European Polymer Journal最新文献

{"title":"Empowering green polymerization: Enzymatic polymerization and low-temperature post-polymerization to produce poly(butylene 2,5-furandicarboxylate)","authors":"C.I. Gkountela,&nbsp;O. Plangesi,&nbsp;S.N. Vouyiouka","doi":"10.1016/j.eurpolymj.2025.114083","DOIUrl":"10.1016/j.eurpolymj.2025.114083","url":null,"abstract":"<div><div>Poly(butylene 2,5-furandicarboxylate), PBF, is a bio-based polymer originating from the 2,5 furan dicarboxylic acid (2,5 FDCA). PBF has shown promising barrier properties, especially CO₂ and O₂ permeability, rendering it a promising candidate for sustainable packaging. However, its chemical synthesis requires metal catalysts and high temperature. A sustainable approach to produce PBF was herein established as an alternative to chemical polymerization: enzymatic polymerization was applied in the presence of the biocatalyst <em>Candida antarctica</em> Lipase B <em>via</em> a two-stage, solventless process of enhanced sustainability and scaling-up potential. The most critical parameters were investigated (reaction temperature, pressure and time) and PBF oligoesters (<span><math><mrow><mover><mrow><msub><mi>M</mi><mi>n</mi></msub></mrow><mrow><mo>¯</mo></mrow></mover></mrow></math></span> 1600 g·mol⁻¹, <span><math><mrow><mover><mrow><msub><mi>M</mi><mi>w</mi></msub></mrow><mrow><mo>¯</mo></mrow></mover></mrow></math></span> 1700 g·mol⁻¹) were easily synthesized thanks to the process’s simplicity. The PBF prepolymer was subsequently submitted to low-temperature post-polymerization, aiming for a molecular weight increase while maintaining its green character. The reaction temperature and time were fine-tuned to reach increased polymerization rates, avoiding thermal degradation, and the received PBF presented <span><math><mrow><mover><mrow><msub><mi>M</mi><mi>w</mi></msub></mrow><mrow><mo>¯</mo></mrow></mover></mrow></math></span> of ca. 5000 g·mol⁻¹ after 16 h of post-polymerization at 125 °C. The suggested approach produces the upcoming bio-based polymer PBF as a promising candidate for applications requiring high purity and a precisely controlled molecular weight.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"235 ","pages":"Article 114083"},"PeriodicalIF":5.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320876","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}

{"title":"Improving the mechanical and high-frequency dielectric properties of the bio-based thermoplastic copolyesters using fatty acid dimer diol and aromatic diester monomers","authors":"Yu-Chiung Li ,&nbsp;Yi-An Tsai ,&nbsp;Po-Yi Lu ,&nbsp;Mitsuru Ueda ,&nbsp;Yan-Cheng Lin ,&nbsp;Wen-Chang Chen","doi":"10.1016/j.eurpolymj.2025.114070","DOIUrl":"10.1016/j.eurpolymj.2025.114070","url":null,"abstract":"<div><div>Thermoplastic copolyesters (TPCs) are crucial structural components in a wide range of high-performance applications where exceptional processing temperatures and remarkable flexibility are essential. Among them, fatty acid dimer diol (DDO), a bio-based compound, has been used as the soft segment in bio-based TPCs through various synthesis methods. However, few studies have compared the mechanical and dielectric properties of TPCs with DDO and aromatic diester monomers of varying structures to evaluate their suitability for soft electronic devices. The objective of this study is to investigate the impact of structural isomerism and rigidity on the properties of TPCs by incorporating three different aromatic diester monomers with distinct structures into the materials. The copolymerization of a series of TPCs via melt polycondensation, catalyzed by titanium butoxide and butyltin hydroxide oxide, was carried out using alkyl diols and aromatic diesters such as DDO, 1,4-butanediol, dimethyl terephthalate, dimethyl isophthalate (DMI), and dimethyl-2,6-naphthalenedicarboxylate (NDC), resulting in promising outcomes. The results show that introducing a higher proportion of DDO not only increases the bio-based content of TPCs but also enhances their flexibility, effectively reducing both the dielectric constant (<em>D</em>_k) and dissipation factor (<em>D</em>_f) at high frequencies. Notably, under the exact condition of adding 20 mol% DDO, copolymerizing with 20 mol% <em>meta</em>-positioned DMI significantly improves the flexibility of TPCs, with the elongation at break increasing to 607 % from 109 % before copolymerization, although the <em>D</em>_k and <em>D</em>_f slightly increase. On the other hand, when 20 mol% DDO is added, copolymerizing with the more rigid NDC increases the mechanical strength. It effectively lowers the dielectric property, as the <em>D</em>_k of the copolymerized 20 mol% NDC decreases from 2.43 to 2.32 at 29 GHz. These results are closely related to the solid-state stacking revealed by their distinct refractive index and crystallinity. This study, through the development of a series of bio-based TPCs, effectively explores the relationship between the mechanical and dielectric properties of these materials, providing valuable insights for the design of flexible electronic components and the development of bio-based materials.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"235 ","pages":"Article 114070"},"PeriodicalIF":5.8,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320873","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}

