrast to the original powders. This study offers valuable examples and new insights for the high-value utilization of bio-based materials.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 48","pages":" 4982-4992"},"PeriodicalIF":4.1,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142563191","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}

{"title":"Increasingly threaded polypseudorotaxanes with reduced enthalpies of melting","authors":"He Sun, Sean Gitter, Kiana Treaster, Joshua Marquez, Brent S Sumerlin, Kenneth Wagener, Austin M. Evans","doi":"10.1039/d4py01006j","DOIUrl":"https://doi.org/10.1039/d4py01006j","url":null,"abstract":"Polymers that contain mechanical bonds have unique and useful properties. It is difficult to prepare linear polyrotaxanes that contain well-defined mechanical bonds, which has made it challenging to establish the influence of mechanical bonding on linear polyrotaxane properties. We disclose the synthesis of 1,9-decadiene-pseudorotaxane linear copolymers with variable densities of threaded macrocycles using acyclic diene metathesis (ADMET) polymerization. This enabled our investigation into how macrocyclic threading impacts the thermomechanical properties of linear polypseudorotaxanes. Specifically, we observed that the melting enthalpy decreased from 67 to 5 J g-1 as we increased the molar incorporation of a pseudorotaxane unit. Going forward, we expect ADMET to be useful for preparing linear mechanically interlocked macromolecules at scales relevant for characterizing their thermomechanical properties.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142488542","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}

{"title":"Diversified synthesis of poly(sulfonyl isourea)s by multicomponent polymerizations of isocyanides, sulfonyl azides, and alcohols/phenols†","authors":"Dongyang Fan ,&nbsp;Fenggang Chen ,&nbsp;Dong Wang ,&nbsp;Ting Han ,&nbsp;Ben Zhong Tang","doi":"10.1039/d4py00953c","DOIUrl":"10.1039/d4py00953c","url":null,"abstract":"<div><div>Multicomponent polymerization (MCP) has become a powerful tool for the preparation of polymers with complex or well-defined structures. The development of MCPs that can take full advantage of the great diversity of monomer combinations is attractive but still remains challenging. Herein, we report a facile MCP method using isocyanides, sulfonyl azides, and alcohol/phenols as monomers, in which the monomer combination can be readily tuned to achieve the diversity-oriented synthesis of poly(sulfonyl isourea)s in excellent atom economy. By systematically optimizing the polymerization conditions and changing the functionalities and combinations of monomers, a series of heteroatom-rich polymers with sulfonyl isourea units and high molecular weights (<em>M</em>_w values of up to 120 500) were successfully prepared. All the obtained polymers exhibit good thermal stability, and the variation in polymer backbone structures led to an obvious difference in their morphological stability. This diversity-oriented MCP strategy may provide inspiration and new possibilities for the development of heterochain polymers with advanced functionalities.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 45","pages":"Pages 4673-4681"},"PeriodicalIF":4.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574594","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}

{"title":"Solvent quality shape control in continuous flow block copolymer self-assembly†","authors":"Axel-Laurenz Buckinx ,&nbsp;Lakshani J. Weerarathna ,&nbsp;Anna Sokolova ,&nbsp;Tanja Junkers","doi":"10.1039/d4py01174k","DOIUrl":"10.1039/d4py01174k","url":null,"abstract":"<div><div>Effects of solvent quality on block copolymer (BCP) self-assembly in flow are investigated. Stable kinetically trapped nanoaggregates are created using a continuous flow technique with turbulent mixing under systematically changing THF/water ratios. To elucidate particles morphologies, small angle neutron scattering (SANS) is used as an online analytical method. At high organic solvent contents, elongated particles are observed while at low contents shorter particles are formed. The method can hence be used in a versatile way to control particle morphologies without changing the BCP block lengths used for self-assembly. This offers a more efficient and flexible approach in drug delivery and biomedical applications where particle morphologies directly influence the cell uptake capabilities and reduces the need to resynthesize BCPs with varying block lengths to control size and morphology.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 45","pages":"Pages 4615-4621"},"PeriodicalIF":4.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142490067","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}

{"title":"Strategies to prepare polymers with cleavable linkages releasing active agents in acidic media","authors":"Nachnicha Kongkatigumjorn ,&nbsp;Daniel Crespy","doi":"10.1039/d4py00854e","DOIUrl":"10.1039/d4py00854e","url":null,"abstract":"<div><div>Incorporating labile bonds in the chemical structure of polymers yields interesting materials that are responsive to changes in environmental stimuli, such as pH. Active agents can be conjugated to various polymers through acid-labile linkages, conferring upon them spatiotemporal control over the cleavage and subsequent release of drugs, antibacterial agents or corrosion inhibitors. One key factor influencing the release of active agents is the hydrolytic stability of the linkages. We compared the hydrolytic kinetics of acid-cleavable linkages and discuss the effect of structural fine tuning of molecules on the hydrolysis rate. Synthetic routes towards various acid-sensitive linkages are discussed in relation with the functional unit available on the active substances to be released.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 44","pages":"Pages 4491-4518"},"PeriodicalIF":4.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142360129","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}