European Polymer Journal最新文献_第3页

Achieving rapid foaming in self-blown non-isocyanate polyurethane foams via controlled epoxy functionality in cyclic carbonates

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-25 DOI: 10.1016/j.eurpolymj.2025.113843

Manal Chaib , Suman Thakur , Hicham Ben Youcef , Mohammed Lahcini , Raquel Verdejo

Non-isocyanate polyurethane (NIPU) foams present a safer and more environmentally friendly alternative to conventional polyurethane (PU) foams, which rely on toxic, petrochemical-based isocyanates. Efficient in-situ CO₂ generation, achieved through the simultaneous aminolysis and hydrolysis of cyclic carbonates, enables replication of traditional PU foaming processes. This study provides the first systematic investigation of the effect of aromatic and aliphatic epoxy functionalities on these reactions and their quantitative correlation with the self-blowing behavior of NIPU foams. Detailed kinetic analysis of model monomers showed significant differences in activation energy, with aromatic systems exhibiting lower activation energy, leading to faster reaction rates, while aliphatic systems had higher activation energy, indicating slower curing. These differences in reactivity were later revealed in the foaming process, where the aromatic groups contributed to rapid foam formation and improved thermal stability, with a glass transition temperature (T_g) of 60 °C. Conversely, aliphatic substituents provided greater material flexibility but revealed a critical threshold, leading to unsuccessful foaming when their content exceeded 30 %, due to slower reaction kinetics. By integrating kinetic data with foaming behavior, we demonstrate that balancing aromatic and aliphatic functionalities enables precise control over foam properties, including T_g, density, and mechanical performance. This work provides new insights into tailoring NIPU foams through epoxy functionality, advancing their potential for sustainable industrial applications.

{"title":"Achieving rapid foaming in self-blown non-isocyanate polyurethane foams via controlled epoxy functionality in cyclic carbonates","authors":"Manal Chaib , Suman Thakur , Hicham Ben Youcef , Mohammed Lahcini , Raquel Verdejo","doi":"10.1016/j.eurpolymj.2025.113843","DOIUrl":"10.1016/j.eurpolymj.2025.113843","url":null,"abstract":"<div><div>Non-isocyanate polyurethane (NIPU) foams present a safer and more environmentally friendly alternative to conventional polyurethane (PU) foams, which rely on toxic, petrochemical-based isocyanates. Efficient in-situ CO<sub>2</sub> generation, achieved through the simultaneous aminolysis and hydrolysis of cyclic carbonates, enables replication of traditional PU foaming processes. This study provides the first systematic investigation of the effect of aromatic and aliphatic epoxy functionalities on these reactions and their quantitative correlation with the self-blowing behavior of NIPU foams. Detailed kinetic analysis of model monomers showed significant differences in activation energy, with aromatic systems exhibiting lower activation energy, leading to faster reaction rates, while aliphatic systems had higher activation energy, indicating slower curing. These differences in reactivity were later revealed in the foaming process, where the aromatic groups contributed to rapid foam formation and improved thermal stability, with a glass transition temperature (T<sub>g</sub>) of 60 °C. Conversely, aliphatic substituents provided greater material flexibility but revealed a critical threshold, leading to unsuccessful foaming when their content exceeded 30 %, due to slower reaction kinetics. By integrating kinetic data with foaming behavior, we demonstrate that balancing aromatic and aliphatic functionalities enables precise control over foam properties, including T<sub>g</sub>, density, and mechanical performance. This work provides new insights into tailoring NIPU foams through epoxy functionality, advancing their potential for sustainable industrial applications.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113843"},"PeriodicalIF":5.8,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143527068","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

Light-controlled assembly and disassembly of cyclodextrin-bisazobenzene supramolecular complexes

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-25 DOI: 10.1016/j.eurpolymj.2025.113849

Carlos Fernández-Clavero , Gonzalo Rivero-Barbarroja , Thais Carmona , Cristina García-Iriepa , Gema Marcelo , Conchita Tros de Ilarduya , Carmen Ortiz Mellet , José M. García Fernández , Juan M. Benito , Francisco Mendicuti

