PolymerPub Date : 2025-07-22DOI: 10.1016/j.polymer.2025.128846
Baogou Wu , Mengju Gao , Xiaohu Bing , Jian Xiao , Yu Cao , Wenge Zheng , Long Wang
{"title":"Multiple synergies for enhancing the toughening efficiency: toward fully biodegradable polylactide-based engineering plastics with superior toughness, strength and heat resistance","authors":"Baogou Wu , Mengju Gao , Xiaohu Bing , Jian Xiao , Yu Cao , Wenge Zheng , Long Wang","doi":"10.1016/j.polymer.2025.128846","DOIUrl":"10.1016/j.polymer.2025.128846","url":null,"abstract":"<div><div>Melt blending with biodegradable poly(butylene adipate-co-terephthalate) (PBAT) is a widely used approach for toughening poly(<span>l</span>-lactide) (PLLA). However, a high PBAT addition (30 wt%) is typically required to achieve supertoughness of PLLA, despite extensive efforts to improve toughening efficiency. Herein, the PLLA/PBAT blends were subjected to a simple one-pot melt blending with an epoxy-functional compatibilizer (ADR) and poly(<span>d</span>-lactide) (PDLA). The enhanced interfacial adhesion resulting from ADR-induced reactive compatibilization, combined with the elevated melt viscosity of the PLLA matrix caused by the generation of stereocomplex (sc) crystallites through PLLA-PDLA interactions, results in a morphological transition from a sea-island to a co-continuous structure. Concurrently, sc crystallites accelerate the PLLA matrix crystallization, achieving a highly crystalline matrix after brief melt crystallization. Owing to the synergistic effects of strong interfacial adhesion, co-continuous structure and highly crystalline matrix, the toughening efficiency of PBAT is markedly enhanced. Consequently, the notched impact strength of PLLA reaches 58.9 kJ/m<sup>2</sup> with only 15 wt% PBAT. Additionally, the reduced PBAT content coupled with increased matrix crystallinity endows the blend with high tensile yield strength (57.5 MPa) and heat resistance (Vicat softening temperature up to 156.4 °C). The comprehensive performance of the resulting blend surpasses that of certain commercially available non-biodegradable engineering plastics, potentially expanding the application of fully biodegradable polylactide-based alloys in engineering fields.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"335 ","pages":"Article 128846"},"PeriodicalIF":4.1,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144677736","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":"Sustainable epigallocatechin gallate-based polycarbonate vitrimers with flame-retardant and antioxidant properties for closed-loop recyclable carbon fiber composites","authors":"Jialiang Zhong, Zhaoyi Luo, Yue Wang, Yanning Zeng","doi":"10.1016/j.polymer.2025.128841","DOIUrl":"10.1016/j.polymer.2025.128841","url":null,"abstract":"<div><div>Sustainable polycarbonate (PC) vitrimers were synthesized through a green one-step reaction between biomass-derived epigallocatechin gallate (EGCG) and bis(6-membered cyclic carbonate) (BCC). These EGCG-based networks exhibit exceptional mechanical properties, flame retardancy, antioxidant capacity, self-healing ability and reprocessability. EGCG content significantly affects the performance of the resulting networks. As the EGCG content increases, the mechanical properties, stress relaxation, flame retardancy, antioxidant capacity were improved. The increased EGCG content enhances crosslinking density, resulting in superior flame retardancy with a UL-94 V-0 rating and limiting oxygen index (LOI) of 28.1 %. The dynamic network structure enables efficient stress relaxation, retaining over 80 % of mechanical properties after three reprocessing cycles. Additionally, the material exhibits thermal self-healing efficiency of 90 % through transcarbonation-driven network rearrangement. Additionally, EGCG-based carbon-fiber composites achieved close loop recycling, addressing environmental concerns while maintaining high performance. Present strategy simultaneously enhances recyclability, fire safety, and sustainability, offering a circular economy-aligned solution for polymers used in electronics, automotive, and aerospace applications.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"335 ","pages":"Article 128841"},"PeriodicalIF":4.1,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144677735","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}
PolymerPub Date : 2025-07-21DOI: 10.1016/j.polymer.2025.128843
Jinqi Wu , Yani Chen , Ting Zhang , Lifen Tong , Xiaobo Liu , Shuning Liu
