Journal of Polymer Science最新文献

{"title":"Optimization of Starting Material Composition in the Synthesis of Highly Active Magnesium Ethoxide-Supported Ziegler–Natta Catalysts for Propylene Polymerization","authors":"Nona Ghasemi Hamedani,&nbsp;Mina Behrouzi-Fardmoghadam,&nbsp;Hossein Abedini,&nbsp;Naeimeh Bahri-Laleh,&nbsp;Albert Poater","doi":"10.1002/pol.20241109","DOIUrl":"https://doi.org/10.1002/pol.20241109","url":null,"abstract":"<div>\u0000 \u0000 <p>We aim to deepen our understanding of the structure-performance relationship in Ziegler–Natta catalysts (ZNCs) for propylene polymerization. To this end, three different Mg(OEt)₂ supports were synthesized by reacting magnesium powder with varying amounts of MnCl₂ during the magnesium-ethanol reaction stage. Despite similar XRD patterns among all obtained Mg(OEt)₂ samples, at an optimal MnCl₂/Mg ratio of 2 g/g, well-spherically shaped Mg(OEt)₂ particles with plate-like building units were formed. The prepared support precursors were then used in ZNC synthesis with different TiCl₄/Mg(OEt)₂ ratios and internal donor types, and their behavior in propylene polymerization was thoroughly explored. The overall results indicated that the optimal Ti/Mg ratio is 8 mol/mol. Additionally, phthalate as an internal donor demonstrated higher activity compared to diethyl ether or succinate-based internal donors. The kinetic curve of propylene uptake versus time in polymerization experiments with varying external donor content was mathematically modeled to evaluate changes in rate constants. The calculated rate constants showed that as the external donor content increases, k_trH, k_d, k_iED and k_tED all enhance, while k_p decreases significantly due to the poisoning of active sites by the external donor. These findings highlight the critical role of the type and amount of catalyst components in achieving optimal performance.</p>\u0000 </div>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 7","pages":"1580-1591"},"PeriodicalIF":3.9,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143761944","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":"Additive-Promoted Grignard Reagent Mediated Polymerization With Increased Radical Characteristic Yielding Polystyrene With Narrow Molecular Weight Distribution","authors":"Can-Ye Qiu,&nbsp;Jia-Rong Lai,&nbsp;Xin-Hui Wang,&nbsp;Shi-Xuan Ye,&nbsp;Xiao-Li Sun,&nbsp;Wen-Ming Wan","doi":"10.1002/pol.20241088","DOIUrl":"https://doi.org/10.1002/pol.20241088","url":null,"abstract":"<div>\u0000 \u0000 <p>Gaining polymer with narrow molecular weight distribution (<i>Đ</i>) by efficient living polymerization methods is fundamental and essential in polymer science. Grignard reagent mediated anionic polymerization is capable of low <i>Đ</i>, however, is not suitable for the polymerization of nonpolar monomers like styrene (St). Here, several kinds of additives like lithium chloride (LiCl) and <i>N,N,N′,N′′,N′′</i>-Pentamethyldiethylenetriamine (PMDETA) are demonstrated as efficient additives that can promote Grignard reagent mediated polymerization of St. Through LiCl-promoted Grignard reagent mediated polymerization, polystyrene (PS) with manipulated low <i>Đ</i> is successfully achieved under mild conditions with full monomer conversion, by using a series of Grignard reagents (RMgX) in the presence of LiCl. In comparison, no PS can be prepared for Grignard reagents in the absence of additive. Electron paramagnetic resonance reveals that radical characteristic of Grignard reagent is increased in the presence of additive, which eventually enables the successful polymerization of St under mild conditions with full monomer conversion. This work therefore opens a simple additive strategy to promote current living polymerization method and expands the monomer library of Grignard reagent mediated living polymerization, which might cause inspirations to current living polymerization and polymer chemistry.</p>\u0000 </div>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 7","pages":"1606-1613"},"PeriodicalIF":3.9,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143761946","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":"Investigation of the Influence of Fiber Stretching on N2-Pretreated PAN-Fibers and Development of a Shortened Stabilization Process Meeting the Requirements of the Carbon Fiber Industry","authors":"Ziwen Liu,&nbsp;Muhsin Mert Akbas,&nbsp;Thomas Gries,&nbsp;Daniel Kaußen,&nbsp;Thomas Henzler","doi":"10.1002/pol.20240994","DOIUrl":"https://doi.org/10.1002/pol.20240994","url":null,"abstract":"<p>Carbon fibers (CF) are characterized by their excellent mechanical properties and low specific weight. However, due to the high production costs of CF, the application areas of this material are highly limited. A more cost-effective production of CF through the use of N₂-pretreatment can further increase the spread in mass markets. In the research presented, the influence of fiber stretching on the properties of pretreated Polyacrylonitrile (PAN)-fibers as well as the resulting carbon