Polymer Chemistry最新文献_第3页

Polymerization Behavior of Biscarbenes Derived by Thermolysis of Bisdiazo Compounds 双重氮化合物热裂解合成双卡宾的聚合行为

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2025-04-23 DOI: 10.1039/d4py01474j

Mark G Moloney, Xiaosong Liu, Koji Okuda

引用次数: 0

Visible Light-Promoted Nickel-NHC Photocatalysts for Free Radical Photopolymerization and 3D Printing Application 用于自由基光聚合和三维打印应用的可见光促进型镍-NHC 光催化剂

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2025-04-23 DOI: 10.1039/d4py01252f

Naralyne Pesqueira, Fabrice Morlet-Savary, Michael Schmitt, Valdemiro P. Carvalho, Jr., Beatriz Eleutério Goi, Jacques Lalevée

{"title":"Visible Light-Promoted Nickel-NHC Photocatalysts for Free Radical Photopolymerization and 3D Printing Application","authors":"Naralyne Pesqueira, Fabrice Morlet-Savary, Michael Schmitt, Valdemiro P. Carvalho, Jr., Beatriz Eleutério Goi, Jacques Lalevée","doi":"10.1039/d4py01252f","DOIUrl":"https://doi.org/10.1039/d4py01252f","url":null,"abstract":"The evaluation of NiII complexes bearing bidentate N-heterocyclic carbene (NHC) ligands has shown great potential as catalysts in various reactions. However, their luminescence properties and photocatalytic applications remain underexplored. Two novel nickel-based NHC complexes, [Ni(py-NHC)2](PF6)2 (NiC1) and [Ni(ph-NHC)2] (NiC2), were synthesized with ligands N-Mesityl-N’-2-pyridylimidazolium Tetrafluorophosphate and 1-Mesityl-3-phenyl-1H-imidazol-3-ium Tetrafluorophosphate, respectively. The complexes were thoroughly characterized using spectroscopy techniques, including FTIR, UV-Vis, 1H NMR, and fluorescence, along with elemental analysis, cyclic voltammetry, and mass spectrometry. NiC1 and NiC2 exhibited emission properties and lifetime ranging of 3.8 and 9.1 ns, respectively. The photocatalytic properties of NiC1 and NiC2 were investigated for initiating free radical photopolymerization of ethoxylated trimethylolpropane triacrylate under violet light. This process incorporated di-tert-butyl-diphenyl iodonium hexafluorophosphate and ethyl dimethylaminobenzoate as additives. NiC2 achieved the highest monomer conversion under air or in laminate and was effective in on-off LED irradiation. Proposed oxidative and reductive mechanisms were supported by photolysis, fluorescence quenching, and electron spin resonance data. The optimized system was applied in 3D printing, producing smooth-surfaced, high-resolution patterns.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862166","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}

引用次数: 0

1,3-Diether-2-Methacrylates with Glycerol Skeletons: Tunable Resins for Stereolithography 3D Printing 1,3-二醚-2-甲基丙烯酸酯与甘油骨架：可调树脂立体光刻3D打印

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2025-04-23 DOI: 10.1039/d5py00198f

Zahra Sekhavat Pour, Pravin S. Shinde, Jun Wang, Cameron Woods, Seth Taylor, Sourav Chatterjee, Jason Edward Bara

{"title":"1,3-Diether-2-Methacrylates with Glycerol Skeletons: Tunable Resins for Stereolithography 3D Printing","authors":"Zahra Sekhavat Pour, Pravin S. Shinde, Jun Wang, Cameron Woods, Seth Taylor, Sourav Chatterjee, Jason Edward Bara","doi":"10.1039/d5py00198f","DOIUrl":"https://doi.org/10.1039/d5py00198f","url":null,"abstract":"The abundance of glycerol associated with biofuel production makes it an interesting substrate for a variety of new molecules. Our prior works have demonstrated the controlled and scalable synthesis of symmetric and asymmetric 1,3-diether-2-propanol compounds with a glycerol skeleton, which serve as versatile intermediates for further chemical modifications. Now we demonstrate that 1,3-diether-2-propanol compounds are useful building blocks to synthesize corresponding methacrylate monomers via Steglich esterification with methacrylic anhydride under mild catalytic conditions. The resulting methacrylate monomers were then successfully 3D printed as neat resins using a consumer-level printer. The thermal and mechanical properties of the printed materials were thoroughly investigated. The 3D-printed samples of 1,3-diethoxypropan-2-yl methacrylate (MAA-DEP) possessed good combinations of mechanical and thermal properties, with a tensile strength of 1.61 MPa, elongation at break of 143%, and a glass transition temperature (Tg) near 0 °C. A notable feature of the MAA-DEP monomer is its ability to dissolve polystyrene (PS). Thus, glycerol-based (meth)acrylate monomers present not only new molecules for 3D printing resins with tunable properties but also offer advancements in additive manufacturing by demonstrating how glycerol-derived acrylates also have solvating power to incorporate (waste) thermoplastics into SLA-printable formulations.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862442","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}