{"title":"Revolutionizing drug delivery: The promise of surface functionalized dendrimers in overcoming conventional limitations","authors":"Calvin A. Omolo ,&nbsp;Eman A. Ismail ,&nbsp;Edith K. Amuhaya ,&nbsp;Victoria Fasiku ,&nbsp;Joshua C. Nwabuife ,&nbsp;Mahir Mohamed ,&nbsp;Mohammed A. Gafar ,&nbsp;Rahul Kalhapure ,&nbsp;Thirumala Govender","doi":"10.1016/j.eurpolymj.2025.114079","DOIUrl":"10.1016/j.eurpolymj.2025.114079","url":null,"abstract":"<div><div>Dendrimers are well-defined hyperbranched macromolecules with characteristic globular structures for the larger systems. The recent strides in supramolecular synthetic approaches have brought to life the functionalization of dendrimers. The application of dendrimers in drug delivery has been one of the most important applications of dendrimers to be explored. Although dendrimers have been of great importance in drug delivery, they have encountered several side effects like toxicities, quick elimination by the body, instabilities, and lack of targeting. This has led to the design of functionalized dendrimers to overcome the conventional dendrimer macromolecules’ limitations. Functionalized dendritic structures potentially possess biomimicry properties, disease, enzyme, and receptor targeting. Here, we review recent findings using these promising novel surface-functionalized dendrimers in drug delivery. We discuss some of the techniques in surface functionalization, their applications, and future perspectives on these functionalized dendritic structures.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"235 ","pages":"Article 114079"},"PeriodicalIF":5.8,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320889","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}

{"title":"RAFT Step-Growth polymerization via the Z-group approach using xanthate and vinyl ether","authors":"Qing Li,&nbsp;Xiaofeng Pan,&nbsp;Qingsong Ying,&nbsp;Wenxuan Zhu,&nbsp;Juntao Hu,&nbsp;Jiajia Li,&nbsp;Jian Zhu","doi":"10.1016/j.eurpolymj.2025.114073","DOIUrl":"10.1016/j.eurpolymj.2025.114073","url":null,"abstract":"<div><div>The development of degradable vinyl polymers is an urgent challenge in polymer chemistry. Herein, we report a ‘Z-group’ RAFT step-growth polymerization strategy based on xanthate and vinyl ether monomers, enabling the construction of polymers with thiocarbonylthio groups embedded directly into the polymer backbone. These polymers are synthesized under mild conditions such as visible light and catalyst-free, using both AB-type and A₂ + B₂-type monomers. The step-growth nature of the polymerization is confirmed by ¹H NMR and SEC analyses. The resulting backbones can undergo controlled degradation via phosphine-based reduction, yielding oligomeric fragments. Furthermore, the step-growth polymers serve as macroRAFT agents for subsequent radical or cationic chain-growth polymerizations, enabling the construction of degradable multiblock copolymers using either vinyl acetate (VAc) or isobutyl vinyl ether (IBVE). This work broadens the scope of RAFT step-growth polymerization toward less activated monomers and provides a facile way for the design of degradable functional polymers.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"235 ","pages":"Article 114073"},"PeriodicalIF":5.8,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320872","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}