fibers is investigated on continuous scale. The investigations show that the fibers can be stretched much more (&gt; 10%) during N₂-pretreatment than in air atmosphere without impairing the mechanical properties of resulting CF. With increasing stretching ratio, the E-modulus and tensile strength of the pretreated fibers are increasing while the elongation remains on a similar level as the reference carbon fibers. Using this effect, a more efficient stabilization process has been developed in which the first of four stabilizations zones has been skipped. This method ensures high acceptance by the industry, as the process parameters of the other three remaining stabilization zones are untouched. As a result, the thermal conversion time of CF has been reduced by 20% while the mechanical properties of the CF are maintained.</p>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 7","pages":"1592-1605"},"PeriodicalIF":3.9,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/pol.20240994","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143761945","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":"Preparation of Amylose-Mimicking Polymers for the Purification of Maltose-Binding Protein","authors":"Atsushi Miyagawa,&nbsp;Nami Yamamoto,&nbsp;Hatsuo Yamamura","doi":"10.1002/pol.20241130","DOIUrl":"https://doi.org/10.1002/pol.20241130","url":null,"abstract":"<div>\u0000 \u0000 <p>Maltose-binding protein (MBP) is used as affinity tags for purifying recombinant proteins via amylose affinity gels. However, the gel often yields a low quantity of the purified protein due to the biodegradability and low water solubility of immobilized amylose. Herein, water-soluble, anti-biodegradation amylose-mimicking polymers are synthesized by polymerizing a maltose monomer with a norbornene group, then copolymerizing it with a glucose monomer and norbornene. The synthesized polymers are further modified via hydrogenation and hydroxylation to alter their properties. The binding affinities of these polymers, which are evaluated using a quartz crystal microbalance instrument, indicated their binding to MBP mimics that of amylose. Furthermore, the polymer is immobilized on an agarose gel to prepare an affinity gel for MBP, which absorbs concanavalin A and MBP before eluting them. However, only 15% of MBP is absorbed, with the majority passing through the gel. This indicates that maltose is short enough to efficiently absorb MBP. However, amylose-mimicking polymers have higher water solubilities and are easier to handle than amylose polymers, making them expected to exhibit a higher MBP absorbability. Hence, optimizing ligand length and structure is key to improving MBP binding. Further, designs should focus on enhancing stability and binding efficiency to improve affinity purification.</p>\u0000 </div>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 7","pages":"1614-1627"},"PeriodicalIF":3.9,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143761925","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":"UV-Curable Polyester Oligomers Containing Triptycene Segments","authors":"Theodore J. Hammer,&nbsp;Coleen Pugh,&nbsp;Mark D. Soucek","doi":"10.1002/pol.20241056","DOIUrl":"https://doi.org/10.1002/pol.20241056","url":null,"abstract":"<div>\u0000 \u0000 <p>A series of UV-curable polyesters containing triptycene segments were synthesized via the melt polycondensation of 1,4-cyclohexanedicarboxylic acid, triptycene-1,4-hydroquinone-bis(2-hydroxyethyl) ether, and various comonomer diols including 1,6-hexanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol. The polyesters were characterized by ¹H nuclear magnetic resonance spectroscopy, Fourier-transform infrared spectroscopy, gel-permeation chromatography, and differential scanning calorimetry. Thin films were prepared by solvent casting and were cured via exposure to UV-light at elevated temperature. The crosslinked films were subsequently analyzed by differential scanning calorimetry, dynamic mechanical analysis, Soxhlet extractions, and tensile tests. Most of the samples that contained a high concentration of the triptycene monomer resulted in brittle materials with relatively high moduli and tensile strengths, but poor extensibilities. However, the 1,6-hexanediol/1,4-cyclohexanedicarboxylic acid polyester with 30 mol% of triptycene-1,4-hydroquinone-bis(2-hydroxyethyl) ether exhibited a <i>T</i>\u0000 _g above room temperature, a relatively high modulus (~1.1 GPa) and tensile strength (~25 MPa), and ductility (144% elongation-at-break). These unique properties were attributed to the triptycene monomer, which is capable of threading polymer chains through its V-shaped cavities to reinforce the polymer network. When these polyesters were formulated into UV-curable coatings, the coatings displayed excellent impact resistance and substrate adhesion.