引用次数: 0

3D Printing via Polymerization-Induced Microphase Separation using Acrylate Macromonomers instead of MacroRAFT Agents 用丙烯酸酯大单体代替MacroRAFT试剂进行聚合诱导微相分离的3D打印

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2025-04-22 DOI: 10.1039/d5py00226e

Maxime Michelas, Nathaniel Corrigan, Cyrille Boyer

{"title":"3D Printing via Polymerization-Induced Microphase Separation using Acrylate Macromonomers instead of MacroRAFT Agents","authors":"Maxime Michelas, Nathaniel Corrigan, Cyrille Boyer","doi":"10.1039/d5py00226e","DOIUrl":"https://doi.org/10.1039/d5py00226e","url":null,"abstract":"Polymerization-induced microphase separation (PIMS) is a versatile technique for manufacturing nanostructured materials. Combining PIMS with 3D printing enables the fabrication of complex objects with nanoscale features, opening possibilities in diverse applications, including nanostructured ceramics, solid polymer electrolytes, and ion-exchange materials. Traditionally, PIMS utilizes polymers synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization (macromolecular Chain Transfer Agents, macroCTAs). However, RAFT-based PIMS can introduce undesirable color and odor into the final materials. To address these limitations, this study explores the use of macromonomers, polymers terminated with acrylate or methacrylate groups, as alternatives to macroCTAs. We synthesized a series of polycaprolactone (PCL) variants with identical molecular weights but differing terminal functionalities: acrylate, methacrylate, trithiocarbonate, and dithiobenzoate. This library enabled a direct comparison of macromonomer and macroCTA approaches for nanostructured material fabrication via PIMS. Small-angle X-ray scattering (SAXS) was employed to determine nanodomain sizes. Notably, both acrylate and trithiocarbonate-terminated PCLs yielded comparable nanodomain sizes. Exploiting PCL degradation, we fabricated nanoporous, 3D-printed objects by selectively etching the PCL from materials formed with both trithiocarbonate and acrylate-terminated PCL. Critically, the acrylate-terminated macromonomer-based PIMS system produced transparent, colorless materials with well-defined microstructures. This work demonstrates the potential of macromonomers to overcome the inherent limitations of RAFT-PIMS, providing a cleaner and more versatile pathway to advanced nanostructured materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857305","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}

引用次数: 0

Cation–π interactions in polymer science: from fundamental insights to material applications 高分子科学中的阳离子-π相互作用：从基础见解到材料应用

IF 4.1 2区化学

Polymer Chemistry Pub Date : 2025-04-22 DOI: 10.1039/D5PY00232J

Tianhang Zhou, Ning Wang, Yang Gao and Xiaoan Li

引用次数: 0

Deep eutectic ion-conductive hybrids produced by combining hydroxyl-functionalized silsesquioxane and mono-/difunctional hydrogen bond acceptors 由羟基功能化的硅氧烷和单/双官能氢键受体结合而成的深共晶离子导电杂合体

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2025-04-22 DOI: 10.1039/d5py00192g

