PolymersPub Date : 2024-10-30DOI: 10.3390/polym16213057
Alejandro Marqués, Jose Antonio Dieste, Iván Monzón, Alberto Laguía, Pascual Gracia, Carlos Javierre, Isabel Clavería, Daniel Elduque
{"title":"Improvements in Injection Moulds Cooling and Manufacturing Efficiency Achieved by Wire Arc Additive Manufacturing Using Conformal Cooling Concept.","authors":"Alejandro Marqués, Jose Antonio Dieste, Iván Monzón, Alberto Laguía, Pascual Gracia, Carlos Javierre, Isabel Clavería, Daniel Elduque","doi":"10.3390/polym16213057","DOIUrl":"10.3390/polym16213057","url":null,"abstract":"<p><p>The plastic injection moulding industry is a constantly developing industrial field. This industrial process requires the manufacturing of metal moulds using complex heating and cooling systems. The purpose of this research is to optimize both the plastic injection moulding process and the mould manufacturing process itself by combining practices in this industry with current additive manufacturing technologies, specifically Wire Arc Additive Manufacturing (WAAM) technology. A mould punch was manufactured by using both WAAM technology, whose internal cooling system has been designed under the concept of Conformal Cooling, and conventional cooling channel designs and manufacturing techniques in order to carry out a comparative analysis. Theoretical results obtained by CAE methods showed an improvement in heat extraction in the WAAM mould. In addition, the WAAM mould was able to achieve better temperature homogeneity in the final part, minimizing deformations in the final part after extraction. Finally, the WAAM manufacturing process was proven to be more efficient in terms of material consumption than the conventional mould, reducing the buy-to-fly ratio of the part by 5.11.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548201/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
PolymersPub Date : 2024-10-30DOI: 10.3390/polym16213050
Vesna Marija Potočić Matković, Ivana Salopek Čubrić, Katarina Krstović
{"title":"The Impact of Chlorinated Water and Sun Exposure on the Durability and Performance of Swimwear Materials.","authors":"Vesna Marija Potočić Matković, Ivana Salopek Čubrić, Katarina Krstović","doi":"10.3390/polym16213050","DOIUrl":"10.3390/polym16213050","url":null,"abstract":"<p><p>Understanding the factors that affect how materials age is essential for creating a durable product with long-lasting properties. It is also important to prioritize defining aging parameters that reflect the real-world conditions the materials will encounter. For this study, a range of swimwear materials were selected consisting of a blend of polymer (polyamide/polyester) and elastane in varying ratios. In order to simulate aging conditions, materials were immersed in chlorinated outdoor pool water during the summer season, either in shade or the sun, for 200 and 300 h. The materials were tested for mass per unit area, thickness, tensile properties, and moisture management. A slight mass per unit area increase was observed, rising from 1.0% after 200 h of chlorine and sunlight exposure to 3.7% after 300 h. Thickness increased by 1.7% after 200 h and 3.2% after 300 h of chlorine exposure, with no significant effect of sunlight. Breaking force dropped by 12.4% after 200 h in chlorine and 8.2% in chlorine and sunlight, becoming more pronounced after 300 h (65.7% in chlorine and 65.1% in chlorine and sunlight). The overall moisture management capability declined from 0.4888 to 0.3457 after 200 h in chlorine and 0.3393 with sunlight, dropping further after 300 h to 0.3838 and 0.3253, respectively.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548456/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626860","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
PolymersPub Date : 2024-10-30DOI: 10.3390/polym16213053
Xiansheng Wang, Jianjun Yang, Jian Zhong, Junsheng Yu, Xinjian Pan
{"title":"Innovative Materials for High-Performance Tin-Based Perovskite Solar Cells: A Review.","authors":"Xiansheng Wang, Jianjun Yang, Jian Zhong, Junsheng Yu, Xinjian Pan","doi":"10.3390/polym16213053","DOIUrl":"10.3390/polym16213053","url":null,"abstract":"<p><p>With the rapid development of lead-based perovskite solar cells, tin-based perovskite solar cells are emerging as a non-toxic alternative. Material engineering has been an effective approach for the fabrication of efficient perovskite solar cells. This paper summarizes the novel materials used in tin-based perovskite solar cells over the past few years and analyzes the roles of various materials in tin-based devices. It is found that self-assembling materials and fullerene derivatives have shown remarkable performance in tin-based perovskite solar cells. Finally, this article discusses design strategies for new materials, providing constructive suggestions for the development of innovative materials in the future.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548353/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