{"title":"Dual-Responsive fluorinated glycopolymers Targeting GLUT1 for enhanced BBB penetration and Activatable 19F MRI imaging","authors":"Xuan Liu ,&nbsp;Feng Liu ,&nbsp;Lu Yuan ,&nbsp;Huijun Zhang ,&nbsp;Bo Zhao ,&nbsp;Xin Wen ,&nbsp;Wenjuan Yin ,&nbsp;Jie Zhang ,&nbsp;Yuangong Zhang ,&nbsp;Xinwu Ba ,&nbsp;Libin Bai","doi":"10.1016/j.eurpolymj.2025.114072","DOIUrl":"10.1016/j.eurpolymj.2025.114072","url":null,"abstract":"<div><div>Fluorine-19 magnetic resonance imaging (¹⁹F MRI) holds significant potential for the accurate diagnosis of deep-seated pathological tissues, particularly in brain disorders. However, the application of polymer-based ¹⁹F MRI for brain disorder diagnosis is still limited, mainly due to the restrictive nature of the blood–brain barrier (BBB). In this study, we developed pH- and glutathione (GSH)-responsive hyperbranched fluorinated polymers (HBP-MBEHs) capable of crossing the BBB. The ¹⁹F MRI of HBP-MBEHs had no signal before activation (OFF) and progressively intensified following exposure to acid conditions and GSH stimulation (ON). The glucose moieties in HBP-MBEHs enable crossing the BBB via glucose transporter-1 (GLUT1)-mediated transport, as demonstrated by in vivo small animal fluorescence imaging. Evaluations of cytotoxicity, hemolysis, and hematoxylin and eosin (H&amp;E) staining confirmed the excellent biocompatibility of HBP-MBEHs. This study establishes a noninvasive detection platform for brain disorders.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"235 ","pages":"Article 114072"},"PeriodicalIF":5.8,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144279385","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}

{"title":"Highly stretchable and transparent hybrid double-network acrylic nanocomposite adhesive based on the synergy between stretchable silica nanoparticles and multifunctional dual crosslinkers","authors":"Soo Young Yang ,&nbsp;Jin-Wook Kim ,&nbsp;Hye Ryeon Park,&nbsp;Gyu Jin Shin,&nbsp;Jun Hyup Lee","doi":"10.1016/j.eurpolymj.2025.114071","DOIUrl":"10.1016/j.eurpolymj.2025.114071","url":null,"abstract":"<div><div>Transparent polymer adhesives that are highly stretchable and optically clear are increasingly required owing to the development of stretchable electronic materials. Conventional acrylic polymer adhesives have low elastic moduli and exhibit poor recoveries following deformation that lead to permanent out-of-plane wrinkle defects. Consequently, acrylic adhesives that are elastic and flexible are sought after to improve stretchability and recoverability; however, the functional trade-off that exists between adhesion and elasticity must first be surmounted. In this study, we developed a hybrid double-network acrylic nanocomposite adhesive that is highly stretchable and optically transparent owing to the synergy between highly stretchable silica nanoparticles and multifunctional dual crosslinkers. Specifically, stretchable silica nanoparticles that behave stretchily and are prepared by attaching photoreactive flexible chains to the surfaces of rigid inorganic silica nanoparticles are added to an acrylic resin along with pentaerythritol triacrylate and poly(propylene glycol) diacrylate, as multifunctional dual crosslinkers, to form an elastic double-network structure through UV curing. The dual-crosslinked acrylic nanocomposite adhesive is highly elastic and flexible, and exhibits a high recovery rate of 83.8 %, a fast stress-relaxation ratio of 10.2 %, and an elongation of 461 %. Furthermore, the new acrylic nanocomposite adhesive exhibited a relative optical transmittance of 92.9 % and an adhesion strength of 18.4 N/25 mm, despite its high (5 wt%) nanoparticle concentration, highlighting its potential as a stretchable optoelectronic adhesive.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"235 ","pages":"Article 114071"},"PeriodicalIF":5.8,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144279386","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}