</p>\u0000 </div>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 7","pages":"1556-1569"},"PeriodicalIF":3.9,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143762165","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":"Synthesis and Metal Ion Adsorption Properties of a Dense Triazole Polymer Carrying Cysteine Residues","authors":"Ryo Ejima,&nbsp;Masaki Nakahata,&nbsp;Yuri Kamon,&nbsp;Akihito Hashidzume","doi":"10.1002/pol.20240752","DOIUrl":"https://doi.org/10.1002/pol.20240752","url":null,"abstract":"<p>Copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) is promising as a reaction to synthesize functional polymers consisting of 1,2,3-triazole units. Recently, we reported a series of dense 1,2,3-triazole polymers of 4-azido-5-hexynoic acid derivatives. Herein, we designed a new water-soluble dense 1,2,3-triazole polymer carrying amino acid residues in the side chains, that is, poly(<i>N</i>-(4-azido-5-hexynoyl)cysteine) (poly(AC)), bearing L-cysteine as a ligand for metal ions. CuAAC polymerization of a protected monomer followed by deprotection and neutralization yielded the sodium salt of poly(AC) (poly(AC)Na). The adsorption capacity of poly(AC)Na with Cd²⁺ was investigated with a colorimetric assay. Furthermore, the interactions for poly(AC) with group 12 metal ions (Zn²⁺, Cd²⁺, and Hg²⁺) were investigated using isothermal titration calorimetry (ITC) and transmittance measurements. Utilizing the colorimetric assay data, the Cd²⁺ adsorption capacity per unit weight of poly(AC)Na was evaluated to be 4–5 mmol g⁻¹, comparable to those of Cd²⁺ adsorbents reported previously. The ITC data demonstrated that the interactions of poly(AC)Na with Zn²⁺, Cd²⁺, and Hg²⁺ were predominantly exothermic. Based on the ITC data, apparent dissociation constants of interactions were roughly estimated to be in the order of 10⁻⁵–10⁻⁴ M, which are comparable to those for metal-binding biomolecules. The transmittance data indicated that the poly(AC)Na/CdCl₂ system underwent phase separation.</p>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 7","pages":"1570-1579"},"PeriodicalIF":3.9,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/pol.20240752","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143762055","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":"Flexible α-Diimine Ni(II) and Pd(II) Catalysts Featuring Backbone and Axial Cycloalkyl Substituents in Ethylene (Co)polymerization","authors":"Jianjian Dai,&nbsp;Shengyu Dai","doi":"10.1002/pol.20241186","DOIUrl":"https://doi.org/10.1002/pol.20241186","url":null,"abstract":"<div>\u0000 \u0000 <p>Recently, axial flexible substituents have found widespread application in ethylene (co)polymerization catalyzed by late transition metals, yielding impressive results. In this research, we designed and synthesized a novel class of flexible α-diimine Ni(II) and Pd(II) catalysts, distinguished by their flexible backbones and axial substituents that both incorporate cycloalkyl moieties. During nickel-catalyzed ethylene polymerization, these flexible nickel catalysts demonstrated high activity (well above 10⁶ g/(mol Ni·h)) and thermal stability, producing polyethylenes with very high molecular weights (up to 1022 kg/mol) and branching densities (up to 103/1000C). Interestingly, the catalyst reported in this study exhibits higher activity compared to nickel catalysts with classic and rigid backbones. The resultant polyethylene materials exhibited outstanding mechanical properties and elastic recovery (with a strain recovery (SR) of up to 79%), qualifying them as high-performance thermoplastic elastomers. In contrast, during palladium-catalyzed ethylene polymerization, these flexible palladium catalysts showed moderate activity (level of 10⁵ g/(mol Pd·h)) and generated polyethylenes with high branching densities (up to 99/1000C) and molecular weights (up to 203 kg/mol). In the case of palladium-catalyzed copolymerization of ethylene with methyl acrylate (MA), the copolymerization activity was notably reduced compared to homopolymerization, resulting in E-MA copolymers with lower molecular weights and higher branching densities. However, under the experimental copolymerization conditions, we successfully obtained copolymers with significant incorporation (1.53–4.54 mol%) of MA. It is worth noting that the cyclohexyl group displayed superior chain transfer inhibition in both nickel and palladium systems compared to the cyclopentyl group. Nevertheless, a notable difference was observed in their influence on branching density regulation: in the nickel system, the cyclohexyl group facilitated the formation of polyethylenes with higher branching, while in the palladium system, it had the opposite effect when compared to the cyclopentyl group.