Pub Date : 2024-11-05DOI: 10.1016/j.eurpolymj.2024.113561
Dan Ji, Yaping Wang, Mengqing Luo, Zihao Zhang, Xiaohua Chang, Yutian Zhu
Dual-responsive shape-transformable block copolymer (BCP) particles have arisen great attentions because of their tunable physical and chemical characteristics triggered by external stimuli. Herein, we developed a simple yet effective strategy to realize pH and light dual-triggered shape-switchable BCP particles through the co-assembly of BCPs with photo-responsive additive 4-hydroxyazobenzene (Azo-OH) within the evaporation emulsion droplets. The formation of hydrogen bonding interactions between the Azo-OH and 4-vinylpyridine (4VP) unit increases the volume fraction of P4VP domain, in turn leading to a morphological transition of the particles from onions to pupas by tuning the Azo-OH content. Subsequent light-induced trans–cis transition of the Azo unit induces the enhancement of the hydrophilicity of the P4VP domains, giving rise to internal shape transitions of the BCP particles from pupas to onions with P4VP at the outmost-layer. Furtherly, since the hydrogen bonds between Azo-OH and 4VP group are sensitive to pH, the interfacial properties of the emulsion droplets and the assembled structures are tuned through adjusting the environment pH of the aqueous solution, causing the formation of various particle shape, including pupas, raspberries, and onions. This work offers a promising method to engineer the microstructures of polymeric assemblies, which may attract more attention on the applications of the stimuli-responsive particles.
{"title":"pH and light-triggered shape transformation of block copolymer particles in emulsion droplets","authors":"Dan Ji, Yaping Wang, Mengqing Luo, Zihao Zhang, Xiaohua Chang, Yutian Zhu","doi":"10.1016/j.eurpolymj.2024.113561","DOIUrl":"10.1016/j.eurpolymj.2024.113561","url":null,"abstract":"<div><div>Dual-responsive shape-transformable block copolymer (BCP) particles have arisen great attentions because of their tunable physical and chemical characteristics triggered by external stimuli. Herein, we developed a simple yet effective strategy to realize pH and light dual-triggered shape-switchable BCP particles through the co-assembly of BCPs with photo-responsive additive 4-hydroxyazobenzene (Azo-OH) within the evaporation emulsion droplets. The formation of hydrogen bonding interactions between the Azo-OH and 4-vinylpyridine (4VP) unit increases the volume fraction of P4VP domain, in turn leading to a morphological transition of the particles from onions to pupas by tuning the Azo-OH content. Subsequent light-induced <em>trans</em>–<em>cis</em> transition of the Azo unit induces the enhancement of the hydrophilicity of the P4VP domains, giving rise to internal shape transitions of the BCP particles from pupas to onions with P4VP at the outmost-layer. Furtherly, since the hydrogen bonds between Azo-OH and 4VP group are sensitive to pH, the interfacial properties of the emulsion droplets and the assembled structures are tuned through adjusting the environment pH of the aqueous solution, causing the formation of various particle shape, including pupas, raspberries, and onions. This work offers a promising method to engineer the microstructures of polymeric assemblies, which may attract more attention on the applications of the stimuli-responsive particles.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113561"},"PeriodicalIF":5.8,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662929","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}
Food waste exacerbates greenhouse gas emissions and environmental degradation, while the prevalent use of conventional plastics in food packaging, characterized by their cost-efficiency, lightweight nature, and durability, has intensified environmental concerns through increased greenhouse gas emissions and waste accumulation. In response, the utilization of biowaste-derived biopolymers for bioplastic production has emerged as a promising strategy within the framework of the circular economy. Although these bioplastics offer advantages such as biodegradability and bio-based origins, early formulations were constrained by suboptimal mechanical strength, hydrophilicity, and barrier properties, necessitating the incorporation of advanced additives. Recent advancements have centred on improving the functionality of bioplastics derived from biowaste through the integration of specialized additives. These enhancements, including the incorporation of functional fillers and reinforcement agents, have significantly augmented the tensile strength, Young’s modulus, thermal stability, and water vapor barrier performance of bioplastics. Additionally, these additives impart notable antimicrobial and antioxidant properties, which enhance food safety and extend shelf life while maintaining eco-friendly characteristics. This review comprehensively examines the latest innovations in biowaste-to-bioplastics technologies, focusing on the integration of antimicrobial, antioxidant, and physiochemical enhancements. By highlighting these advancements, the review emphasizes the transformative potential of biowaste-derived bioplastics in developing sustainable food packaging solutions and advancing a circular economy.