{"title":"Gelatin-guar gum hydrogel for topical application: cytotoxicity, antibacterial activity against MRSA, and non-irritant characteristics","authors":"Francisca Vanessa C. Canafístula ,&nbsp;Matheus X. Oliveira ,&nbsp;Ana Jérsia Araújo ,&nbsp;José Delano B. Marinho Filho ,&nbsp;Rodrigo Elísio de Sá ,&nbsp;Alyne R. Araujo-Nobre ,&nbsp;Sansara Sanny M. Araújo ,&nbsp;Fábio Oliveira S. Ribeiro ,&nbsp;Roberta Jeane B. Jorge ,&nbsp;Ana Celeste X. Oliveira ,&nbsp;Fpelipe Rhaynan S. Andrade ,&nbsp;Jeanny S. Maciel ,&nbsp;Regina Celia M. de Paula ,&nbsp;Judith Pessoa A. Feitosa","doi":"10.1016/j.eurpolymj.2025.114059","DOIUrl":"10.1016/j.eurpolymj.2025.114059","url":null,"abstract":"<div><div>Hydrogels based on oxidized guar gum (OxGG) and gelatin (Gel) were synthesized via Schiff base crosslinking using three different gelatin proportions (60–80 wt%). The hydrogels were characterized by rheology, FT-IR, GPC, SEM, swelling behavior, and degradation analyses. Variations in gelatin content led to hydrogels with distinct physicochemical properties; higher gelatin concentrations resulted in shorter gelation times, increased crosslinking density, lower swelling capacity, smaller interconnected porous structures, and faster degradation in PBS. All three hydrogels exhibited strong intrinsic antibacterial activity, inhibiting <em>methicillin/oxacillin-resistant Staphylococcus aureus</em> (MRSA) by &gt;98 % and <em>Staphylococcus epidermidis</em> and <em>Staphylococcus aureus</em> by &gt;95 %. The performance of these hydrogels was compared with that of other recently reported gels exhibiting high MRSA inhibition as well as with gelatin-containing hydrogels. Notably, OxGG:Gel hydrogels stood out because of their high antibacterial activity, which was achieved without the addition of antibiotic agents or the need for additional treatments such as photothermal therapy. Furthermore, all hydrogels demonstrated good cell viability and did not induce significant changes in the CAM blood vessels, such as vascular lysis, hemorrhage, or coagulation, confirming their non-irritating nature. The OxGG:Gel70 hydrogel exhibited superior cell viability, intermediate degradation rate, and strong efficacy against MRSA. In addition to being nonirritating, it exhibited a protective effect against vascular events. Moreover, this hydrogel exhibited key functional properties, including injectability, self-healing, and adhesiveness. Given these characteristics, OxGG:Gel70 stands out among MRSA-active hydrogels and has great potential for topical applications, including dermatitis, skin inflammation, ophthalmic formulations, and wound healing.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"235 ","pages":"Article 114059"},"PeriodicalIF":5.8,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144307873","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}

{"title":"Planar or not planar is A problem. Electrochromic polyamides with The monomer containing dibenzofluorene fused to triphenylamine for smart windows with high contrast ratio aimed for energy conservation","authors":"Minghao Zhai ,&nbsp;Chunli Ma ,&nbsp;Jingtao An ,&nbsp;Wanan Cai ,&nbsp;Tingting Zhou ,&nbsp;Haijun Niu ,&nbsp;Wen Wang","doi":"10.1016/j.eurpolymj.2025.114074","DOIUrl":"10.1016/j.eurpolymj.2025.114074","url":null,"abstract":"<div><div>According to requirement of energy conservation and environmental protection, electrochromic (EC) smart windows have been widespread implemented in building recently. However, there is challenge to tackle short life time and instability. During the EC smart windows (ESW) operation, as the electrolyte ions insert and detach from the EC film, the film will swell and shrink resulting in the collapse of the film. The molecules having planar part together with some twisted modification will take effect. Therefore, diphenylfluorene fused with triphenylamine (TPA) monomer is designed, followed by a series of polyamides (PAs) having been synthesized by polycondensation from the monomer and four dicarboxylic acids which exhibit superior solubility in polar solvents facile to form films. The solubility is mainly contributed to two benzene rings at the C9 position of the fluorene group, together with the two bulky TPA, which provide more pathways for the penetration of counter ions. The core fluorene moiety provides appropriate aggregate between mainchain resulting in the fast electrons hopping from polymer chain to conductive substrate. The polymer film (named DPFTPA-OA) exhibits 79 % transmittance change at 520 nm, as well as fast and stable EC behaviors (coloring/bleaching times of 2.2 s/1.3 s, and 1200 cycles of stabilization). Based on the superior voltage-controlled solar modulation capability of DPFTPA-OA, <em>EnergyPlus</em> simulation demonstrates that ESWs assembled with DPFTPA-OA by optimizing radiant heat exchange between indoor and outdoor environments in most China cities, have higher energy savings compared to commercial standard glass, so it exhibits considerable potential for energy management. In addition, DPFTPA-CA shows PL sensitive to 2,4,6-trinitrophenol (TNP) with <em>K_sv</em> = 2.2 × 10⁵ M^-1 and <em>LOD</em> = 43 nM, exhibiting great potential in environmental hazard test.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"235 ","pages":"Article 114074"},"PeriodicalIF":5.8,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144279387","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}