The inclusion complexation of a water soluble bis-azobenzene derivative (bis-Azo) and its monotopic analog (mono-Azo) with α-, β-, and γ-cyclodextrins (CyDs) was investigated as a prototype for light-responsive self-assembling systems. Using spectroscopic techniques (UV–vis, induced circular dichroism, ¹H NMR), computational methods (molecular mechanics and dynamics), and thermodynamic analyses, we examined the photoswitching properties, stability, and structural dynamics of these systems. The azobenzene moieties in the E-isomer of mono-Azo and bis-Azo consistently showed strong affinity for the αCyD cavity, characterized by high association constants. In contrast, no complex formation was observed upon photoinduced E-to-Z isomerization. For bis-Azo, this implies the formation of supramolecular αCyD dimers, with the spatial separation between the oppositely oriented host components determined by the connector linking the two azobenzene moieties in the E-configured ditopic guest. This complex disassembles upon photoswitching, driven by the structural disruption associated with the Z-form. Both the E-and Z-isomers fitted in the cavity of βCyD, with moderate selectivity towards the E-form. A similar scenario was found for complexes with γCyD when using low concentrations of the host. Interestingly, at high concentrations γCyD formed low-solubility pseudopolyrotaxane-type supramolecular architectures with bis-Azo, which were disrupted upon Z-isomer photoisomerization. All the complexes demonstrated high fatigue resistance, maintaining structural integrity after multiple isomerization cycles. This work advances the design of stimuli-responsive preorganized supramolecular systems, with potential applications in nucleic acid delivery through dual pH/light-sensitive mechanisms.

{"title":"Light-controlled assembly and disassembly of cyclodextrin-bisazobenzene supramolecular complexes","authors":"Carlos Fernández-Clavero , Gonzalo Rivero-Barbarroja , Thais Carmona , Cristina García-Iriepa , Gema Marcelo , Conchita Tros de Ilarduya , Carmen Ortiz Mellet , José M. García Fernández , Juan M. Benito , Francisco Mendicuti","doi":"10.1016/j.eurpolymj.2025.113849","DOIUrl":"10.1016/j.eurpolymj.2025.113849","url":null,"abstract":"<div><div>The inclusion complexation of a water soluble bis-azobenzene derivative (bis-Azo) and its monotopic analog (mono-Azo) with α-, β-, and γ-cyclodextrins (CyDs) was investigated as a prototype for light-responsive self-assembling systems. Using spectroscopic techniques (UV–vis, induced circular dichroism, <sup>1</sup>H NMR), computational methods (molecular mechanics and dynamics), and thermodynamic analyses, we examined the photoswitching properties, stability, and structural dynamics of these systems. The azobenzene moieties in the <em>E</em>-isomer of mono-Azo and bis-Azo consistently showed strong affinity for the αCyD cavity, characterized by high association constants. In contrast, no complex formation was observed upon photoinduced <em>E</em>-to-<em>Z</em> isomerization. For bis-Azo, this implies the formation of supramolecular αCyD dimers, with the spatial separation between the oppositely oriented host components determined by the connector linking the two azobenzene moieties in the <em>E</em>-configured ditopic guest. This complex disassembles upon photoswitching, driven by the structural disruption associated with the <em>Z</em>-form. Both the <em>E</em>-and <em>Z</em>-isomers fitted in the cavity of βCyD, with moderate selectivity towards the <em>E</em>-form. A similar scenario was found for complexes with γCyD when using low concentrations of the host. Interestingly, at high concentrations γCyD formed low-solubility pseudopolyrotaxane-type supramolecular architectures with bis-Azo, which were disrupted upon <em>Z</em>-isomer photoisomerization. All the complexes demonstrated high fatigue resistance, maintaining structural integrity after multiple isomerization cycles. This work advances the design of stimuli-responsive preorganized supramolecular systems, with potential applications in nucleic acid delivery through dual pH/light-sensitive mechanisms.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113849"},"PeriodicalIF":5.8,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143521305","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

pH-induced in suit aggregation of Cu2-xSe-POED with extended tumor retention for enhanced chemodynamic /photothermal therapy

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-23 DOI: 10.1016/j.eurpolymj.2025.113859

Xiaofei Shen , Wei Fang , Tianci Sun , Yunfeng Yao , Xiangshun Chen , Lei Xia , Longxiang Tang , Bin Xia , Chang-Tong Yang , Tao He , Rupei Tang

