European Polymer Journal最新文献_第4页

Degradation and in vivo evaluation of an innovative delayed release implant of medical grade poly(glycolide-co-trimethylene carbonate-co-ε-caprolactone) 创新型医用聚（乙二醇-三亚甲基碳酸酯-ε-己内酯）缓释植入物的降解和体内评估

IF 5.8 2区化学

European Polymer Journal Pub Date : 2024-11-09 DOI: 10.1016/j.eurpolymj.2024.113569

Norman L. Ilich , Enoch Chan , M. Scott Taylor , Brian Gaerke , Sinduja Suresh , Damien G. Harkin , Flavia Medeiros Savi , Siamak Saifzadeh , Dietmar W. Hutmacher , Tim R. Dargaville

{"title":"Degradation and in vivo evaluation of an innovative delayed release implant of medical grade poly(glycolide-co-trimethylene carbonate-co-ε-caprolactone)","authors":"Norman L. Ilich , Enoch Chan , M. Scott Taylor , Brian Gaerke , Sinduja Suresh , Damien G. Harkin , Flavia Medeiros Savi , Siamak Saifzadeh , Dietmar W. Hutmacher , Tim R. Dargaville","doi":"10.1016/j.eurpolymj.2024.113569","DOIUrl":"10.1016/j.eurpolymj.2024.113569","url":null,"abstract":"<div><div>Delayed release implants are a potential method to deliver a therapeutic after a specified lag time. A reservoir implant fabricated by dip-coating allows facile loading of a payload designed to be injected subcutaneously with release controlled by the physicochemical properties of a soft biodegradable terpolymer, poly(glycolide-<em>co</em>-trimethylene carbonate-<em>co</em>-ε-caprolactone). A triphasic profile is achieved, consisting of a lag period (Phase 1) due to negligible terpolymer degradation preventing payload release. By 37 days (Phase 2) bulk erosion of the terpolymer reaches a state where payload begins to diffuse into the surrounding medium, accounting for 75 % of release and 20 % mass loss, indicating a combination of diffusion and erosion-mediated release. Lastly, Phase 3 is predominately diffusion-controlled as 20 % payload release is achieved with minimal mass loss of the polymer. In a rodent preclinical model, the terpolymer was well-integrated within host tissue with a balanced foreign body reaction. This study demonstrates the feasibility of using a unique medical grade poly(ester)-based polymer to develop a delayed release implant with excellent potential for translation. Prospective applications of this device include the delivery of sensitive payloads such as protein vaccines as polymer-payload interactions during manufacturing are avoided.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113569"},"PeriodicalIF":5.8,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662634","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}

引用次数: 0

Balancing hydrophobicity and surface potential in bio-based bisfuran-containing polyamide coatings for enhanced long-term antibacterial efficacy and endotoxin adsorption 平衡生物基含双呋喃聚酰胺涂层的疏水性和表面电位，提高长期抗菌效果和内毒素吸附性

IF 5.8 2区化学

European Polymer Journal Pub Date : 2024-11-09 DOI: 10.1016/j.eurpolymj.2024.113571

Liuqi Shi , Hong-Hui Shu , Zhiyuan Zhu , Cheng-Mei Liu , Jingyi Rao

{"title":"Balancing hydrophobicity and surface potential in bio-based bisfuran-containing polyamide coatings for enhanced long-term antibacterial efficacy and endotoxin adsorption","authors":"Liuqi Shi , Hong-Hui Shu , Zhiyuan Zhu , Cheng-Mei Liu , Jingyi Rao","doi":"10.1016/j.eurpolymj.2024.113571","DOIUrl":"10.1016/j.eurpolymj.2024.113571","url":null,"abstract":"<div><div>To develop antimicrobial protective materials based on renewable polymers, we synthesized a series of bio-based bisfuran-based polyamide (<strong>bFPA</strong>) polymers with various functional groups, including allyl quaternary ammonium cations, decyl quaternary ammonium cations, and sulfonate betaine. These <strong>bFPA</strong>-based coating materials, featuring excellent thermal stability (>230 °C) and biocompatibility, were facilely fabricated on polyurethane (PU) substrates by blending and crosslinking with unsaturated aliphatic PU resin. By altering the combination of different functional groups in <strong>bFPA</strong> polymers, we controlled the hydrophilicity/hydrophobicity and surface charge properties of the bio-based coating. Compared to pure PU coatings, the <strong>bFPA</strong>-based coatings with moderate hydrophilicity/hydrophobicity and surface potential significantly reduced the adhesion of model protein and bacteria by approximately 70 % and >99 %, respectively, demonstrating outstanding anti-protein and anti-bacterial adhesion properties. Even after seven cycles of use, the coatings maintained the ability to kill ∼80 % and >99 % of Gram-negative <em>Escherichia coli</em> and Gram-positive <em>Staphylococcus aureus</em> bacteria, respectively, indicating long-lasting antibacterial activity. Additionally, the optimized <strong>bFPA</strong>-based coatings effectively adsorbed ∼80 % of endotoxins from damaged Gram-negative bacteria through electrostatic interactions, thereby reducing the risk of inflammation and sepsis. The development of bio-based polyamide coatings with long-term antibacterial and endotoxin adsorption properties significantly advances their safe and reliable application of in the field of biomedical devices.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113571"},"PeriodicalIF":5.8,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662635","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