PolymersPub Date : 2024-10-30DOI: 10.3390/polym16213051
Maria Daniela Stelescu, Ovidiu-Cristian Oprea, Doina Constantinescu, Ludmila Motelica, Anton Ficai, Roxana-Doina Trusca, Maria Sonmez, Dana Florentina Gurau, Mihai Georgescu, Rodica Roxana Constantinescu, Bogdan-Stefan Vasile, Denisa Ficai
{"title":"Characterization of Mixtures Based on High-Density Polyethylene and Plasticized Starch.","authors":"Maria Daniela Stelescu, Ovidiu-Cristian Oprea, Doina Constantinescu, Ludmila Motelica, Anton Ficai, Roxana-Doina Trusca, Maria Sonmez, Dana Florentina Gurau, Mihai Georgescu, Rodica Roxana Constantinescu, Bogdan-Stefan Vasile, Denisa Ficai","doi":"10.3390/polym16213051","DOIUrl":"10.3390/polym16213051","url":null,"abstract":"<p><p>This paper presents the obtaining and characterization of blends based on high-density polyethylene (HDPE) and plasticized starch. In addition to plasticized starch (28.8% <i>w</i>/<i>w</i>), the compositions made also contained other ingredients, such as polyethylene-graft-maleic anhydride as a compatibilizer, ethylene propylene terpolymer elastomer, cross-linking agents, and nanoclay. Plasticized starch contains 68.6% <i>w</i>/<i>w</i> potato starch, 29.4% <i>w</i>/<i>w</i> glycerin, and 2% <i>w</i>/<i>w</i> anhydrous citric acid. Blends based on HDPE and plasticized starch were made in a Brabender Plasti-Corder internal mixer at 160 °C, and plates for testing were obtained using the compression method. Thermal analyses indicate an increase in the crystallization degree of the HDPE after the addition of plasticized starch. SEM micrographs indicate that blends are compatibilized, with the plasticized starch being well dispersed as droplets in the HDPE matrix. Samples show high hardness values (62-65° ShD), good tensile strength values (14.88-17.02 N/mm<sup>2</sup>), and Charpy impact strength values (1.08-2.27 kJ/m<sup>2</sup> on notched samples, and 7.96-20.29 kJ/m<sup>2</sup> on unnotched samples). After 72 h of water immersion at room temperature, mixtures containing a compatibilizer had a mass variation below 1% and water absorption values below 1.7%. Upon increasing the water immersion temperature to 80 °C, the sample without the compatibilizer showed a mass reduction of -2.23%, indicating the dissolution of the plasticized starch in the water. The samples containing the compatibilizer had a mass variation of max 8.33% and a water absorption of max 5.02%. After toluene immersion for 72 h at room temperature, mass variation was below 8%.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548385/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626789","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
PolymersPub Date : 2024-10-30DOI: 10.3390/polym16213055
El Mokhtar Saoudi Hassani, Hugo Duarte, João Brás, Abdeslam Taleb, Mustapha Taleb, Zakia Rais, Alireza Eivazi, Magnus Norgren, Anabela Romano, Bruno Medronho
{"title":"On the Valorization of Olive Oil Pomace: A Sustainable Approach for Methylene Blue Removal from Aqueous Media.","authors":"El Mokhtar Saoudi Hassani, Hugo Duarte, João Brás, Abdeslam Taleb, Mustapha Taleb, Zakia Rais, Alireza Eivazi, Magnus Norgren, Anabela Romano, Bruno Medronho","doi":"10.3390/polym16213055","DOIUrl":"10.3390/polym16213055","url":null,"abstract":"<p><p>Currently, industrial water pollution represents a significant global challenge, with the potential to adversely impact human health and the integrity of ecosystems. The continuous increase in global consumption has resulted in an exponential rise in the use of dyes, which have become one of the major water pollutants, causing significant environmental impacts. In order to address these concerns, a number of wastewater treatment methods have been developed, with a particular focus on physicochemical approaches, such as adsorption. The objective of this study is to investigate the potential of a bio-based material derived from olive oil pomace (OOP) as an environmentally friendly bio-adsorbent