Tomohito Inoue, Sota Saito, Akihiro Nishioka, Hideharu Mori

{"title":"Deep eutectic ion-conductive hybrids produced by combining hydroxyl-functionalized silsesquioxane and mono-/difunctional hydrogen bond acceptors","authors":"Tomohito Inoue, Sota Saito, Akihiro Nishioka, Hideharu Mori","doi":"10.1039/d5py00192g","DOIUrl":"https://doi.org/10.1039/d5py00192g","url":null,"abstract":"The use of ion-conductive organic–inorganic hybrids with high ionic conductivity, suitable flexibility/viscosity, and good thermal and mechanical properties is a promising approach for the development of next-generation, safer solid-state electrolytes. In this study, a series of new deep eutectic silsesquioxane (SQ) hybrids (DESQs) were developed by simply mixing hydroxyl-functionalized SQ acting as a polyol-type hydrogen bond donor (HBD) with imidazolium- and ammonium-based organic salts acting as hydrogen bond acceptors (HBAs) in the presence of a small amount of difunctional HBAs without the use of volatile organic solvents. The use of cross-linkable HBAs results in improved thermal stability and tunable flexibility (glass transition temperature and viscosity). The combination of hydroxyl-functionalized SQs and imidazolium salt-based mono-/difunctional HBAs afforded hybrids with hydrogen bond networks, showing a suitable balance between thermal properties and high ionic conductivity (4.17 × 10−4 S cm−1 at 25 °C), while maintaining reasonable viscosity (5.62 × 106 mPa S at 25 °C). The ionic conductivity can be improved by adding a lithium salt, allowing for an efficient approach for obtaining safer, greener, and cost-effective electrolytes with good ionic conductivity.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857302","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}

引用次数: 0

Biobased Oleyl Glycidyl Ether: Copolymerization with Ethylene Oxide, Postmodification, Thermal Properties, and Micellization Behavior 生物基油基缩水甘油醚：与环氧乙烷共聚，后改性，热性能和胶束行为

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2025-04-21 DOI: 10.1039/d5py00159e

Gregor M. Linden, Sandra Schüttner, Nora Fribiczer, Sebastian Seiffert, Holger Frey

{"title":"Biobased Oleyl Glycidyl Ether: Copolymerization with Ethylene Oxide, Postmodification, Thermal Properties, and Micellization Behavior","authors":"Gregor M. Linden, Sandra Schüttner, Nora Fribiczer, Sebastian Seiffert, Holger Frey","doi":"10.1039/d5py00159e","DOIUrl":"https://doi.org/10.1039/d5py00159e","url":null,"abstract":"Oleyl glycidyl ether (OlGE) is a highly hydrophobic monomer synthesized from a biobased fatty alcohol and epichlorohydrin. When combined with hydrophilic monomethoxy poly(ethylene glycol) (mPEG) macroinitiators, well-defined, highly amphiphilic AB block copolymers are obtained via anionic ring-opening polymerization (Đ ≤ 1.08). Surprisingly, an investigation of the copolymerization kinetics of OlGE and ethylene oxide revealed an almost ideally random copolymerization (rEO = 1.27, rOlGE = 0.78) despite the significant structural differences. Both statistical and block copolymers were investigated regarding their behavior in aqueous solution. The block copolymers of the type mPEG-b-POlGE featured two distinct melting temperatures (Tms). Besides a melting transition of mPEG, a second Tm is attributed to the crystallization of the cis-alkenyl side chain of the OlGE units. Varying degrees of side chain hydrogenation of the POlGE homopolymer using potassium azodicarboxylate (PADA) allowed for tailoring of the Tm. The thiol-ene click reaction allowed subsequent functionalization. This work not merely highlights the prospect of novel polyether surfactants, it also suggests the potential of biobased long-chain polyethers for the development of drug delivery systems featuring temperature-controlled release.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853393","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}

引用次数: 0

Alkali Lignin Stabilization of Oil-in-Water Emulsions via Simple Dispersion and Ozonation Processes 水包油乳状液中碱木质素的简单分散和臭氧化稳定

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2025-04-21 DOI: 10.1039/d5py00319a

Maëva Peloille, Henri Cramail, Frédérique Ham-Pichavant, Marie Reulier, Cécile Joseph, Stéphane Grelier