Modifiers for the preparation of starch composites under mechanochemical activation: An extended set of criteria 在机械化学活化条件下制备淀粉复合材料的改性剂：一套扩展标准

IF 5.8 2区化学

European Polymer Journal Pub Date : 2024-11-09 DOI: 10.1016/j.eurpolymj.2024.113560

V.A. Burmistrov , I.P. Trifonova , N.V. Losev , J.N. Larina , I.M. Lipatova

{"title":"Modifiers for the preparation of starch composites under mechanochemical activation: An extended set of criteria","authors":"V.A. Burmistrov , I.P. Trifonova , N.V. Losev , J.N. Larina , I.M. Lipatova","doi":"10.1016/j.eurpolymj.2024.113560","DOIUrl":"10.1016/j.eurpolymj.2024.113560","url":null,"abstract":"<div><div>Modification of starch with synthetic polymers under mechanochemical activation is a convenient way to regulate the operational properties of composite materials. The widespread use of this approach is limited by the lack of data on the influence of synthetic polymer nature on the properties of starch and the absence of clear criteria for modifiers selection in the form of aqueous dispersions. To eliminate existing problems, the work proposes to use five integral criteria − polarity, hydrophilicity, and flexibility of synthetic modifiers, as well as particle size and ζ-potential of their aqueous dispersions. To achieve this goal, we studied the dielectric constant, contact angles, IR spectra, and dynamic mechanical properties of four acrylic copolymers and an aliphatic polyurethane. Using the mechanochemical activation, blends and composite films based on corn starch and synthetic modifiers (80:20) were manufactured. Methods of rotational viscometry, X-ray diffraction analysis, DMA, mechanical tests, and moisture permeability allowed us to reveal the influence of the modifier integral parameters on the rheological characteristics of the molding blends and the impact of joint mechanical activation on them, as well as on the crystal structure of the composites, their storage modulus, strength, and transport characteristics.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113560"},"PeriodicalIF":5.8,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142703903","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

Facile synthesis of polyhedral oligomeric silsesquioxanes with excellent thermosetting, fibrous and crystalline properties 轻松合成具有优异热固性、纤维性和结晶性的多面体低聚硅倍半氧烷

IF 5.8 2区化学

European Polymer Journal Pub Date : 2024-11-08 DOI: 10.1016/j.eurpolymj.2024.113568