{"title":"Ternary formulations of bio-based grapeseed oil-based monomers for 3D printing: Effect of thiol-ene reaction on acrylic radical photopolymerization","authors":"Rafael Turra Alarcon ,&nbsp;Alberto Cellai ,&nbsp;Carla Cristina Schmitt ,&nbsp;Éder Tadeu Gomes Cavalheiro ,&nbsp;Marco Sangermano","doi":"10.1016/j.eurpolymj.2025.114068","DOIUrl":"10.1016/j.eurpolymj.2025.114068","url":null,"abstract":"<div><div>The development of new renewable resin formulation for VAT 3D printing is one of the most actively researched topics in chemistry and materials science. In this sense, a good balance of sustainability and final properties should be developed. Therefore, this work aims to use grapeseed oil-GSO, acrylated seed oil-AGSO, and Trimethylolpropane tris(3-mercapto propionate) – 3SH as monomers for new printable formulations. These formulations were investigated to understand the types of reactions that can occur during photopolymerization. Therefore, two reactions can occur depending on the system: thiol-ene polymerization (TEP) and free radical polymerization (FRP). All formulations showed conversion values superior to 80% and are feasible to be applied in VAT 3D printing to print complex structures. Moreover, formulations containing a higher quantity of GSO-3SH presented biobased carbon content superior to 72% and gel content higher than 99%. Last, the amount of the TE part (GSO-3SH) affects the glass transition temperature, mechanical properties (toughness, stress, strain), and hydrophobicity. Therefore, materials with different stress, strain, and toughness can be designed using various concentrations of each monomer.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"235 ","pages":"Article 114068"},"PeriodicalIF":5.8,"publicationDate":"2025-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144242750","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}

{"title":"Isospecific polymerization of (E)-4,8-dimethyl-1,3,7-nonatriene (DMNT) and its binary copolymerization with ethylene and styrene using Ti[OSSO]/MAO catalysts","authors":"Yulin Zheng ,&nbsp;Ilaria Grimaldi ,&nbsp;Benoit Lacombe ,&nbsp;Dirong Gong ,&nbsp;David Hermann Lamparelli ,&nbsp;Carmine Capacchione","doi":"10.1016/j.eurpolymj.2025.114065","DOIUrl":"10.1016/j.eurpolymj.2025.114065","url":null,"abstract":"<div><div>The inertness of saturated C–C bonds renders polyolefins exceptionally stable, yet making chemical modification prohibitively difficult. The presence of double bonds in the backbone grants these polymers diverse reactivities and, therefore, offers universal platforms for building an array of new-generation functional polyolefins. This study explores the polymerization of the bio-based monomer (E)-4,8-dimethyl-1,3,7-nonatriene (DMNT) using titanium complexes with [OSSO]-type ligands, showing notable <em>regio</em>- and stereoselectivity. The catalyst <strong>2</strong>, bearing cumyl substituents, exhibits exceptional performance, producing highly isotactic poly(DMNT) with a predominance of 1,2-insertion. Furthermore, the binary copolymerization of DMNT with ethylene and styrene was exploited to produce corresponding copolymers with varying levels of unsaturation. Successful incorporation of the comonomer was also evidenced by NMR characteristic signals. Even in these cases, DMNT was preferentially inserted in the 1,2-insertion at a remarkably high ratio (up to 98.0 mol%). At a constant DMNT concentration, increasing the ethylene pressure from 0.2 bar to 1.0 bar promoted DMNT conversion from 28.8 mol% to 85.8 mol%, accompanied by a two-fold increase in polymer yield. This result underscores the crucial role of ethylene-terminated chains in enhancing cross-propagation efficiency. DMNT incorporation and molecular weights were more precisely controlled for styrene copolymers. This control nature allowed for the unprecedented synthesis of styrene-DMNT block-like copolymers via carefully sequential monomer addition. Subsequent modification of the internal olefin group led to the formation of corresponding epoxidized copolymers. A variety of characterization techniques confirmed the desired chemical structures, improved surface wettability, and latent reactivity of the resultant epoxy-functionalized copolymers.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"235 ","pages":"Article 114065"},"PeriodicalIF":5.8,"publicationDate":"2025-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144264072","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}