</p>\u0000 </div>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 7","pages":"1527-1535"},"PeriodicalIF":3.9,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143762164","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":"Self-Healing Ionogels Based on Ternary Polymer With Tunable Adhesion and Stretchability for Strain Sensing Applications","authors":"Senyuan Hao,&nbsp;Qizhi Ma,&nbsp;Menghui Cao,&nbsp;Yunchao Jia,&nbsp;Yilong Li","doi":"10.1002/pol.20241038","DOIUrl":"https://doi.org/10.1002/pol.20241038","url":null,"abstract":"<div>\u0000 \u0000 <p>Ionogels play a significant role in advancing flexible electronic devices due to their exceptional ion conductivity, thermal stability, biocompatibility, and electrical reliability. However, achieving integrated high-stretchability, self-adhesiveness, and self-healing properties simultaneously in a single system remains a huge challenge, which limits their range of applications. Here, a multifunctional ionogel is proposed for wearable strain sensors. The ionogel exhibits promising and adjustable mechanical properties, tunable adhesion, and good self-healing properties. We demonstrate that ionogels exhibit high strength (~1.3 MPa) along with exceptional elongation (~1700% strain), fracture energy (~1300 J m⁻²), self-healing capability, adhesion properties, and high sensitivity, thus expanding their potential applications to a wider range of scenarios. The method of adjusting the ionogel's molecular structure and enhancing its flexibility through a one-step copolymerization can also be applied to other monomers and ionic liquids, demonstrating potential as engineering materials and wearable sensors.</p>\u0000 </div>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 7","pages":"1536-1545"},"PeriodicalIF":3.9,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143762163","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":"Room-Temperature Healable and Mechanically Robust Polyurea-Urethane Based on Dynamic Tetrahedral Boronate-Esters Bonds and Hydrogen Bonds","authors":"Yujia Hao,&nbsp;Guangming Zhu,&nbsp;Ben Li","doi":"10.1002/pol.20241101","DOIUrl":"https://doi.org/10.1002/pol.20241101","url":null,"abstract":"<div>\u0000 \u0000 <p>Although some studies have reported high-toughness or high-strength self-healing materials, the self-healing process still requires demanding conditions such as high temperatures. It remains challenging to achieve a balance between mechanical properties and self-healing efficiency under mild conditions. Herein, we design a novel self-healing polyurea-urethane (PUU) material. The polymer has crosslinked internal “cores” and well-designed flexible chains with multiple alicyclic structures, which are crosslinked via tetrahedral boronate-esters bonds (TBEs) and hydrogen bonds, resulting in a dynamic crosslinked PUU network (denoted as TBE-PUU). The resulting materials (TBE-PUU₂) not only exhibit outstanding tensile strength (28.5 MPa), stretchability (1217%), toughness (166.1 MJ m⁻³), etc., but also possess excellent self-healing ability in response to water or thermal stimuli. It achieves high self-healing efficiency of 92.0% at room temperature for 48 h with the aid of water and 97.7% at 60°C for only 8 h. The new strategy offers new possibilities to seek a balance between material dynamic properties and mechanical robustness.</p>\u0000 </div>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 7","pages":"1546-1555"},"PeriodicalIF":3.9,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143762166","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":"Investigation of the Mechanical, Thermal, and Morphological Properties of ABS Composite Reinforced With Bentonite and DEHPA-Modified Bentonite","authors":"İdris Karagöz,&nbsp;B. Şebnem Şimşiroğlu,&nbsp;Elif Nur Özer,&nbsp;Harun Sepetcioglu,&nbsp;Jülide Hızal","doi":"10.1002/pol.20240925","DOIUrl":"https://doi.org/10.1002/pol.20240925","url":null,"abstract":"<p>This study investigates the mechanical, thermal, and surface characteristics of acrylonitrile–butadiene–styrene (ABS) composites reinforced with bentonite and bis(2-ethylhexyl) phosphate (DEHPA)-modified bentonite. The addition of bentonite significantly reduced the tensile strength and elongation at break due to the filler's inherent brittleness. Pure ABS exhibited a tensile strength of 42.2 MPa, which decreased by 16.1% with the incorporation of 20% bentonite (ABS1). Impact strength tests showed that the inclusion of bentonite lowered impact resistance, particularly in notched samples. Bentonite also increased the hardness and density, reflecting improved rigidity but reduced flexibility. Surface gloss changed from semigloss to matte, and FT-IR spectroscopy confirmed the successful integration of bentonite. Water absorption tests revealed that DEHPA-modified bentonite composites had higher absorption over time, highlighting the modification's effect on hydrophilicity. While bentonite improves certain properties, the balance between mechanical strength and flexibility needs to be further explored to meet the requirements of specific applications such as automotive components, electronics casings, and construction materials.</p>","PeriodicalId":16888,"journal":{"name":"Journal of Polymer Science","volume":"63 6","pages":"1505-1517"},"PeriodicalIF":3.9,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/pol.20240925","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622440","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}