Weiwei Zhang , Yukuan Niu , Wenchao Zhang , Rongjie Yang

{"title":"Facile synthesis of polyhedral oligomeric silsesquioxanes with excellent thermosetting, fibrous and crystalline properties","authors":"Weiwei Zhang , Yukuan Niu , Wenchao Zhang , Rongjie Yang","doi":"10.1016/j.eurpolymj.2024.113568","DOIUrl":"10.1016/j.eurpolymj.2024.113568","url":null,"abstract":"<div><div>The development of multifunctional polyhedral oligomeric silsesquioxanes (POSS) that are more serialized than traditional POSS is essential to reduce the economic investment and expand the category of high-performance POSS. This work employed a simple one-step method to synthesize a series of different physical states of methacryloxypropyl-phenyl POSS (AcPhPOSS). The FTIR, NMR and MS results showed that the products were mainly composed of regular T<sub>8</sub>, T<sub>10</sub> and T<sub>12</sub> cage-like structures, and the outer periphery of the AcPhPOSS cage carried different proportions of flexible methacryloxypropyl (R<sub>1</sub>) and rigid phenyl (R<sub>2</sub>) groups. In addition, the curable, fibrous, and crystalline properties of liquid, semi-solid, and powder AcPhPOSS were studied through thermal curing, electrospinning, and crystallization methods, respectively. The results showed that AcPhPOSS in three different states, especially AcPhPOSS@1:0 (liquid), AcPhPOSS@1:3 (semi-solid) and AcPhPOSS@0:1 (powder), exhibited good thermal curing properties, fiber and crystallization, respectively. Hence, this work proposes a facile strategy for producing multifunctional materials with good curing properties, fiber-forming properties, and crystallinity, which have broad application potential in thermosetting resins, fiber materials, and single crystal materials.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113568"},"PeriodicalIF":5.8,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662930","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

Studies on preparation of silicon-containing polyester via ring-opening polymerization and new type of elastomers derived from the resulting diols 通过开环聚合法制备含硅聚酯以及由所得二元醇衍生出的新型弹性体的研究

IF 5.8 2区化学

European Polymer Journal Pub Date : 2024-11-08 DOI: 10.1016/j.eurpolymj.2024.113570

Zedong He , Hao Zhang , Ju Xie , Ti Zhou , Jie Zhang

{"title":"Studies on preparation of silicon-containing polyester via ring-opening polymerization and new type of elastomers derived from the resulting diols","authors":"Zedong He , Hao Zhang , Ju Xie , Ti Zhou , Jie Zhang","doi":"10.1016/j.eurpolymj.2024.113570","DOIUrl":"10.1016/j.eurpolymj.2024.113570","url":null,"abstract":"<div><div>Silicon-containing polyesters represent a novel class of polymers that integrate silicone and polyester units within their main chain. Polysiloxanes typically consist of flexible chain segments, while polyesters are characterized by their rigidity. The combination of these two components in the main chain offers the potential for tunable properties across a broad range. For the first time, a new organosilicon cyclic ester monomer (Si-Mon) was synthesized using a pseudo-high dilution condensation method. Both theoretical and experimental studies confirm that the ring-opening reaction site of Si-Mon is the ester group, rather than the Si-O-Si bond. Silicon-containing polyesters (SiPET-Series 1) with molecular weights exceeding 20,000 Da were efficiently and rapidly synthesized at room temperature, utilizing benzyl alcohol as the initiator and t-BuP<sub>4</sub> as the catalyst. Organosilicon polyester diols (SiPET-Series 2) with varying molecular weights were produced using 1,4-benzenedimethanol as the initiator. Additionally, a new type of organosilicon polyester elastomer (SiPET-E) was developed by employing SiPET-Series 2 as the base gum and (2,4,6-trioxotriazine-1,3,5(2H,4H,6H)- triyl)tris(hexamethylene)isocyanate (THDI) as the crosslinking agent. The stress–strain behavior of SiPET-E is influenced by the molecular weight of SiPET-Series 2. Notably, SiPET-E exhibits remarkable properties; for instance, it demonstrates superelastic characteristics when the molecular weight of SiPET-Series 2 is 13,000 g/mol, achieving a tensile strength of 2.56 MPa and an elongation at break of 776 % without the use of reinforcing fillers.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113570"},"PeriodicalIF":5.8,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662623","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

Mechanically robust, self-healing and stretchable electromagnetic shielding materials based on multi-component dynamic bonded polyurethane elastomer 基于多组分动态粘合聚氨酯弹性体的机械坚固、自修复和可拉伸电磁屏蔽材料

IF 5.8 2区化学

European Polymer Journal Pub Date : 2024-11-07 DOI: 10.1016/j.eurpolymj.2024.113556