for the removal of methylene blue (MB), a cationic dye commonly found in textile effluents. The biobased material was initially characterized by determining the point of zero charge (pHpzc) and using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). Subsequently, a comprehensive analysis was conducted, evaluating the impact of specific physicochemical parameters on MB adsorption, which included a thorough examination of the kinetic and thermodynamic aspects. The adsorption process was characterized using Langmuir, Freundlich, Brunauer-Emmett-Teller (BET), and Dubinin Radushkevich (D-R) isotherms. The results suggest that the equilibrium of adsorption is achieved within ca. 200 min, following pseudo-second-order kinetics. The optimal conditions, including adsorbent mass, temperature, bulk pH, and dye concentration, yielded a maximum adsorption capacity of ca. 93% (i.e., 428 mg g<sup>-1</sup>) for a pomace concentration of 450 mg L<sup>-1</sup>. The results suggest a monolayer adsorption process with preferential electrostatic interactions between the dye and the pomace adsorbent. This is supported by the application of Langmuir, BET, Freundlich, and D-R isotherm models. The thermodynamic analysis indicates that the adsorption process is spontaneous and exothermic. This work presents a sustainable solution for mitigating MB contamination in wastewater streams while simultaneously valorizing OOP, an agricultural by-product that presents risks to human health and the environment. In conclusion, this approach offers an innovative ecological alternative to synthetic adsorbents.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548672/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626601","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
PolymersPub Date : 2024-10-30DOI: 10.3390/polym16213062
Samer Adwan, Teiba Obeidi, Faisal Al-Akayleh
{"title":"Chitosan Nanoparticles Embedded in In Situ Gel for Nasal Delivery of Imipramine Hydrochloride: Short-Term Stage Development and Controlled Release Evaluation.","authors":"Samer Adwan, Teiba Obeidi, Faisal Al-Akayleh","doi":"10.3390/polym16213062","DOIUrl":"10.3390/polym16213062","url":null,"abstract":"<p><p>Imipramine hydrochloride (IMP), a tricyclic antidepressant used for major depression, enuresis, and neuropathic pain, is limited by gastrointestinal complications, low oral bioavailability (44%), and complex dosing requirements. This study aimed to explore a novel non-invasive nasal delivery system using chitosan nanoparticles (Cs NPs) embedded in an in situ gel to address the limitations of oral IMP administration. Cs NPs loaded with IMP were synthesized via ionic gelation and assessed for precision in drug concentration using a validated HPLC method. The particles were integrated into a thermoresponsive polymer, Pluronic F127, to form an in situ gel suitable for nasal administration. The formulation was characterized for gelation temperature, duration, viscosity, mucoadhesive strength, and overall gel robustness. Drug release kinetics and the controlled release mechanism were studied using ex vivo permeation tests with Franz diffusion cells and nasal sheep mucosa. The optimized nanoparticle formulation (F4-50) exhibited a consistent PS of 141.7 ± 2.2 nm, a zeta potential (ZP) of 16.79 ± 2.1 mV, and a high encapsulation efficiency of 67.71 ± 1.9%. The selected in situ gel formulation, F4-50-P1, demonstrated a gelation temperature of 33.6 ± 0.94 °C and a rapid gelation time of 48.1 ± 0.7 s. Transform-attenuated total reflectance infrared spectroscopy (ATR-IR) confirmed the compatibility and effective encapsulation of IMP within the formulation. The release profile of F4-50 included an initial burst release followed by a sustained release phase, with F4-50-P1 showing improved control over the burst release. The flux rates were 0.50 ± 0.01 mg/cm<sup>2</sup>/h for F4-50 and 0.33 ± 0.06 mg/cm<sup>2</sup>/h for F4-50-P1, indicating effective permeation. The developed chitosan nanoparticle-based in situ gel formulation provides a promising approach for the controlled release of IMP, enhancing therapeutic efficacy and patient compliance while mitigating the disadvantages associated with oral delivery.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548429/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626838","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
PolymersPub Date : 2024-10-30DOI: 10.3390/polym16213056
Huiming Liu, Youcai Xiao, Yu Zou, Yong Han, Chenyang Fan, Yi Sun