{"title":"Molecularly engineered Polyarylene ether nitrile copolymers integrating high thermal resistance with ultralow dielectric loss for advanced electronic applications","authors":"Jinqi Wu , Yani Chen , Ting Zhang , Lifen Tong , Xiaobo Liu , Shuning Liu","doi":"10.1016/j.polymer.2025.128843","DOIUrl":"10.1016/j.polymer.2025.128843","url":null,"abstract":"<div><div>The development of polymer materials combining exceptional heat resistance with ultralow dielectric characteristics remains critical for advancing high-frequency communication systems and miniaturized high-temperature electronic devices. This study introduces an innovative array of polyarylene ether nitrile (PEN) statistical copolymers that were synthesized by nucleophilic substitution polymerization, strategically incorporating biphenol AP (BPAP) for dielectric optimization, fluorene-based bisphenol (BPF) for thermal stability enhancement, and 2,6-dichlorobenzonitrile (DCBN) as the activating monomer. Systematic characterization reveals that the optimized PEN-50 copolymer exhibits superior comprehensive performance, achieving a glass transition temperature (T<sub>g</sub>) of 237 °C while maintaining excellent dielectric properties (ε = 3.3, tanδ = 0.008, @1 MHz). The semi-crystalline film exhibits exceptional tensile performance, attaining 66 MPa tensile strength and 2.03 GPa elastic modulus. These outstanding thermomechanical properties combined with ultralow dielectric losses position the PEN-50 copolymer as a promising candidate for advanced applications in next-generation high-frequency communication devices, aerospace electronics, and high-density integrated circuits requiring simultaneous high-temperature stability and signal integrity preservation.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"335 ","pages":"Article 128843"},"PeriodicalIF":4.1,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144677737","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}
PolymerPub Date : 2025-07-21DOI: 10.1016/j.polymer.2025.128844
Barthélémy Gros, Jean-François Gérard, Paul Sotta, Xavier P. Morelle
{"title":"Double yielding in PA11: discriminating the mechanical contributions of the amorphous and crystalline fractions","authors":"Barthélémy Gros, Jean-François Gérard, Paul Sotta, Xavier P. Morelle","doi":"10.1016/j.polymer.2025.128844","DOIUrl":"10.1016/j.polymer.2025.128844","url":null,"abstract":"<div><div>The stress-strain curve of PA11 exhibits two well-distinct successive yield points during tensile deformation below T<sub>g</sub>. This phenomenon, denoted double yielding (DY), has been observed as well in other semicrystalline polymers such as PA6 or PE. An investigation of the origin of such phenomenon and its relationship to the deformation mechanisms occurring in the amorphous and crystalline phases of PA11 has been conducted. PA11 samples were purposely modified prior to or during tensile testing and the resulting effects on the two yield points were systematically monitored. A strong link between ageing-, temperature/rate- or plasticity-induced molecular mobility in the amorphous phase and the first yield point has been established. On the other hand, the second yield point is clearly sensitive to crystalline restructuring due to annealing or slow cooling from the melt. However, it is also sensitive to changes in mobility in the amorphous phase. A thermomechanical activation model describing the DY phenomenon that predicts the non-trivial evolution of σ<sub>y2</sub> and suggests that plastic flow in the amorphous phase must first be activated to initiate crystalline mechanisms has been proposed. More generally new insights into the complex microscopic deformation mechanisms in semicrystalline thermoplastics have been provided.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"335 ","pages":"Article 128844"},"PeriodicalIF":4.1,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144677738","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}
PolymerPub Date : 2025-07-19DOI: 10.1016/j.polymer.2025.128839
Tao Yang , Ruiyao Lu , Jingyao Yan , Shuai Jin , Yanhu Xue
