Michael Czuczola, Munshi Sahid Hossain, Declan P. Shannon, Parker T. Morris, Patrick T. Getty, Christopher M. Bates, Javier Read de Alaniz, Craig J. Hawker
{"title":"Telechelic Dithiol Copolymers as Tunable Building Blocks for Synthesizing Multiblock Materials","authors":"Michael Czuczola, Munshi Sahid Hossain, Declan P. Shannon, Parker T. Morris, Patrick T. Getty, Christopher M. Bates, Javier Read de Alaniz, Craig J. Hawker","doi":"10.1002/pol.20240876","DOIUrl":"https://doi.org/10.1002/pol.20240876","url":null,"abstract":"<p>A new strategy is reported to access <i>α</i>,<i>ω</i>-dithiol polymer building blocks with tunable molecular weights and compositions for the preparation of random multiblock copolymers based on styrenic, acrylic, and siloxane repeat units. This facile synthetic approach provides access to dithiols through a two-step process: (1) an initial copolymerization of vinyl monomers with ethyl lipoate followed by (2) disulfide bond reduction, producing dithiol terminated polymer products. Thiol-terminated polymers are easily prepared over a wide range of molecular weights (2–32 kDa) by simply controlling the feed ratio of vinyl monomer to ethyl lipoate. Mixtures of these linear dithiol-terminated building blocks were repolymerized via oxidative coupling to create random multiblock copolymers with high molecular weights (68–95 kDa) and controlled degradability. In summary, this approach for preparing and recombining telechelic dithiol polymers creates opportunities to manipulate the mechanical and physical properties of multiblock copolymers using a synthetically simple and versatile platform.</p>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 3","pages":"759-765"},"PeriodicalIF":3.9,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/pol.20240876","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143113244","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Michaela Vaňková, Lucie Havelková, Jiří Brus, Olga Kočková, Eliška Vyskočilová, Alice Vagenknechtová, Radek Coufal, Bogdana Bashta, Jan Sedláček
{"title":"Rh(I) Catalyzed Polymerization of Propargylated Monosaccharides to Electrospinable Helically Chiral Linear Polyacetylenes and Sorption-Active Porous Polyacetylene Networks","authors":"Michaela Vaňková, Lucie Havelková, Jiří Brus, Olga Kočková, Eliška Vyskočilová, Alice Vagenknechtová, Radek Coufal, Bogdana Bashta, Jan Sedláček","doi":"10.1002/pol.20240639","DOIUrl":"https://doi.org/10.1002/pol.20240639","url":null,"abstract":"<p>We report the Rh(I)-catalyzed chain-growth polymerizations of propargylated monosaccharides to form π-conjugated polyacetylene-type products with the monosaccharide substituents attached to the polyacetylene backbone via short methylene spacers. The homopolymerization provides helically chiral linear polyacetylenes of <i>M</i>\u0000 <sub>\u0000 <i>w</i>\u0000 </sub> ~ 20,000 soluble in either water (monosaccharide substituents with free <span></span>OH groups) or organic solvents (acetylated monosaccharide substituents). The methodology is established for the transformation of prepared chiral polymers into fibers (average diameter ~2.7 μm) taking advantage of the electrospinning technique. Copolymerization of propargylated monosaccharides with 1,3,5-triethynylbenzene cross-linker provides hyper-cross-linked polyacetylene networks with monosaccharide units content up to 46 wt.%, permanent micro/mesoporosity and <i>S</i>\u0000 <sub>BET</sub> area up to 482 m<sup>2</sup> g<sup>−1</sup>. The monosaccharide substituents of the networks serve as centers active in reversible isothermal adsorption of water vapor from the air. The achieved H<sub>2</sub>O capture capacity of 200 mg g<sup>−1</sup> (298 K, RH = 90%) shows monosaccharides as promising (co)building blocks for the construction of porous materials effective in water harvesting from air.</p>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 3","pages":"748-758"},"PeriodicalIF":3.9,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/pol.20240639","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143113245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Study of Nanocomposites Based on Organoclay-Filled Polypropylene/Poly(Butylene Succinate) Blends With Improved Electrical Properties","authors":"Sirine Taktak, Slim Fakhfakh, Omar Jbara, Sébastien Rondot","doi":"10.1002/pol.20240844","DOIUrl":"https://doi.org/10.1002/pol.20240844","url":null,"abstract":"<div>\u0000 \u0000 <p>This study explores the behavior of the polypropylene/polybutylene succinate (PP*/PBS) polymer blend and its nanocomposites containing varying amounts of organically modified montmorillonite (OMMT) (Cloisite20: C20) (1%, 2%, 3%, 5%, and 10%) when subjected to electron beam irradiation in a scanning electron microscope (SEM). More specifically, we have studied the electrical properties of nanocomposites, in particular the trapping and transport of electrons in the material, as well as the emission of electrons. To examine the storage and spreading of injected electrical charge in nanocomposites under electron irradiation, we used time-resolved current analysis method by measuring the induced currents (displacement and leakage currents). In order to verify whether there is a link between the electrical properties and the dispersion of the nanoclay particles in the polymer matrix, structural analyses were also carried out by x-ray diffraction (XRD). The results revealed a significant increase in the equilibrium trapped charge as the amount of clay nanoparticles introduced into the matrix increased. This trend can be attributed to both an increase in the number of involved traps and the presence of interfaces that act as defect sites. This was checked by determining the energy distribution of the traps using Simmons' approach. Correlating the measured displacement and leakage currents allowed us to demonstrate that the presence of clay nanoparticles leads to a decrease in the electron emission efficiency.