Various functional nanoparticle platforms have been used as alternative approaches for tumor treatment such as chemodynamic (CDT) and photothermal therapies (PTT). However, the tumor microenvironment with dense extracellular matrices and increased interstitial fluid pressure is adverse for enrichment and retention of nanoparticles. Herein, a pH-sensitive Cu_2-xSe-POED nanoparticles (CS-POED NPs) platform is developed to promote the hydrophilic-hydrophobic transition, that contribute to the formation of CS aggregates with large size in tumor tissue. pH-sensitivity of CS-POED NPs results from modifying the surface with pH-sensitive poly(ethylene glycol)-ortho ester-dihydrolipoic acid (POED). The accumulation of CS-POED NPs led to a Fenton-like reaction, generating considerable amounts of ROS to boost the effectiveness of CDT. Meanwhile, the agglomeration CS-POED NPs prolongs their tumor retention resulting in enhanced PTT. According to in vitro and in vivo studies, CS-POED NPs substantially kills tumor cells with laser irradiation, leading to a significant regression of the tumors. In addition, CS-POED NPs have exhibited a favorable biosafety profile based on their in vitro and in vivo evaluations. The novel pH-sensitive CS-POED nanoparticles platform certainly offers a new strategy for enhanced chemodynamic/photothermal tumor therapy.

{"title":"pH-induced in suit aggregation of Cu2-xSe-POED with extended tumor retention for enhanced chemodynamic /photothermal therapy","authors":"Xiaofei Shen , Wei Fang , Tianci Sun , Yunfeng Yao , Xiangshun Chen , Lei Xia , Longxiang Tang , Bin Xia , Chang-Tong Yang , Tao He , Rupei Tang","doi":"10.1016/j.eurpolymj.2025.113859","DOIUrl":"10.1016/j.eurpolymj.2025.113859","url":null,"abstract":"<div><div>Various functional nanoparticle platforms have been used as alternative approaches for tumor treatment such as chemodynamic (CDT) and photothermal therapies (PTT). However, the tumor microenvironment with dense extracellular matrices and increased interstitial fluid pressure is adverse for enrichment and retention of nanoparticles. Herein, a pH-sensitive Cu<sub>2-x</sub>Se-POED nanoparticles (CS-POED NPs) platform is developed to promote the hydrophilic-hydrophobic transition, that contribute to the formation of CS aggregates with large size in tumor tissue. pH-sensitivity of CS-POED NPs results from modifying the surface with pH-sensitive poly(ethylene glycol)-ortho ester-dihydrolipoic acid (POED). The accumulation of CS-POED NPs led to a Fenton-like reaction, generating considerable amounts of ROS to boost the effectiveness of CDT. Meanwhile, the agglomeration CS-POED NPs prolongs their tumor retention resulting in enhanced PTT. According to <em>in vitro</em> and <em>in vivo</em> studies, CS-POED NPs substantially kills tumor cells with laser irradiation, leading to a significant regression of the tumors. In addition, CS-POED NPs have exhibited a favorable biosafety profile based on their <em>in vitro</em> and <em>in vivo</em> evaluations. The novel pH-sensitive CS-POED nanoparticles platform certainly offers a new strategy for enhanced chemodynamic/photothermal tumor therapy.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113859"},"PeriodicalIF":5.8,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143487420","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

Construction of a novel GAP/PCL energetic self-healing blend adhesive system for propellants based on the synergistic effect of hydrogen bond reorganization and disulfide bond exchange reactions

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-23 DOI: 10.1016/j.eurpolymj.2025.113860

Mianji Qiu , Zhi Geng , Wangjian Cheng , Chengyuan Hua , Xing Yan , Baoyun Ye , Chongwei An , Jingyu Wang

Solid propellants are essential for rocket engine efficiency and safety. The introduction of energetic self-healing adhesives can improve its energy density, mechanical properties, and safety, while extending its service life. Therefore, this paper proposes a novel energetic self-healing adhesive that utilizes asymmetric alicyclic isophorone diisocyanate (IPDI) and 2-(aminophenyl) disulfide (2-AFD), which has a bent biphenyl ring structure, as hard segments, combined with semicrystalline polymer polycaprolactone (PCL) and energetic adhesive glycidyl azide polymer (GAP) as soft segments to synthesize a series of self-healing adhesives. By adjusting the hard segment content, a balance between mechanical properties and self-healing performance is achieved. Results show that increasing the hard segment content enhances toughness (from 26.60 MJ·m⁻³ to 58.54 MJ·m⁻³), but decreases self-healing efficiency (from 90 % to 58 %). GPPU-2 exhibits 38.95 MJ·m⁻³ toughness and recovers 86 % of its toughness within 90 min at 80 °C via dynamic disulfide and hydrogen bond interactions. The GPPU-2-based propellant, GPPU80, recovers 88.22 % of tensile strength after 24 h at 80 °C, demonstrating effective crack propagation inhibition. Compared to inert adhesive-based propellants, GPPU80 shows superior combustion performance and energy release. This study offers insights for designing high-performance self-healing adhesives to enhance propellant safety and energy density.