{"title":"Alkali Lignin Stabilization of Oil-in-Water Emulsions via Simple Dispersion and Ozonation Processes","authors":"Maëva Peloille, Henri Cramail, Frédérique Ham-Pichavant, Marie Reulier, Cécile Joseph, Stéphane Grelier","doi":"10.1039/d5py00319a","DOIUrl":"https://doi.org/10.1039/d5py00319a","url":null,"abstract":"An alkali lignin was subjected to successive processes enabling the stabilization of oil-in-water (O/W) emulsions. Firstly, by merely using a water/acetone mixture and evaporating acetone, more than 90% of this lignin could be dispersed in pure water, with no chemical modification involved. The obtained lignin dispersion was then subjected to an ozonation reaction, without requiring any additional steps, resulting in an increase of the carboxylic acid content (+193%), through effective cleavage of phenolic structures (-93%), and a decrease in the lignin molar masses, as evidenced by 31P quantitative NMR, 2D HSQC NMR, FT-IR spectroscopy and size-exclusion chromatography. These features allowed this alkali lignin to be easily re-dispersed in water. Aqueous dispersions of lignin before and after ozonation were characterized by an acidic pH and a bimodal nano-objects composition. These nano-objects exhibited a great affinity for interfaces, especially the ozonated lignin with an ability to reduce the surface tension of water down to 48 mN/m and the interfacial tension of a water/sunflower oil system down to 8 mN/m. Both lignins were consequently involved in the preparation of O/W emulsions and were able to stabilize micro-sized oil droplets, through a Pickering mechanism, preventing oil release under both accelerated and real-time conditions (30 days). These results demonstrated that stable emulsions could be obtained from simply processed lignins for potential applications in cosmetic formulations or for the entrapment of hydrophobic compounds in the agrochemical or pharmaceutical industries.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"41 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857303","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}

引用次数: 0

Ring-opening polymerization of six-membered 1,3-dioxa-2-silacycloalkanes by an organobase catalyst: precision polymerization and monomer regeneration by polymer degradation 有机碱催化剂开环聚合六元1,3-二氧杂环烷：精密聚合和聚合物降解再生单体

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2025-04-21 DOI: 10.1039/d5py00204d

Ikuto Tanaka, Sadahito Aoshima, Arihiro Kanazawa

引用次数: 0

Two-Stepping: Sol-gel-gel transitions in mixed thermoresponsive polymer systems 两步：混合热响应聚合物体系中的溶胶-凝胶-凝胶转变

IF 4.6 2区化学

Polymer Chemistry Pub Date : 2025-04-19 DOI: 10.1039/d4py00771a

Mohamad A. Abou-Shamat, Alan Reader, Eleanor Hilton, Niamh Haslett, Michael T Cook, Jesus Calvo-Castro, Jacqueline Leslie Stair, Najet Mahmoudi, Abhishek Rajbanshi, Marcelo Alves da Silva

{"title":"Two-Stepping: Sol-gel-gel transitions in mixed thermoresponsive polymer systems","authors":"Mohamad A. Abou-Shamat, Alan Reader, Eleanor Hilton, Niamh Haslett, Michael T Cook, Jesus Calvo-Castro, Jacqueline Leslie Stair, Najet Mahmoudi, Abhishek Rajbanshi, Marcelo Alves da Silva","doi":"10.1039/d4py00771a","DOIUrl":"https://doi.org/10.1039/d4py00771a","url":null,"abstract":"Conventional thermoreversible gels exhibit a sol-gel transition upon modulation of temperature. These systems are typically comprised of block copolymers in which one block exhibits a lower critical solution temperature (LCST), triggering a solvophilic to relatively solvophobic switch to that moiety when heated. The systems, which include poly(ethylene oxide)(PEO)-b-poly(propylene oxide)(PPO)-b-PEO (“Poloxamers”) and poly(N-isopropylacrylamide) (PNIPAM)-based block copolymers, thus exhibit a single step in their rheological profile upon heating, switching from a predominantly dissipative response to an elastic one. It has been found that a mixed tertiary system of PNIPAM-PEO-PNIPAM and Poloxamer 407 displays an unconventional sol-gel-gel transition. The rheological behaviours of this system have been studied to demonstrate the rheological profiles of the sol, “Gel I” and “Gel II” phases, as well as the reversibility of the gelation. A mechanism is proposed for this process, learning from dynamic light scattering and small-angle neutron-scattering experiments in dilute and concentrated regimes, respectively.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"65 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143851028","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}

引用次数: 0