{"title":"Dynamic Mechanical Properties and Constitutive Modeling of Polyurethane Microporous Elastomers.","authors":"Huiming Liu, Youcai Xiao, Yu Zou, Yong Han, Chenyang Fan, Yi Sun","doi":"10.3390/polym16213056","DOIUrl":"https://doi.org/10.3390/polym16213056","url":null,"abstract":"<p><p>The present study fabricated samples of polyurethane elastomers (PUEs) with three distinct densities and assessed their mechanical responses using split Hopkinson pressure bar (SHPB) tests. The findings reveal a significant increase in PUE stress with increasing strain rate and density. To further investigate the influence of strain rate sensitivity on PUEs, a strain rate sensitivity coefficient was employed to quantify the impact of strain rate on the mechanical properties of PUEs. Separate quantifications were performed for collapse stress, plateau stress, and densification strain as indicators of the strain rate sensitivity coefficient. The results demonstrate that the collapse stress sensitivity coefficient was notably affected by the applied strain rate. Additionally, both collapse and plateau stresses exhibited an increase with increasing density, which could be described by a power function relationship. Based on the theory of strain energy function, a constitutive model considering density and strain rate effects was developed to describe the stress-strain behavior of PUEs under various densities and strain rates. A comparison between this constitutive relationship and experimental results showed good agreement, highlighting its potential in describing dynamic mechanical behavior.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548374/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626983","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
PolymersPub Date : 2024-10-30DOI: 10.3390/polym16213060
Timo Meireman, Erik Verboven, Mathias Kersemans, Wim Van Paepegem, Karen De Clerck, Lode Daelemans
{"title":"Low-Velocity Impact Resistance and Compression After Impact Strength of Thermoplastic Nanofiber Toughened Carbon/Epoxy Composites with Different Layups.","authors":"Timo Meireman, Erik Verboven, Mathias Kersemans, Wim Van Paepegem, Karen De Clerck, Lode Daelemans","doi":"10.3390/polym16213060","DOIUrl":"10.3390/polym16213060","url":null,"abstract":"<p><p>This study investigates the effectiveness of polyether block amide (PEBA) thermoplastic elastomeric nanofibers in reducing low-velocity impact damage across three carbon fiber composite lay-up configurations: a cross-ply [0°/90°]2s (CP) and a quasi-isotropic [0°/45°/90°/-45°]s (QI) lay-up utilizing unidirectional plies, and a stacked woven [(0°,90°)]4s (W) lay-up using twill woven fabric plies. The flexural strength and interlaminar shear strength of the composites remained unaffected by the addition of nanofibers: around 750 MPa and 63 MPa for CP, 550 MPa and 58 MPa for QI, and 650 MPa and 50 MPa for W, respectively. The incorporation of nanofibers in the interlaminar regions resulted in a substantial reduction in projected damage area, ranging from 30% to 50% reduction over an impact energy range of 5-20 J. Microscopic analysis showed that especially the delamination damage decreased in toughened composites, while intralaminar damage remained similar for the cross-ply and quasi-isotropic lay-ups and decreased only in the woven lay-up. This agrees with the broad body of research that shows that interleaved nanofibers result in a higher delamination resistance due to toughening mechanisms related to nanofiber bridging of cracks. Despite their ability to mitigate delamination during impact, nanofibers showed limited positive effects on Compression After Impact (CAI) strength in quasi-isotropic and cross-ply composites. Interestingly, only the woven fabric composites demonstrated improved CAI strength, with a 12% improvement on average over the impact energy range, attributed to a reduction in both interlaminar and intralaminar damage. This study indicates the critical role of fiber integrity over delamination size in determining CAI performance, suggesting that the delaminations are not sufficiently large to induce buckling of sub-layers, thereby minimizing the effect of nanofiber toughening on the CAI strength.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548298/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142635792","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
PolymersPub Date : 2024-10-30DOI: 10.3390/polym16213052