{"title":"Construction of a novel GAP/PCL energetic self-healing blend adhesive system for propellants based on the synergistic effect of hydrogen bond reorganization and disulfide bond exchange reactions","authors":"Mianji Qiu , Zhi Geng , Wangjian Cheng , Chengyuan Hua , Xing Yan , Baoyun Ye , Chongwei An , Jingyu Wang","doi":"10.1016/j.eurpolymj.2025.113860","DOIUrl":"10.1016/j.eurpolymj.2025.113860","url":null,"abstract":"<div><div>Solid propellants are essential for rocket engine efficiency and safety. The introduction of energetic self-healing adhesives can improve its energy density, mechanical properties, and safety, while extending its service life. Therefore, this paper proposes a novel energetic self-healing adhesive that utilizes asymmetric alicyclic isophorone diisocyanate (IPDI) and 2-(aminophenyl) disulfide (2-AFD), which has a bent biphenyl ring structure, as hard segments, combined with semicrystalline polymer polycaprolactone (PCL) and energetic adhesive glycidyl azide polymer (GAP) as soft segments to synthesize a series of self-healing adhesives. By adjusting the hard segment content, a balance between mechanical properties and self-healing performance is achieved. Results show that increasing the hard segment content enhances toughness (from 26.60 MJ·m<sup>−3</sup> to 58.54 MJ·m<sup>−3</sup>), but decreases self-healing efficiency (from 90 % to 58 %). GPPU-2 exhibits 38.95 MJ·m<sup>−3</sup> toughness and recovers 86 % of its toughness within 90 min at 80 °C via dynamic disulfide and hydrogen bond interactions. The GPPU-2-based propellant, GPPU80, recovers 88.22 % of tensile strength after 24 h at 80 °C, demonstrating effective crack propagation inhibition. Compared to inert adhesive-based propellants, GPPU80 shows superior combustion performance and energy release. This study offers insights for designing high-performance self-healing adhesives to enhance propellant safety and energy density.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113860"},"PeriodicalIF":5.8,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511166","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

Photoresponsive cryogels based on poly(2-oxazoline)s

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-21 DOI: 10.1016/j.eurpolymj.2025.113845

Tim Hoffmann , Florian Behrendt , Lukas Dietz , Caroline T. Holick , Pascal Scharfenberg , Michael Gottschaldt , Bernd W. Sigusch , Ulrich S. Schubert

Herein, we present the synthesis of two poly(2-oxazoline)-based photodegradable cross-linkers. For that 1-(piperazin-1-yl)ethan-1-one-O-methacryloyl oxime (PipOxim) was synthesized as new photocleavable, polymerizable endcapping agent for the termination of the cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazoline (EtOx), to yield in the bifunctional cross-linker B-Et(10)PipOxim. Secondly, bifunctional poly(2-ethyl-2-oxazoline)s (PEtOx) carrying photocleavable, polymerizable triazene phenyl methacrylate (TAz) ω-end groups were prepared by post-polymerization functionalization (B-Et(10,20,40)TAz). The process of decomposition under UV–Vis irradiation was successfully demonstrated for all cross-linkers that had been produced using UV–Vis spectroscopy. From the photodegradable POx-based cross-linkers, cryogels were prepared with 100% of the two different cross-linkers. Additionally, mixed cryogels made of B-Et(40)TAz and acrylic acid were produced. All cryogels were characterized by thermogravimetric analysis (TGA), solid-state NMR (ssNMR), scanning electron microscopy (SEM) and swelling investigations. Notably, the use of 92 mol% acrylic acid led to the formation of cryogels susceptible to a complete dissolution in water after exposure to UV–Vis light.

