European Polymer Journal最新文献

{"title":"Mechanistic insights into the calcium-mediated gelation of poly(4-tert-butylstyrene-alt-maleic acid)-block-poly(N-acryloylmorpholine) double hydrophilic block copolymers","authors":"Lauren E. Ball ,&nbsp;Bennie Motloung ,&nbsp;Michael-Phillip Smith ,&nbsp;Rueben Pfukwa ,&nbsp;Bert Klumperman","doi":"10.1016/j.eurpolymj.2026.114504","DOIUrl":"10.1016/j.eurpolymj.2026.114504","url":null,"abstract":"<div><div>Stimuli responsive double hydrophilic block copolymers (DHBCs) are ubiquitous in water-based applications, such as drug/gene delivery, nanoreactor and sensor development, photocatalysis, 3D inkjet printing, etc. DHBC-based gels, cross-linked with calcium ions, are particularly valuable for the development of biomedically relevant materials (such as wound dressings or injectable formulations), due to the benignity of Ca²⁺ in biological systems. Therefore, gels formed <em>via</em> the calcium-mediated crosslinking of poly(4-<em>tert</em>-butylstyrene-<em>alt</em>-maleic acid)-<em>block</em>-poly(<em>N</em>-acryloylmorpholine) (P<em>t</em>BuSMA-<em>b</em>-PNAM), which in itself constitutes polymers with established biomedical relevance, are promising candidates for the development of the aforementioned biomedical materials. To this end, P<em>t</em>BuSMA-<em>b</em>-PNAM diblock copolymers were synthesized with different block ratios (1:1, 1:2 and 2:1) and treated with Ca²⁺, whereby the concentration of the two constituents, the pH or the block copolymer architecture was varied, in order to tune the mechanical properties of the P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca²⁺ gels. P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca²⁺ with the lowest P<em>t</em>BuSMA composition (1:2 block ratio) could not form gels and rather formed micelles, whereas P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca²⁺ with the highest P<em>t</em>BuSMA composition (2:1 block ratio) exhibited enhanced mechanical properties compared to the 1:1 block ratio. The overall amphiphilic balance of the P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca²⁺ complexes was therefore proven vital for the design and formation of gels with desirable mechanical properties. P<em>t</em>BuSMA-<em>b</em>-PNAM/Ca²⁺ gels exhibited shear thinning when subjected to high shear conditions and demonstrated some self-healing properties, suggesting these materials have value in the formulation of injectable gels.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114504"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976413","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":"sPAF-225/QAOPBI composite high-temperature proton exchange membrane with robust acid-base interaction and controlled phosphoric acid","authors":"Kun Xu ,&nbsp;Haina Mi ,&nbsp;Xinyi Zong ,&nbsp;Yunji Xie ,&nbsp;Zhaoyan Sun ,&nbsp;Baijun Liu ,&nbsp;Xiaobo Liu ,&nbsp;Wei Hu","doi":"10.1016/j.eurpolymj.2026.114518","DOIUrl":"10.1016/j.eurpolymj.2026.114518","url":null,"abstract":"<div><div>Since phosphoric acid (PA) has a critical effect on HT-PEM performance, a porous aromatic framework with triazine and –OH groups (PAF-225) was synthesized, and sulfonation was utilized for generating sPAF-225 in this work. On the other hand, OPBI was modified by quaternary ammonium (QA) to prepare QAOPBI containing QA groups. The acid-base effect of QA⁺⋅⋅H₂PO₄⁻ ion pairs resulted by the charge interaction between cations and bisphosphonates, can successfully prevent the loss of PA. Furthermore, the –OH, triazine groups and −SO₃H of sPAF-225 can form hydrogen bonds with QAOPBI and PA, this can improve the proton conduction efficiency by the increasing proton transport sites and PA retention rate. The PA retention rate of sPAF-225-6/QAOPBI-30 was 34.7 %, which was considerably greater than OPBI (31.4 %) and sPAF-225-6/OPBI (31.4 %), confirming the effect of QA group on the retention of PA. The peak power density of the H₂/O₂ fuel cells assembled with sPAF-225-6/QAOPBI-30 membrane reached 688.75 mW cm⁻² with low Pt loading of 0.3 mg cm⁻² at 200 °C without additional humidification, effectively optimizing the capability of fuel cell.