</p>\u0000 </div>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 3","pages":"766-779"},"PeriodicalIF":3.9,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143113243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Sodium Alginate Composite Films Incorporated by Glycerol and Oxidized MWCNT for Driving Dielectric Elastomers","authors":"Chuang Li, Chenyu Xu, Xiangyu Song, Li Ma, Dehai Zhang, Dongjie Guo","doi":"10.1002/pol.20240734","DOIUrl":"https://doi.org/10.1002/pol.20240734","url":null,"abstract":"<div>\u0000 \u0000 <p>Dielectric elastomer actuators (DEAs) are widely used in many fields such as bionic robotics and wearable electronics. Due to a high elastic modulus and a poor flexibility, pure sodium alginate (SA) film constrains the deflection of DEA and is not suitable for using as the electrode. By incorporating the plasticizer of glycerol and the conductive fillers of oxidized multi-walled carbon nanotubes (MWCNTs), the resultant MWCNT/SA composite film exhibits a high flexibility and a high electrical conductivity (129 Ω·sq.<sup>−1</sup>), enabling it as the electrode to drive the dielectric matrix of VHB4910 for out-of-plane actuations. Driven by a relatively low electric field of 20.8 V/μm, the MWCNT/SA electrode DEA presents a desired areal strain of 3.8%. Long-term actuations reveal that the MWCNT/SA electrode DEA exhibits very stable electromechanical behaviors with a relative displacement shift (RDS) of 19.8% over 500 cycles, which is far lower than the commercial silicone electrode DEA, whose RDS is 127.8% under the same driven conditions.</p>\u0000 </div>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 3","pages":"739-747"},"PeriodicalIF":3.9,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143112319","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mariana Tasso, Jimena S. Tuninetti, Diego E. Pissinis, Sergio Moya, Omar Azzaroni
{"title":"Nanolayered Films of Spin-Coated, Covalently-Assembled Poly(Vinylpyrrolidone)- and Poly(Vinylpyridine)-Based Copolymers","authors":"Mariana Tasso, Jimena S. Tuninetti, Diego E. Pissinis, Sergio Moya, Omar Azzaroni","doi":"10.1002/pol.20240394","DOIUrl":"https://doi.org/10.1002/pol.20240394","url":null,"abstract":"<div>\u0000 \u0000 <p>Sequential deposition of polymer layers of very diverse characteristics has been applied to produce nanoassemblies of well-controlled thickness and physico-chemical properties. While conventional layer-by-layer approaches are based on the sequential deposition of distinct, mutually interacting materials, nanoassemblies formed by a single, unique polymer are challenged by the need of chemically interacting units to ensure layer-to-layer binding. Here, pyrrolidone and pyridine-containing polymers are mixed with the bifunctional crosslinker 1,6-dibromohexane and sequentially spin-coated as single, neutral polymers. The incorporation of the crosslinker within each deposited layer enables stepwise covalent bond formation while the nanofilm is being assembled. <i>N</i>-alkylation of amine groups by the crosslinker's alkyl halides during thermal annealing post-layer deposition ensures both intra and interlayer crosslinking with a single formulation. Thickness, growth profile, surface roughness, and wettability of the covalently bound nanoassemblies are evaluated together with their interaction with \u0000 <i>Staphylococcus aureus</i>\u0000 and HeLa cancer cells. The antibacterial and non-adhesive properties of a set of nanofilms are investigated and discussed in light of the physico-chemical characteristics of the films.</p>\u0000 </div>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 3","pages":"699-708"},"PeriodicalIF":3.9,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143110260","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
S. Rasoul Varedi, Bart Buffel, Frederik Desplentere
{"title":"Biaxial Thermo–Mechanical Response of ABS Sheet Above T\u0000 g Using DIC–Based Bubble Inflation Technique","authors":"S. Rasoul Varedi, Bart Buffel, Frederik Desplentere","doi":"10.1002/pol.20240690","DOIUrl":"https://doi.org/10.1002/pol.20240690","url":null,"abstract":"<div>\u0000 \u0000 <p>In this study, we examine the biaxial, large, and rapid deformation characteristics of heavy-gauge ABS sheets within the temperature range of 120°C to 160°C, relevant to the industrial forming process. A custom-built bubble inflation apparatus with a 300 mm diameter was designed for this purpose. Temperature uniformity across the sheet was verified using a thermal camera, while the temperature profile through the material's thickness was monitored during the heating using thermocouples near the top and bottom surfaces of the sheet. The bubble inflation test, combined with displacement, strain fields, and deformation rates at different locations, enables detailed characterization of the bubble's shape under large deformation. To address early-stage geometric instabilities due to sagging from thermal expansion, airflow was regulated with a precise flow control valve before inflation, while 3D-DIC monitored the real-time displacements to correct for sag deformation. The inflation pressure profile was recorded and synchronized with 3D-DIC strain evolution data for each test, allowing for analysis of the characteristic stress–strain curve at the pole. By evaluating the material's equi-biaxial properties at the pole and biaxial strain measurements away from the pole, the collected data provides a strong basis for future calibration of constitutive material models through an inverse approach, enabling accurate integration into process simulations.</p>\u0000 </div>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 3","pages":"724-738"},"PeriodicalIF":3.9,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143110262","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}