{"title":"Photoresponsive cryogels based on poly(2-oxazoline)s","authors":"Tim Hoffmann , Florian Behrendt , Lukas Dietz , Caroline T. Holick , Pascal Scharfenberg , Michael Gottschaldt , Bernd W. Sigusch , Ulrich S. Schubert","doi":"10.1016/j.eurpolymj.2025.113845","DOIUrl":"10.1016/j.eurpolymj.2025.113845","url":null,"abstract":"<div><div>Herein, we present the synthesis of two poly(2-oxazoline)-based photodegradable cross-linkers. For that 1-(piperazin-1-yl)ethan-1-one-<em>O</em>-methacryloyl oxime (<strong>PipOxim</strong>) was synthesized as new photocleavable, polymerizable endcapping agent for the termination of the cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazoline (EtOx), to yield in the bifunctional cross-linker <strong>B-Et(10)PipOxim</strong>. Secondly, bifunctional poly(2-ethyl-2-oxazoline)s (PEtOx) carrying photocleavable, polymerizable triazene phenyl methacrylate (TAz) ω-end groups were prepared by post-polymerization functionalization (<strong>B-Et(10,20,40)TAz</strong>). The process of decomposition under UV–Vis irradiation was successfully demonstrated for all cross-linkers that had been produced using UV–Vis spectroscopy. From the photodegradable POx-based cross-linkers, cryogels were prepared with 100% of the two different cross-linkers. Additionally, mixed cryogels made of <strong>B-Et(40)TAz</strong> and acrylic acid were produced. All cryogels were characterized by thermogravimetric analysis (TGA), solid-state NMR (ssNMR), scanning electron microscopy (SEM) and swelling investigations. Notably, the use of 92 mol% acrylic acid led to the formation of cryogels susceptible to a complete dissolution in water after exposure to UV–Vis light.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113845"},"PeriodicalIF":5.8,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143551746","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

Tailoring chain structures in Ethylene/Propylene copolymers through controlled monomer feeding strategies

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-21 DOI: 10.1016/j.eurpolymj.2025.113847

Minghao Sun , Yangke Xiao , Kan Liu , Haitao Wang , Bangban Zhu , Yinlong Chang , Jieyuan Zheng , Xingfen Huang , Shengbin Shi , Pingwei Liu , Wen-Jun Wang

Polyolefins with desired properties can be achieved through precise control of chain structure. This study emphasizes the critical role of monomer feeding strategies in determining chain sequence distribution and topology to enhance the performance of ethylene/propylene rubbers (EPMs). Linear EPMs were synthesized via continuously feeding a fixed composition ethylene/ propylene mixture or through sequential monomer feeding. In contract, long-chain branched (LCB) EPMs (B-EPs) were produced via a tandem catalytic polymerization process, in which macromonomers were first synthesized and subsequently copolymerized with a continuous feed of ethylene/ propylene mixture with fixed composition. The impact of these feeding strategies on the resulting polymer chain structures, as well as their mechanical, thermal, and rheological properties, were systematically investigated. Incorporating 0.7 isotactic polypropylene (iPP) LCBs into the EPM backbone significantly improved the B-EP properties, yielding a high melting point of 141 °C and a low-temperature tensile strength of 52.1 MPa, while having a tensile strength of 8.0 MPa and an elastic recovery of 71.5 %. Furthermore, the B-EP with iPP LCBs demonstrated excellent compatibility with isotactic polypropylene, enhancing the impact resistance of a 30 wt% B-EP/ commercial isotactic polypropylene blend by 23.5 % compared to a similar compound with commercial EPDM. The study provides valuable insights into optimizing EPM performance by tailoring chain structures through controlled monomer feeding strategies.

{"title":"Tailoring chain structures in Ethylene/Propylene copolymers through controlled monomer feeding strategies","authors":"Minghao Sun , Yangke Xiao , Kan Liu , Haitao Wang , Bangban Zhu , Yinlong Chang , Jieyuan Zheng , Xingfen Huang , Shengbin Shi , Pingwei Liu , Wen-Jun Wang","doi":"10.1016/j.eurpolymj.2025.113847","DOIUrl":"10.1016/j.eurpolymj.2025.113847","url":null,"abstract":"<div><div>Polyolefins with desired properties can be achieved through precise control of chain structure. This study emphasizes the critical role of monomer feeding strategies in determining chain sequence distribution and topology to enhance the performance of ethylene/propylene rubbers (EPMs). Linear EPMs were synthesized via continuously feeding a fixed composition ethylene/ propylene mixture or through sequential monomer feeding. In contract, long-chain branched (LCB) EPMs (B-EPs) were produced via a tandem catalytic polymerization process, in which macromonomers were first synthesized and subsequently copolymerized with a continuous feed of ethylene/ propylene mixture with fixed composition. The impact of these feeding strategies on the resulting polymer chain structures, as well as their mechanical, thermal, and rheological properties, were systematically investigated. Incorporating 0.7 isotactic polypropylene (iPP) LCBs into the EPM backbone significantly improved the B-EP properties, yielding a high melting point of 141 °C and a low-temperature tensile strength of 52.1 MPa, while having a tensile strength of 8.0 MPa and an elastic recovery of 71.5 %. Furthermore, the B-EP with iPP LCBs demonstrated excellent compatibility with isotactic polypropylene, enhancing the impact resistance of a 30 wt% B-EP/ commercial isotactic polypropylene blend by 23.5 % compared to a similar compound with commercial EPDM. The study provides valuable insights into optimizing EPM performance by tailoring chain structures through controlled monomer feeding strategies.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"229 ","pages":"Article 113847"},"PeriodicalIF":5.8,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143527069","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