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114518"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035774","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":"Paracetamol-based benzoxazines for surface protection applications: Hydrophobicity, antimicrobial activity and corrosion resistance","authors":"Praba Nagarajan ,&nbsp;Latha Govindraj ,&nbsp;Balaji Krishnasamy ,&nbsp;Subramanian Sathy Srikandan","doi":"10.1016/j.eurpolymj.2026.114523","DOIUrl":"10.1016/j.eurpolymj.2026.114523","url":null,"abstract":"<div><div>Paracetamol based benzoxazines (PA-Bz) were synthesized using structurally different amines namely 4-aminoacetanilide (AAC), aniline (AN), adamantylamine (AM) and 1,12-diaminododecane (DAD) through Mannich condensation (PA-AAC, PA-AN, PA-AM, PA-DAD). The molecular structure of the synthesized benzoxazines was confirmed through spectroscopic techniques. DSC studies showed that curing temperature of the synthesized benzoxazines are ranged between 205 and 232°C. TGA results showed that poly(PA-DAD) showed the highest maximum degradation temperature of 452°C. Contact angle measurement revealed that poly(PA-AM) exhibited the maximum water contact angle value of 142°. The contact angle studies clearly showed that the resulting polymer can be used for the coating purpose as a hydrophobic sealant. Both PA-AM and its corresponding polymer demonstrated the higher antimicrobial activity. All the synthesized compounds showed 99% corrosion inhibition efficiency. The swelling ratio and high gel content of poly(PA-AN) and poly(PA-DAD) proved its higher crosslinking density. The results obtained on different analysis indicated that the synthesized benzoxazines can be used effectively in coating application, oil–water separation process and also to inhibit the microbial growth on the surface.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114523"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035770","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":"Morphology control in benzoic imine-linked polymer-drug conjugates for adaptive drug delivery and enhanced in vivo efficacy","authors":"Martina Vragović ,&nbsp;Jan Pankrác ,&nbsp;Peter Páral ,&nbsp;Martin Báječný ,&nbsp;Alessandro Jäger ,&nbsp;Vladimir Sincari ,&nbsp;Jan Kučka ,&nbsp;Martin Hrubý ,&nbsp;Marcela Filipová ,&nbsp;Rafał Konefał ,&nbsp;Fernando Carlos Giacomelli ,&nbsp;Luděk Šefc ,&nbsp;Eliézer Jäger","doi":"10.1016/j.eurpolymj.2026.114500","DOIUrl":"10.1016/j.eurpolymj.2026.114500","url":null,"abstract":"<div><div>Nanomedicines have shown significant potential in advancing treatment for a variety of cancer types. Despite these advances, further research is essential to improve the efficacy and selectivity of anticancer nanomedicines, particularly by developing delivery systems capable of achieving high efficacy with minimal off-target toxicity. We herein report novel pH-responsive block copolymer-drug conjugates based on poly(<em>N</em>-(2-hydroxypropyl)methacrylamide) (PHPMAm) and benzoic imine linkages, uniquely combining stealth performance with tunable, acid-triggered drug release. By engineering block and random copolymer architectures with controlled hydrophilic shell length, we systematically evaluated how polymer structure governs self-assembly, release kinetics, and therapeutic outcomes. The conjugates achieve up to 10–12 wt% doxorubicin loading, with pH-selective release half-live spanning within 2–40 h. In contrast to most Schiff base polymer-drug systems limited to <em>in vitro</em> data, the synthesized polymer-drug conjugates demonstrated outstanding antitumor efficacy and 100 % survival for spherical assemblies in aggressive murine lymphoma models, with superior safety. Unlike conventional PEG systems, PHPMAm-based copolymers can potentially avoid anti-PEG immunogenicity and exhibit exceptional <em>in vivo</em> stability and tumor accumulation.