{"title":"Influence of molecular weight on the thermal degradation of poly(lactic acid): A crystallization perspective","authors":"Tao Yang , Ruiyao Lu , Jingyao Yan , Shuai Jin , Yanhu Xue","doi":"10.1016/j.polymer.2025.128839","DOIUrl":"10.1016/j.polymer.2025.128839","url":null,"abstract":"<div><div>In this study, the thermal degradation behavior of poly(lactic acid) (PLA) with different molecular weights (S1, S2 and S3 are 40.58 × 10<sup>3</sup>, 49.06 × 10<sup>3</sup> and 67.49 × 10<sup>3</sup> g/mol, respectively), was systematically investigated using thermogravimetric analysis (TGA). Through deconvolution of differential thermogravimetric (DTG) curves using the Fraser-Suzuki function, two distinct degradation components were identified: Pseudo 1 (associated with ester exchange reactions) and Pseudo 2 (associated with free radical reactions). A comprehensive kinetic analysis was performed using four model-free methods to elucidate the thermal degradation mechanism. The results revealed a significant molecular weight dependence of activation energies (E<sub>α</sub>). The E<sub>α</sub> range had a decreasing trend with the increase of molecular weight, which were 152∼247, 144–232, and 111–197 kJ/mol for S1, S2 and S3, respectively. This inverse correlation between molecular weight and E<sub>α</sub> indicates that lower molecular weight PLA exhibits slower thermal degradation kinetics and enhanced thermal stability. Complementary analysis of non-isothermal cold crystallization kinetics using Liu-Mo and Kissinger methods demonstrated that decreasing molecular weight resulted in higher F(T) values. The calculated activation energies (ΔE) for cold crystallization were 66.17 kJ/mol, 70.92 kJ/mol, and 85.76 kJ/mol for S1, S2 and S3, respectively, which accelerated crystallization kinetics in lower molecular weight PLA. From a crystallization perspective, lower molecular weight PLA exhibited superior non-isothermal cold crystallization capability, forming more abundant lamellar crystals. This crystalline architecture preserves the integrity of long polymer chains during thermal degradation, thereby decelerating degradation rates and improving overall thermal stability. The study establishes a fundamental relationship between molecular weight, crystallization, and thermal degradation mechanisms in PLA.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"335 ","pages":"Article 128839"},"PeriodicalIF":4.1,"publicationDate":"2025-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144664608","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}
PolymerPub Date : 2025-07-18DOI: 10.1016/j.polymer.2025.128837
Hidayet Mazi, Kevser Erbalci
{"title":"Adsorption of methylene blue from wastewater using poly(acrylamide-co-itaconic acid-co-stearyl methacrylate) hydrogels","authors":"Hidayet Mazi, Kevser Erbalci","doi":"10.1016/j.polymer.2025.128837","DOIUrl":"10.1016/j.polymer.2025.128837","url":null,"abstract":"<div><div>In this study, copolymer hydrogels of itaconic acid with acrylamide and stearyl methacrylate were synthesized. Ammonium persulfate (APS), tetramethyl ethylenediamine (TMEDA) and methylenebisacrylamide (mBAAm) were used as initiators, catalysts and crosslinkers, respectively in the synthesis carried out at 60 °C. The effects of temperature and pH on swelling behavior were investigated. The synthesized hydrogels were used in the recovery of methylene blue (MB). Characterization of gels and MB adsorbed forms was done by SEM and FTIR techniques. The effects of temperature and pH of the solution on adsorption capacity were investigated. In adsorption processes carried out at different temperatures (between 25 and 70 °C), it was observed that the adsorption capacity increased as the temperature increased, reaching the maximum value (1658 mg/g) at 55 °C and starting to decrease after this temperature. Adsorption studies also revealed that the adsorption capacity increased with increasing solution pH. It was determined that the adsorption obeyed the Langmuir isotherm and the pseudo-second-order kinetic model. The reuse of the synthesized hydrogels in adsorption was also investigated. The results showed that there was a slight decrease in the adsorption capacity after 20 reuses and the desorption was around 91 %. MB desorbed by solvent washing technique was recovered. The results revealed that MB could be easily and economically recovered using the synthesized hydrogels.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"335 ","pages":"Article 128837"},"PeriodicalIF":4.1,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144664620","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}
PolymerPub Date : 2025-07-18DOI: 10.1016/j.polymer.2025.128836
Zongzheng Zuo , Shuxue Zhou