High efficient mechanically induced atom transfer radical polymerization in aqueous media facilitated by piezoelectric heterostructures

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-21 DOI: 10.1016/j.eurpolymj.2025.113837

Junle Zhang , Shuo Xu , Wenjie Zhang , Ge Shi , Yanjie He , Xiaoguang Qiao , Xinchang Pang

With ZnO/BaTiO₃ piezoelectric heterostructures as the catalyst, highly efficient ultrasonication-induced atom transfer radical polymerization (ATRP) in aqueous media was developed. Under ultrasonic action, the ZnO/BaTiO₃ heterostructure undergoes polarization and generates hole-electron pairs. The transfer of electrons to copper ions promotes the ATRP, while the strong oxidizing effect of the holes decomposes water molecules to generate hydroxyl radicals which lead to the loss of control of polymerization. By using ethanol as the co-solvent (V/V = 1/1) to capture the hydroxyl radicals and NaBr (0.66 mg/mL) to restrict the dissociation of bromide anions from the deactivator, the conversion of the monomer hydroxyethyl acrylate (HEA) reached 59.1 % within 12 min and 89.2 % within 30 min, in the presence of 600 ppm CuBr₂/tris(2-pyrodylmethyl) (TPMA) and 3 mg/mL ZnO/BaTiO₃ heterostructure, with low molecular weight distribution (M_w/M_n < 1.25). The polymerization can be temporally controlled by switching the ultrasound on and off, and it has also been demonstrated that the polymerization exhibits high chain-end fidelity. In addition, research was also conducted on the recycling of ZnO/BaTiO₃, and the results indicated that the polymerization catalytic system possesses characteristics of sustainable development.

{"title":"High efficient mechanically induced atom transfer radical polymerization in aqueous media facilitated by piezoelectric heterostructures","authors":"Junle Zhang , Shuo Xu , Wenjie Zhang , Ge Shi , Yanjie He , Xiaoguang Qiao , Xinchang Pang","doi":"10.1016/j.eurpolymj.2025.113837","DOIUrl":"10.1016/j.eurpolymj.2025.113837","url":null,"abstract":"<div><div>With ZnO/BaTiO<sub>3</sub> piezoelectric heterostructures as the catalyst, highly efficient ultrasonication-induced atom transfer radical polymerization (ATRP) in aqueous media was developed. Under ultrasonic action, the ZnO/BaTiO<sub>3</sub> heterostructure undergoes polarization and generates hole-electron pairs. The transfer of electrons to copper ions promotes the ATRP, while the strong oxidizing effect of the holes decomposes water molecules to generate hydroxyl radicals which lead to the loss of control of polymerization. By using ethanol as the co-solvent (V/V = 1/1) to capture the hydroxyl radicals and NaBr (0.66 mg/mL) to restrict the dissociation of bromide anions from the deactivator, the conversion of the monomer hydroxyethyl acrylate (HEA) reached 59.1 % within 12 min and 89.2 % within 30 min, in the presence of 600 ppm CuBr<sub>2</sub>/tris(2-pyrodylmethyl) (TPMA) and 3 mg/mL ZnO/BaTiO<sub>3</sub> heterostructure, with low molecular weight distribution (<em>M</em><sub>w</sub>/<em>M</em><sub>n</sub> < 1.25). The polymerization can be temporally controlled by switching the ultrasound on and off, and it has also been demonstrated that the polymerization exhibits high chain-end fidelity. In addition, research was also conducted on the recycling of ZnO/BaTiO<sub>3</sub>, and the results indicated that the polymerization catalytic system possesses characteristics of sustainable development.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113837"},"PeriodicalIF":5.8,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143508378","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