Zongyi Zheng , Jiaji Zhu , Huagao Fang , Jiewu Cui , Yong Zhang , Yunsheng Ding

{"title":"Mechanically robust, self-healing and stretchable electromagnetic shielding materials based on multi-component dynamic bonded polyurethane elastomer","authors":"Zongyi Zheng , Jiaji Zhu , Huagao Fang , Jiewu Cui , Yong Zhang , Yunsheng Ding","doi":"10.1016/j.eurpolymj.2024.113556","DOIUrl":"10.1016/j.eurpolymj.2024.113556","url":null,"abstract":"<div><div>Stretchable self-healing electromagnetic interference (EMI) shielding materials can automatically restore their original performance after mechanical damage, and can still maintain over 20 dB EMI shielding effectiveness (EMI SE) under tensile state. In this work, a series of highly stretchable self-healing polyurethane elastomer PUBNS-X was prepared by introducing dynamic disulfide bonds, boronic ester bonds and boron-nitrogen coordination (B-N) on the polyurethane main chain. It was found that B-N coordination significantly increased the elongation at break and the tensile strength. The high dynamic reversibility of boronic ester, disulfide bond and B-N coordination bond synergistically endowed PUBNS-X with excellent temperature-triggered self-healing properties. The mechanical properties of PUBNS-X can be restored to more than 90 % at 60 °C. The pre-assembled silver nanowires (AgNWs) conductive network was then introduced into the polyurethane surface by taking advantage of the fluidity of the dynamically bonded polyurethane backbone to obtain a series of stretchable self-healing electromagnetic shielding composites (AgNWs/PUBNS-Y). The results showed that the EMI SE of AgNWs/PUBNS-Y can reach ∼55 dB, and the conductivity can be restored to 82 % of the original value after healing at 60 °C. The investigation of the electromagnetic interference shielding performance of composites under different strains showed that the EMI SE of AgNWs/PUBNS-3 can still maintain 20 dB under 90 % strain. These composites will have broad potential applications in the fields of flexible wearable electronic products, bionic intelligent materials and soft robots.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113556"},"PeriodicalIF":5.8,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142663016","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

Visible-light-switchable glass transition temperatures and optical actuation in crosslinked fluoroazopolymers 可见光可切换玻璃化转变温度和交联氟唑聚合物中的光学致动作用

IF 5.8 2区化学

European Polymer Journal Pub Date : 2024-11-06 DOI: 10.1016/j.eurpolymj.2024.113563

Youfeng Yue

引用次数: 0

Multifunctional performance of gallic acid in biodegradable food packaging films and coatings: Mechanisms, developments, applications, and horizons 没食子酸在可生物降解食品包装薄膜和涂料中的多功能表现：机理、发展、应用和前景

IF 5.8 2区化学

European Polymer Journal Pub Date : 2024-11-06 DOI: 10.1016/j.eurpolymj.2024.113559

Behnam Bahramian , Reza Abedi-Firoozjah , Narges Kiani-Salmi , Asghar Azizian , Nazli Dorud , Seyyed Mohammad Ali Noori , Mohammad Hashemi , Elham Assadpour , Milad Tavassoli , Ehsan Sadeghi , Fuyuan Zhang , Seid Mahdi Jafari

{"title":"Multifunctional performance of gallic acid in biodegradable food packaging films and coatings: Mechanisms, developments, applications, and horizons","authors":"Behnam Bahramian , Reza Abedi-Firoozjah , Narges Kiani-Salmi , Asghar Azizian , Nazli Dorud , Seyyed Mohammad Ali Noori , Mohammad Hashemi , Elham Assadpour , Milad Tavassoli , Ehsan Sadeghi , Fuyuan Zhang , Seid Mahdi Jafari","doi":"10.1016/j.eurpolymj.2024.113559","DOIUrl":"10.1016/j.eurpolymj.2024.113559","url":null,"abstract":"<div><div>There is an increasing interest in the development of degradable and biopolymeric food packaging films (FPFs) based on green ingredients and strategies. To enhance the performance of these films, modifications can be made to the biopolymer molecules, or additives can be incorporated, such as nanomaterials, crosslinkers, bioactive compounds, and other polymers. The use of green compounds is an effective method to improve the performance of degradable FPFs, with gallic acid (GA) being a widely used natural green compound in various biopolymeric films. This review provides an in-depth analysis of GA chemistry and discusses the different types of biopolymeric FPFs crosslinked by GA. Furthermore, it summarizes the recent applications of GA crosslinked biopolymeric FPFs/coatings for food preservation. The comprehensive improvement of biopolymeric films due to GA crosslinking is evident, with the effect on the films’ properties dependent on the concentration of GA and reaction state. The cross-linking of GA with polymer molecules increases the cohesion of the polymer network, with physical and chemical covalent crosslinking being the two main types of cross-linking. Notably, biopolymeric FPFs/coatings crosslinked by GA have demonstrated remarkable effectiveness in preserving fresh foods.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113559"},"PeriodicalIF":5.8,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142663006","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