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114500"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035777","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":"Solvent-free mechanochemical polycondensation to generate tyrosine-based polyphosphoramidates","authors":"Anastasia E. Gater ,&nbsp;Mitchell A. Nascimento ,&nbsp;Malachy M. Gilbert ,&nbsp;Erin M. Leitao","doi":"10.1016/j.eurpolymj.2026.114506","DOIUrl":"10.1016/j.eurpolymj.2026.114506","url":null,"abstract":"<div><div>Polyphosphoramidates are polymers featuring phosphorus-nitrogen bonds within their side or main chain, which impart unique characteristics such as acid-lability and flame retardancy. However, polyphosphoramidates generally require clever design of (P-N)-containing monomers which can then be linked together through conventional polymerisation strategies. Herein, we report the synthesis and characterisation of tyrosine-based polyphosphoramidates with up to ca. 30 repeat units via solvent-free mechanochemically-assisted polycondensation. This polymer synthesis takes advantage of the bifunctional amino and phenolic moieties of tyrosine to form a random copolymer of <strong>N-P-N</strong>, <strong>N-P-O</strong>, and <strong>O-P-O</strong> bonding motifs between tyrosine methyl ester and phenyldichlorophosphate. While polycondensation routes to polyphosphoramidates have been reported previously, this work also represents the first example of a mechanochemical synthesis of a polyphosphoramidate. The use of solid phase synthesis enables the formation of high molecular weight linear species unobtainable under traditional solution phase methods. The obtained polymer exhibits a <em>T_g</em> of ca. 81 ℃, resists degradation up to 250 ℃, and has a char yield of 45.0% remaining at 700 ℃ in N₂. These results demonstrate a solvent-free mechanochemical route to partially bio-based polyphosphoramidates.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114506"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075195","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":"A star in the window: triazine-based 3D polymer for multicolor electrochromic device applications","authors":"Merve Guzel ,&nbsp;Metin Ak","doi":"10.1016/j.eurpolymj.2026.114537","DOIUrl":"10.1016/j.eurpolymj.2026.114537","url":null,"abstract":"<div><div>In materials science, molecular architecture becomes an art, enabling the creation of advanced materials with precise functionality. Here, we introduce a star-shaped monomer, 3SNS-T, designed with a s-triazine core and three amide-substitute 2.5-bis(2-thienyl)-1H-pyrrole arms. This rationally engineered structure enables the formation of a three-dimensional, electroactive network. The star monomer was synthesized and fully characterized by spectroscopic techniques, and its electronic properties were elucidated via DFT analysis. Electrochemical polymerization of 3SNS-T on an ITO substrate yielded a crosslinked polymer film (p3SNS-T) with remarkable optoelectronic properties, exhibiting high optical contrast, enhanced coloration efficiency, and a rainbow-like multicolor transition. A dual electrochromic device incorporating p3SNS-T and PEDOT demonstrated rapid switching, good stability, and dynamic color modulation under redox control. These findings highlight the power of molecular design in creating functional materials for next-generation smart window technologies.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114537"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075130","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":"Preparation of magnetic UiO-66-NH2/alginate beads via emulsification/internal gelation technique for efficient adsorption of lead (Pb) from aqueous solution","authors":"Jay Yee Lo ,&nbsp;Lee Hong Tee ,&nbsp;Eng-Seng Chan ,&nbsp;Weng Hoong Lam","doi":"10.1016/j.eurpolymj.2026.114525","DOIUrl":"10.1016/j.eurpolymj.2026.114525","url":null,"abstract":"<div><div>Alginate, a naturally derived polysaccharide, has attracted significant attention because of its biocompatibility, low cost, and versatile applications in environmental and biomedical fields. The immobilization of metal organic frameworks (MOFs) within alginate beads for Pb(II) adsorption has attracted considerable interest, owing to the synergistic integration of the high surface area and tunable porosity of MOFs with the functional-group-rich alginate matrix. Previous studies immobilising nanomaterials within alginate biopolymer matrices have predominantly rely on the extrusion-dripping/external gelation technique. The crosslinking of alginate beads in this technique forms large and inhomogeneous gel beads with reduced internal porosity. This study aims to prepare magnetically-responsive alginate beads immobilising UiO-66-NH₂ (MUA beads) using a emulsification/internal gelation technique. This technique