Expanding the horizons of polymer engineering: Advances in PDMS modification through RDRP techniques

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-21 DOI: 10.1016/j.eurpolymj.2025.113844

Kinga Ślusarczyk , Monika Flejszar , Faustyna Stopyra , Paweł Chmielarz

Polydimethylsiloxane (PDMS) constitutes one of the most interesting representants of the silicones, with application in numerous fields, including biomedicine or microprinting, due to its flexibility, excellent transparency and biocompatibility. For this reason, the development of the PDMS-based materials continue to abide. To fully expand the PDMS potential, reversible deactivation radical polymerization (RDRP) methods are being employed to achieve di- and triblock copolymers or cross-linked PDMS films modified with polymer brushes, attributing new, unique features, such as marine antifouling, self-polishing properties, pH-sensitivity or increased durability of the coatings. Following the current trends in the material engineering of designing smart materials, the superior performance of the newly developed materials for controlled drug delivery, gas sorption, photocatalysts and many others was presented. Thus, this review does not only summarize the recent advances in the PDMS materials functionalization via RDRP techniques, but also raises a crucial question whether PDMS, although already used for several decades, may yet become the material of the future.

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引用次数: 0

Application of new photoinitiating systems based on BODIPY derivatives in long-wavelength photo-induced free radical polymerization

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-20 DOI: 10.1016/j.eurpolymj.2025.113833

Hui Deng , Jiansong Yin , Yingzhu Sun , Wenlong Tang , Yijie Yu , Hao Li , Yangyang Xu , Changjiang Yu , Ke Sun , Jacques Lalevée

Efficient photopolymerization activated by photoinitiators or photoinitiating systems (PISs) under visible light irradiation, especially at long wavelengths, has remained as a challenging research focus. In this work, four novel boron dipyrromethene (BODIPY) derivatives with high fluorescence properties were systematically investigated as light-harvesting organic dyes, which exhibited remarkable photoinitiation capacities under long-wavelength light irradiation. Markedly, these BODIPY derivatives efficiently induced the free radical photopolymerization of acrylates under irradiation from violet-to-green light-emitting diodes (LEDs), benefiting from the construction of three-component PISs comprising an amine and an iodonium salt. The high photoreactivity of these BODIPY dyes was assessed through steady-state photolysis and excited-state fluorescence quenching analyses, while the corresponding photochemical parameters were attained by theoretical calculations under the density functional theory (DFT) method. In order to expand potential application areas, photopolymerized acrylate monomers by direct laser writing experiments using the investigated PIS, resulting in 3D patterns with smooth surfaces. high spatial resolution and significant fluorescence were successfully fabricated, providing a promising opportunity for developing efficient PIs with high fluorescence in photo-curing 3D printing area.

{"title":"Application of new photoinitiating systems based on BODIPY derivatives in long-wavelength photo-induced free radical polymerization","authors":"Hui Deng , Jiansong Yin , Yingzhu Sun , Wenlong Tang , Yijie Yu , Hao Li , Yangyang Xu , Changjiang Yu , Ke Sun , Jacques Lalevée","doi":"10.1016/j.eurpolymj.2025.113833","DOIUrl":"10.1016/j.eurpolymj.2025.113833","url":null,"abstract":"<div><div>Efficient photopolymerization activated by photoinitiators or photoinitiating systems (PISs) under visible light irradiation, especially at long wavelengths, has remained as a challenging research focus. In this work, four novel boron dipyrromethene (BODIPY) derivatives with high fluorescence properties were systematically investigated as light-harvesting organic dyes, which exhibited remarkable photoinitiation capacities under long-wavelength light irradiation. Markedly, these BODIPY derivatives efficiently induced the free radical photopolymerization of acrylates under irradiation from violet-to-green light-emitting diodes (LEDs), benefiting from the construction of three-component PISs comprising an amine and an iodonium salt. The high photoreactivity of these BODIPY dyes was assessed through steady-state photolysis and excited-state fluorescence quenching analyses, while the corresponding photochemical parameters were attained by theoretical calculations under the density functional theory (DFT) method. In order to expand potential application areas, photopolymerized acrylate monomers by direct laser writing experiments using the investigated PIS, resulting in 3D patterns with smooth surfaces. high spatial resolution and significant fluorescence were successfully fabricated, providing a promising opportunity for developing efficient PIs with high fluorescence in photo-curing 3D printing area.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113833"},"PeriodicalIF":5.8,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143487419","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