Miroslaw Pluta, Joanna Bojda, Mariia Svyntkivska, Tomasz Makowski, Ele L de Boer, Ewa Piorkowska
{"title":"Crystallization-Controlled Structure and Thermal Properties of Biobased Poly(Ethylene2,5-Furandicarboxylate).","authors":"Miroslaw Pluta, Joanna Bojda, Mariia Svyntkivska, Tomasz Makowski, Ele L de Boer, Ewa Piorkowska","doi":"10.3390/polym16213052","DOIUrl":"10.3390/polym16213052","url":null,"abstract":"<p><p>Crystallization-controlled structure and thermal properties of biobased poly(ethylene 2,5-furandicarboxylate) (PEF) were studied. The cold-crystallization temperature controlled the structure and thermal properties of the biobased PEF. The melting was complex and evidenced the presence of a significant fraction of less-stable crystals with a low melting temperature that linearly increased with <i>T</i><sub>c</sub>, which formed already during the early stages of crystallization, together with those melting at a higher temperature. Low <i>T</i><sub>c</sub> resulted in the α'-phase formation, less crystallinity, and greater content of the rigid amorphous phase. At high <i>T</i><sub>c</sub>, the α-phase formed, higher crystallinity developed, the rigid amorphous phase content was lower, and the melting temperature of the less-stable crystals was higher; however, slight polymer degradation could have occurred. The applied thermal treatment altered the thermal behavior of PEF by shifting the melting of the less stable crystals to a significantly higher temperature. SEM examination revealed a spherulitic morphology. A lamellar order was evidenced with an average long period and small average lamella thickness, the latter about 3-3.5 nm, only slightly increasing with <i>T</i><sub>c</sub>.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548705/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626885","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Hydrogen Bond Donors in the Catalytic Pocket: The Case of the Ring-Opening Polymerization of Cyclic Esters Catalyzed by an Amino-Propoxide Aluminum Complex.","authors":"Salvatore Impemba, Antonella Viceconte, Irene Tozio, Shoaib Anwar, Gabriele Manca, Stefano Milione","doi":"10.3390/polym16213047","DOIUrl":"10.3390/polym16213047","url":null,"abstract":"<p><p>A new aluminum complex (NSO)AlMe<sub>2</sub> featuring a hydrogen bond donor on the ligand backbone has been synthesized via the reaction of AlMe<sub>3</sub> with 1-((2-(isopropylamino)phenyl)thio)propan-2-ol (NSO-H) and spectroscopically characterized. In the complex, the aluminum atom is in a distorted tetrahedral coordination sphere determined by the anionic oxygen and neutral nitrogen atoms of the ligand and by the two carbon atoms of the alkyl groups. After proper activation, the complex (NSO)AlMe<sub>2</sub> was able to promote the ring-opening polymerization of <i>L</i>-, <i>rac</i>-lactide, <i>ε</i>-caprolactone and <i>rac</i>-<i>β</i>-butyrolactone. The polymerization of <i>rac</i>-lactide was faster than that of <i>L</i>-lactide: in a toluene solution at 80 °C, the high monomer conversion of 100 equivalents was achieved in 1.5 h, reaching a turnover frequency of 63 mol<sub>LA</sub>·mol<sub>Al</sub><sup>-1</sup>·h<sup>-1</sup>. The experimental molecular weights of the obtained polymers were close to those calculated, assuming the growth of one polymer chain for one added alcohol equivalent and the polydispersity indexes were monomodal and narrow. The kinetic investigation of the polymerization led to the determination of the apparent propagation constants and the Gibbs free energies of activation for the reaction; the terminal groups of the polymers were also identified. The complex (NSO)AlMe<sub>2</sub> was active in harsh conditions such as at a very low concentration or in the melt using technical-grade <i>rac</i>-lactide. A relatively high level of activity was observed in the ring-opening polymerization of <i>ε</i>-caprolactone and <i>rac</i>-<i>β</i>-butyrolactone. DFT calculations were performed and revealed the central role of the NH function of the coordinated ligand. Acting as a hydrogen bond donor, it docks the monomer in the proximity of the metal center and activates it toward the nucleophilic attack of the growing polymer chain.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"16 21","pages":""},"PeriodicalIF":4.7,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11548642/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142626023","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}