enables the formation of micrometric-sized MUA beads with tunable porosity by manipulating the gelation process with CaCO₃, acetic acid, and UiO-66-NH₂ concentration. The physiochemical properties and Pb(II) adsorption efficacy of the beads were investigated. The results indicated that increasing the CaCO₃ content decreased the bead porosity, while higher concentrations of acetic acid and UiO-66-NH₂ increased it. The kinetics and isotherms of the beads followed the pseudo-second-order and Sips models, respectively. MUA-5.0%UiO beads exhibited the fastest adsorption rate (6.38 × 10⁻⁴ g/mg·min). The beads were reusable for at least five cycles without compromising efficacy. Despite the competition from Cu(II), Pb(II) removal efficacy remained above 96%, demonstrating the strong selectivity of the MUA beads. This excellent Pb(II) removal performance is primarily attributed to the synergistic effects of complexation and ion-exchange mechanisms, highlighting the potential of MUA beads for scalable industrial wastewater treatment.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114525"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075112","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":"Lignin-Derived hydrogel exhibiting underwater self-healing under harsh reservoir conditions","authors":"Xiaoyun Qing ,&nbsp;Keyan Wang ,&nbsp;Jiajun Qiu ,&nbsp;Mengting Hu ,&nbsp;Qinpei Wang ,&nbsp;Liang Li ,&nbsp;Zhen Fang ,&nbsp;Yangbing Wen","doi":"10.1016/j.eurpolymj.2026.114522","DOIUrl":"10.1016/j.eurpolymj.2026.114522","url":null,"abstract":"<div><div>In this study, a self-healing lignin-based polyacrylamide/polyvinyl alcohol (SL-cPAM/PVA) hydrogel featuring excellent high temperature and salt resistance was successfully synthesized via a two-step method. Sodium lignosulfonate (S-Lignin) was first incorporated into a chemically crosslinked polyacrylamide (cPAM) network, followed by the formation of dynamic boronate ester linkages among polyvinyl alcohol (PVA), catechol groups, and borax to construct a dual crosslinked structure. The rheological, thermal, and mechanical properties of the hydrogel were comprehensively characterized. The results indicate that the introduction of S-Lignin improved the initial decomposition temperature from 150 °C to 178 °C, and enabled the hydrogel to achieve self-healing behavior at 130 °C, supported by reversible borate ester bonds, hydrogen bonding, and ionic interactions. The hydrogel maintained structural integrity in high-salinity environments (up to 21 × 10⁴ mg/L) and demonstrated remarkable recovery in mechanical strength and microstructure after damage. Even after 30 days of thermal aging at 130 °C, brine-healed hydrogel remained intact without signs of hydrolysis. These findings indicate the excellent potential of SL-cPAM/PVA hydrogel as a water-plugging material in high-temperature, high-salinity oilfield environments, providing a sustainable and functional approach for enhanced oil recovery.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114522"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035769","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":"Fluorine-free triptycene-based poly(ester imide) films: Role of mesogen units in balancing free volume and structural order for low Dk and low Df","authors":"Shiying Qi,&nbsp;Yuqing Lu,&nbsp;Chi Zhang,&nbsp;Zengjin Liu,&nbsp;Jiou Zhang,&nbsp;Jianchao Jiang,&nbsp;Yuanrong Cheng","doi":"10.1016/j.eurpolymj.2026.114516","DOIUrl":"10.1016/j.eurpolymj.2026.114516","url":null,"abstract":"<div><div>Due to the rapid progress in high frequency and high speed communication technologies, there is an urgent demand for polyimide (PI) films that exhibit both low dielectric constant (<em>D</em>_k) and low dielectric loss (<em>D</em>_f) at high frequencies. Achieving a reduction in the <em>D</em>_k of PIs at high frequencies is relatively straightforward in accordance with the Clausius–Mossotti equation. However, the optimization of <em>D</em>_f is more complex and challenging than that of <em>D</em>_k. From the perspective of polarization mechanisms, suppressing dipolar orientational polarization (<em>P</em>_d) provides an effective way to lower <em>D</em>_f. Inspired by liquid crystalline polyesters (LCPs), poly(ester imide)s (PEIs) can achieve ultralow <em>D</em>_f (<em>D</em>_f &lt; 0.0030) by reducing intermolecular friction, but they still exhibit relatively high <em>D</em>_k (<em>D</em>_k &gt; 3.20). In this work, a high free volume triptycene-based diamine (TPC-NH₂) was copolymerized with three ester-containing dianhydrides—phenyl ester (TAHQ), naphthalene ester (NAHQ), and biphenyl ester (BAHQ)—to prepare a series of PEI films with different mesogen units. The influence of the molecular conformations of the mesogen unit on aggregation structure, dielectric properties, thermal properties, mechanical properties, and moisture absorption was systematically evaluated. Wide-angle X-ray diffraction, polarized optical microscopy, and molecular dynamics simulations revealed that phenyl ester dianhydride (TAHQ) and naphthalene ester dianhydride (NAHQ) units yielded amorphous PEIs with low <em>D</em>_k values of 2.62 and 2.55 at 10 GHz, respectively. The “crankshaft-like” <em>para</em>-aromatic ester linkage (Ph–COO–Ph-OCO–Ph) in TPC-TAHQ and TPC-NAHQ restricted imide group deflection through interchain dipole–dipole interactions, thereby lowering <em>D</em>_f to 0.0068 and 0.0051 at 10 GHz, respectively. In contrast, biphenyl ester dianhydride BAHQ-based PEI (TPC-BAHQ) promoted the formation of liquid–crystal-like ordered structure, achieving the lowest <em>D</em>_f of 0.0047 and a relatively low <em>D</em>_k of 2.84 at 10 GHz. Moreover, TPC-BAHQ exhibited outstanding comprehensive properties, including a 5 wt% decomposition temperature (<em>T</em>_d5%) of 502 ℃, a coefficient of thermal expansion (CTE) of 56.3 ppm/℃, a tensile strength (<em>σ</em>_max) of 112.2 MPa, and a water absorption (<em>W</em>_a) of 0.24 %.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114516"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035775","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":"Enzyme biocatalyst for removal of residual monomer fractions in waterborne polymers","authors":"Ana Trajcheva ,&nbsp;Christina Gkountela ,&nbsp;Justine Elgoyhen ,&nbsp;Oihane Sanz ,&nbsp;Stamatina Vouyiouka ,&nbsp;Radmila Tomovska","doi":"10.1016/j.eurpolymj.2026.114507","DOIUrl":"10.1016/j.eurpolymj.2026.114507","url":null,"abstract":"<div><div>This study explores a sustainable post-polymerization approach for waterborne methyl methacrylate/butyl acrylate (MMA/BA) polymer dispersions (latexes) using horseradish peroxidase (HRP) in the presence of hydrogen peroxide and acetylacetone to catalyze radical initiation at extremely low monomer concentrations (ppm level). In the heterogeneous latex system, where residual monomers are primarily confined within polymer particles, the initial monomer conversion was hindered by aqueous-phase radical generation via the enzymatic catalyst, limited monomer diffusion, and restricted penetration of growing oligomers into the particles. Extending the post-polymerization reaction time and supplying an additional fraction of initiator successfully overcame these constraints, enabling very high conversion at 22 °C (&gt;95 % for MMA and ∼ 90 % for BA). As a result, the biocatalytic latex treatment at 22 °C reduced the residual monomer content in the latex from 2345 to 114 ppm. Polymer films prepared from the treated latexes contained MMA/BA oligomers formed during post-polymerization and traces of the enzyme, which reduced mechanical strength but did not affect water uptake. However, the films exhibited improved thermal stability, likely due to enhanced char formation from residual HRP that delayed thermal degradation. Overall, this work demonstrates that HRP-mediated post-polymerization provides a greener strategy for eliminating residual monomers in waterborne polymers, with minimal adverse impact on polymer performance. Traditional polymerization methods, especially chemical ones, often require relatively high monomer concentrations to drive chain propagation efficiently. Demonstrating enzymatic polymerization in very dilute systems reveals previously unexplored operational regimes, providing enhanced mechanistic understanding under these conditions.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"244 ","pages":"Article 114507"},"PeriodicalIF":6.3,"publicationDate":"2026-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145957767","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}