Bio-polyol chemical design for self-healing boronate ester gels by green oxyalkylation of organosolv lignin 通过对有机溶胶木质素进行绿色氧烷基化，为自愈合硼酸酯凝胶设计生物多元醇化学方法

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal

Pub Date : 2025-02-19 DOI: 10.1016/j.eurpolymj.2025.113846

Bram Jacobs , Ine Van Nieuwenhove , Sander Driesen , Pablo Reyes , Dagmar R. D’hooge , Geert-Jan Graulus , Katrien V. Bernaerts , An Verberckmoes

Lignin, the most abundant aromatic biopolymer, has a high potential as an alternative to fossil resources in the chemical industry. However, the non-uniformity of lignin is currently a drawback for high-end applications. In this work, glycerol carbonate being a green and safe cyclic carbonate was therefore applied in the oxyalkylation of organosolv lignin (weight average molecular weight of ≈ 8,300 g mol⁻¹; aliphatic OH content of ca. 2.61 mmol g⁻¹) to obtain a lignin-based polyol with solely aliphatic OH functionalities. The catalyst type, reaction temperature and time and additional solvents were evaluated in the oxyalkylation with optimal settings using K₂CO_3, 175 °C, 30 min reaction time without any additional solvent to make a modified lignin with a weight average molecular weight of ca. 15,000 g mol⁻¹ and an aliphatic OH content of ca. 4.59 mmol g⁻¹. To support mechanistic understanding it is shown that the carboxylic acid and phenolic hydroxyl functionalities are converted completely into 1,2-diols, while native aliphatic OH functionalities take at most slightly part in the modification reaction. Furthermore, upon the formation of vicinal diols, the functionalities partially react with glycerol carbonate by an internal transesterification into cyclic carbonate functionalities, this undesirable reaction being more dominant at lower temperatures. Notably, the performance of the oxyalkylation strategy is sufficient to crosslink the modified lignin with benzene-1,4-diboronic acid into a gel-like material with identical shear storage and loss moduli before destruction and immediately after destruction (for the lowest amount of crosslinker added = 1:1.15 diol/boronic acid functionalities molar ratio).

{"title":"Bio-polyol chemical design for self-healing boronate ester gels by green oxyalkylation of organosolv lignin","authors":"Bram Jacobs , Ine Van Nieuwenhove , Sander Driesen , Pablo Reyes , Dagmar R. D’hooge , Geert-Jan Graulus , Katrien V. Bernaerts , An Verberckmoes","doi":"10.1016/j.eurpolymj.2025.113846","DOIUrl":"10.1016/j.eurpolymj.2025.113846","url":null,"abstract":"<div><div>Lignin, the most abundant aromatic biopolymer, has a high potential as an alternative to fossil resources in the chemical industry. However, the non-uniformity of lignin is currently a drawback for high-end applications. In this work, glycerol carbonate being a green and safe cyclic carbonate was therefore applied in the oxyalkylation of organosolv lignin (weight average molecular weight of ≈ 8,300 g mol<sup>−1</sup>; aliphatic OH content of ca. 2.61 mmol g<sup>−1</sup>) to obtain a lignin-based polyol with solely aliphatic OH functionalities. The catalyst type, reaction temperature and time and additional solvents were evaluated in the oxyalkylation with optimal settings using K<sub>2</sub>CO<sub>3,</sub> 175 °C, 30 min reaction time without any additional solvent to make a modified lignin with a weight average molecular weight of ca. 15,000 g mol<sup>−1</sup> and an aliphatic OH content of ca. 4.59 mmol g<sup>−1</sup>. To support mechanistic understanding it is shown that the carboxylic acid and phenolic hydroxyl functionalities are converted completely into 1,2-diols, while native aliphatic OH functionalities take at most slightly part in the modification reaction. Furthermore, upon the formation of vicinal diols, the functionalities partially react with glycerol carbonate by an internal transesterification into cyclic carbonate functionalities, this undesirable reaction being more dominant at lower temperatures. Notably, the performance of the oxyalkylation strategy is sufficient to crosslink the modified lignin with benzene-1,4-diboronic acid into a gel-like material with identical shear storage and loss moduli before destruction and immediately after destruction (for the lowest amount of crosslinker added = 1:1.15 diol/boronic acid functionalities molar ratio).</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"228 ","pages":"Article 113846"},"PeriodicalIF":5.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143487411","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