{"title":"Comparative study on random and block fluorinated polyacrylates for fabrication of hydrophobic 2K polyurethane clearcoats","authors":"Zongzheng Zuo , Shuxue Zhou","doi":"10.1016/j.polymer.2025.128836","DOIUrl":"10.1016/j.polymer.2025.128836","url":null,"abstract":"<div><div>In this study, 2-(perfluorohexyl)ethyl methacrylate, hydroxyethyl methacrylate and methyl methacrylate were used to synthesize three random fluorinated polyacrylates with various fluorine contents (<em>i.e.</em>, F1H1, F3H1, and F5H1) and one block fluorinated polyacrylate (<em>i.e.</em>, PFPHM) through traditional radical polymerization and atom transfer radical polymerization, respectively. These copolymers were further adopted as hydrophobic additives to incorporate into 2K polyurethane (PU) clearcoats. Effect of the type and dosage of the fluorinated polyacrylate on the haze, surface hydrophobicity, outdoor hydrophobicity durability and dirt pick-up resistance (DPUR) of modified coatings were investigated. Fluorinated polyacrylate additive with higher fluorine content is easier to cause haze of 2K PU clearcoats, nevertheless, hydrophobic surface could be acquired at lower dosage, alleviating its negative effect on transparency. PFPHM showed extremely higher hydrophobicity modification efficiency compared to the random polyacrylate additive, due to its easy enrichment at the superficial layer of 2K PU clearcoats. Moreover, PFPHM-modified 2K PU coatings presented the best hydrophobicity durability and dirt pick-up resistance in outdoor exposure test. The loss of hydrophobicity outdoors was mainly due to the aging of PU matrix, loss of fluoroalkyl chains, and partially to the dirt adhesion.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"335 ","pages":"Article 128836"},"PeriodicalIF":4.1,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144664611","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}
PolymerPub Date : 2025-07-18DOI: 10.1016/j.polymer.2025.128829
Maxim A. Zotkin , Dmitry A. Alentiev , Natalia N. Gavrilova , Maxim V. Bermeshev
{"title":"Porous organic polymers derived from norbornenes based on methyl-substituted anthracene","authors":"Maxim A. Zotkin , Dmitry A. Alentiev , Natalia N. Gavrilova , Maxim V. Bermeshev","doi":"10.1016/j.polymer.2025.128829","DOIUrl":"10.1016/j.polymer.2025.128829","url":null,"abstract":"<div><div>A set of new metathesis and vinyl-addition polymers bearing different bulky framed 9,10-dihydroanthracene moieties in side chains has been prepared and studied as promising porous organic materials. The desired monomers have been readily synthesized in good yields via Diels-Alder reaction between 2,5-norbornadiene and methyl derivatives of anthracene. The ring-opening metathesis polymerization of these monomers in the presence of the 1st generation Grubbs catalyst afforded soluble high-molecular-weight products (<em>M</em><sub>w</sub> > 9 × 10<sup>5</sup>). Vinyl-addition polymerization over Pd-system led to saturated polymers with rigid backbones. As a result, five new polynorbornenes with regularly changed structure have been synthesized. The polymers are glassy, thermally stable, and amorphous. The investigation into their N<sub>2</sub>, CH<sub>4</sub> and CO<sub>2</sub> sorption properties showed that the addition of methyl groups is an efficient approach to increase micro- and mesoporosity and CO<sub>2</sub> solubility coefficients of such polymers. The polymers with methylated 9,10-dihydroanthracene moieties exhibited large specific surface areas (up to 740 m<sup>2</sup>/g), volume of micropores up to 0.17 cm<sup>3</sup>/g and infinite dilution solubility coefficients up to 2.2 mmol g<sup>−1</sup> atm<sup>−1</sup>.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"335 ","pages":"Article 128829"},"PeriodicalIF":4.1,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652189","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}
PolymerPub Date : 2025-07-18DOI: 10.1016/j.polymer.2025.128835
Jingqing Li , Yunxiang Shi , Weihua Wang , Xinle Li , Changli Ma , Hongfei Li , He Cheng , Shixuan Xin , Shichun Jiang