Intrinsic self-healing Polyurethanes: Advances, Applications, and future prospects 内在自愈合聚氨酯：进展、应用和未来展望

IF 5.8 2区化学

European Polymer Journal Pub Date : 2024-11-06 DOI: 10.1016/j.eurpolymj.2024.113566

Roham Ghanbari , Azam Serajian , Shahla Ataei , Ehsan Nazarzadeh Zare

{"title":"Intrinsic self-healing Polyurethanes: Advances, Applications, and future prospects","authors":"Roham Ghanbari , Azam Serajian , Shahla Ataei , Ehsan Nazarzadeh Zare","doi":"10.1016/j.eurpolymj.2024.113566","DOIUrl":"10.1016/j.eurpolymj.2024.113566","url":null,"abstract":"<div><div>Polyurethane (PU), a versatile and widely used polymer, has garnered significant research attention due to its intrinsic properties such as extended lifetime and durability, with diverse applications, ranging from clothing to industrial components. Self-healing mechanisms in PU primarily rely on intrinsic and extrinsic driving forces, in which the intrinsic process got sough after because of its reversible features. The intrinsic mechanism can be categorized into reversible covalent bonds (e.g., Diels-Alder reactions and disulfide bonds,) and dynamic non-covalent interactions (e.g., hydrogen bonds and ionic bonds). These mechanisms enable the spontaneous reconfiguration and healing of the polymer structure. Furthermore, the integration of new functional groups into PU structures introduces additional properties such as shape memory, degradability, and biocompatibility, broadening the scope of applications, particularly in flexible sensors and biomedical engineering. This paper delves into the self-healing mechanisms of PU, its functional integration, and potential applications in emerging fields such as coatings, adhesives, photo-thermal conversion, and biomedical devices, highlighting the challenges and future prospects in the development of self-healing PUs. Through a synthesis of recent studies, this article also discusses the balance between self-healing capabilities and mechanical properties, proposing new research directions for enhancing the efficacy and utility of self-healing PUs.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113566"},"PeriodicalIF":5.8,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142663007","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

Disparity between rate and selectivity in the controlled synthesis of gradient conjugated copolymers 梯度共轭共聚物受控合成中速率与选择性之间的差异

IF 5.8 2区化学

European Polymer Journal Pub Date : 2024-11-06 DOI: 10.1016/j.eurpolymj.2024.113562

Annelien Van Oosten , Florian Matz , Valentina Parravicini , Thomas Christian Jagau , Guy Koeckelberghs

{"title":"Disparity between rate and selectivity in the controlled synthesis of gradient conjugated copolymers","authors":"Annelien Van Oosten , Florian Matz , Valentina Parravicini , Thomas Christian Jagau , Guy Koeckelberghs","doi":"10.1016/j.eurpolymj.2024.113562","DOIUrl":"10.1016/j.eurpolymj.2024.113562","url":null,"abstract":"<div><div>In this report, a one-pot synthesis of gradient copolymers is attempted employing Kumada catalyst transfer condensative polymerization (KCTCP). The hypothesis that a more reactive monomer is preferentially being built into the chain at the beginning, while the slower reacting monomer is only being built into the chain at the end due to it being in excess, is investigated. The monomer rate constants are influenced by the usage of differently sized sidechains (octyl <em>versus</em> 3-octyldodecyl) and nucleophilicity of the monomers (thiophene <em>versus</em> selenophene). Nonetheless, while the rate constants differ by a factor 2, no selectivity is obtained. The cause thereof is further investigated by increasing the sterical crowdedness around the catalyst-complex by employing a 4-substituted monomer, the polymerization of which also gave rise to random copolymers. Accompanied by density functional theory calculations of the geometry and Gibbs free energy, it is concluded that the distance between the nickel catalyst and the polymer chain is much smaller compared to the distance between the catalyst and the incoming monomer. This results in different polymerization rates (depending on the polymer-nickel complex), while having no selectivity for one incoming monomer over the other.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113562"},"PeriodicalIF":5.8,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662631","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