{"title":"Crystallization and rheological behaviors of metallocene polyethylene","authors":"Jingqing Li , Yunxiang Shi , Weihua Wang , Xinle Li , Changli Ma , Hongfei Li , He Cheng , Shixuan Xin , Shichun Jiang","doi":"10.1016/j.polymer.2025.128835","DOIUrl":"10.1016/j.polymer.2025.128835","url":null,"abstract":"<div><div>Metallocene catalysts enable precise synthesis of polyolefins including metallocene polyethylene(mPE) with uniform molecular weight distribution, controlled branching, and tailored co-monomer incorporation, yielding polymers with superior properties, thus advancing high-performance applications while optimizing production efficiency and sustainability. A zirconium dichloride complex, three intermediates and methylaluminoxane were chosen as a metallocene catalyst for synthesis of the mPE samples with different molecular weights <em>M</em><sub>w</sub>s. The long-chain branches and fractal architecture of the mPE chains were confirmed by investigations of the rheology and crystallization behaviors. The branch content of the mPE samples was obtained by small angle neutron scattering(SANS) technology and analyzed according to the local scattering laws and mass-fractal power laws. The SANS results showed that all the four mPE samples have the same persistence length <em>l</em><sub>p</sub> and the mole fraction branches <em>Φ</em><sub>br</sub> increased with the weight-average molecular weight (determined by gel permeation chromatography, GPC) <em>M</em><sub>w,GPC</sub> of the samples. From melt linear viscoelastic rheology, the <em>M</em><sub>w</sub>s of the main chain of the mPEs had been determined. It was found that the <em>M</em><sub>w,GPC</sub> of mPE is overestimated at low <em>M</em><sub>w</sub> but underestimated at high <em>M</em><sub>w</sub> with a critical actual <em>M</em><sub>w</sub> value of around 2 × 10<sup>5</sup> g <span><math><mrow><mo>·</mo></mrow></math></span> mol<sup>−1</sup>. Thus, by combination of melt rheology and SANS, the more accurate <em>M</em><sub>w</sub>s of the mPEs were estimated to provide details of the long-chain branched (LCB) molecular structures of the mPEs. The results would shed lights on experimental characterization of LCB architectures of polymers for further investigations on relations between their structures and properties.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"335 ","pages":"Article 128835"},"PeriodicalIF":4.1,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144664614","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}
PolymerPub Date : 2025-07-17DOI: 10.1016/j.polymer.2025.128827
Yang Gou, Yi-fan Zha, De-xiang Sun, Jing-hui Yang, Yong Wang
{"title":"Synchronously enhanced flame-retardance and mechanical properties of epoxy resin via a P/N-containing active curing agent","authors":"Yang Gou, Yi-fan Zha, De-xiang Sun, Jing-hui Yang, Yong Wang","doi":"10.1016/j.polymer.2025.128827","DOIUrl":"10.1016/j.polymer.2025.128827","url":null,"abstract":"<div><div>The inherent flammability of epoxy resin remains a critical challenge in material applications. To address this issue while overcoming the common drawbacks of flame-retardant additives-including poor miscibility with epoxy matrices, deterioration of mechanical properties, and long-term leaching - recent research has focused on developing efficient reactive flame retardants capable of participating in epoxy curing reactions. In this study, a novel multifunctional reactive flame retardant (TD-DOPO) synthesized through a one-step reaction of tyramine, 1,4-benzaldehyde, and 9,10-dihydro-9-oxo-10-phosphanthracene-10-oxide (DOPO) was presented. In the epoxy system, TD-DOPO demonstrated exceptional flame-retardant performance via a biphasic synergistic mechanism, achieving UL-94 V-0 rating at a remarkably low phosphorus content of merely 0.2 wt%, and the peak heat release rate (PHRR) and total heat release (THR) were also reduced by 31.5 % and 22.4 %, respectively. Concurrently, the limiting oxygen index (LOI) increased significantly from 22.2 % to 33.1 %. Notably, the multiple reactive sites of TD-DOPO not only synergistically modulated the epoxy ring-opening kinetics but also facilitated the formation of a hierarchical crosslinked network due to its inherent rigid molecular structure. This unique molecular architecture simultaneously enhanced the mechanical properties of the composite, resulting in a 29.6 % improvement in toughness. Furthermore, the tensile and flexural modulus increased to 2183.5 MPa and 3909.8 MPa, respectively, while excellent thermal properties were maintained. This work demonstrates that the design and synthesis of novel multi-reactive center flame retardants represents a straightforward yet effective strategy for developing flame retardant epoxy resin with good comprehensive performances.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"335 ","pages":"Article 128827"},"PeriodicalIF":4.1,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144645612","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}