{"title":"Ecofriendly bioplastics from biowaste: Antimicrobial and functional enhancements for sustainable packaging","authors":"Dilip Kumar Chandra , Awanish Kumar, Chinmaya Mahapatra","doi":"10.1016/j.eurpolymj.2024.113557","DOIUrl":"10.1016/j.eurpolymj.2024.113557","url":null,"abstract":"<div><div>Food waste exacerbates greenhouse gas emissions and environmental degradation, while the prevalent use of conventional plastics in food packaging, characterized by their cost-efficiency, lightweight nature, and durability, has intensified environmental concerns through increased greenhouse gas emissions and waste accumulation. In response, the utilization of biowaste-derived biopolymers for bioplastic production has emerged as a promising strategy within the framework of the circular economy. Although these bioplastics offer advantages such as biodegradability and bio-based origins, early formulations were constrained by suboptimal mechanical strength, hydrophilicity, and barrier properties, necessitating the incorporation of advanced additives. Recent advancements have centred on improving the functionality of bioplastics derived from biowaste through the integration of specialized additives. These enhancements, including the incorporation of functional fillers and reinforcement agents, have significantly augmented the tensile strength, Young’s modulus, thermal stability, and water vapor barrier performance of bioplastics. Additionally, these additives impart notable antimicrobial and antioxidant properties, which enhance food safety and extend shelf life while maintaining eco-friendly characteristics. This review comprehensively examines the latest innovations in biowaste-to-bioplastics technologies, focusing on the integration of antimicrobial, antioxidant, and physiochemical enhancements. By highlighting these advancements, the review emphasizes the transformative potential of biowaste-derived bioplastics in developing sustainable food packaging solutions and advancing a circular economy.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113557"},"PeriodicalIF":5.8,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142663010","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}
Pub Date : 2024-11-05DOI: 10.1016/j.eurpolymj.2024.113554
Ying Liu , Qingyun Ma , Zhixuan Wang , Xinxin Shang , Yuting Lan , Guoping Guan , Lu Wang
Thrombosis and infection are the primary challenges limiting the clinical application of small-diameter artificial blood vessels. Numerous studies have focused on improving the hemocompatibility of artificial vascular materials, addressing properties such as anticoagulant activity, antithrombogenicity, low hemolysis rates, and reduced platelet adhesion. However, there has been comparatively less attention given to the antibacterial properties of these materials. This study utilizes polyester braided tubes and PVA/PAAm hydrogel materials, combined with surface modification techniques, to develop a pH-responsive antibacterial hydrogel artificial blood vessel graft. The hydrogel surface was grafted with a polymer brush hierarchical structure, and antimicrobial peptide MLT was immobilized to confer antibacterial properties. Additionally, 2,3-dimethylmaleic anhydride (DMMA) was covalently attached as a shielding group to achieve an environment-responsive strategy. The research demonstrates that this artificial blood vessel graft exhibits structural stability, excellent mechanical properties, and good cellular and hemocompatibility. Furthermore, it exhibits pH-responsive capabilities, triggering efficient antibacterial activity in low pH environments. The modified antibacterial hydrogel artificial blood vessel material shows low hemolysis rates, excellent anticoagulant properties, and reduced platelet adhesion. Therefore, the strategy of combining MLT with DMMA may effectively enhance the hemocompatibility and responsive antibacterial performance of artificial blood vessel materials.
{"title":"Antimicrobial peptide-based pH-responsive Polyvinyl alcohol hydrogel artificial vascular grafts with excellent antimicrobial and hematologic compatibility","authors":"Ying Liu , Qingyun Ma , Zhixuan Wang , Xinxin Shang , Yuting Lan , Guoping Guan , Lu Wang","doi":"10.1016/j.eurpolymj.2024.113554","DOIUrl":"10.1016/j.eurpolymj.2024.113554","url":null,"abstract":"<div><div>Thrombosis and infection are the primary challenges limiting the clinical application of small-diameter artificial blood vessels. Numerous studies have focused on improving the hemocompatibility of artificial vascular materials, addressing properties such as anticoagulant activity, antithrombogenicity, low hemolysis rates, and reduced platelet adhesion. However, there has been comparatively less attention given to the antibacterial properties of these materials. This study utilizes polyester braided tubes and PVA/PAAm hydrogel materials, combined with surface modification techniques, to develop a pH-responsive antibacterial hydrogel artificial blood vessel graft. The hydrogel surface was grafted with a polymer brush hierarchical structure, and antimicrobial peptide MLT was immobilized to confer antibacterial properties. Additionally, 2,3-dimethylmaleic anhydride (DMMA) was covalently attached as a shielding group to achieve an environment-responsive strategy. The research demonstrates that this artificial blood vessel graft exhibits structural stability, excellent mechanical properties, and good cellular and hemocompatibility. Furthermore, it exhibits pH-responsive capabilities, triggering efficient antibacterial activity in low pH environments. The modified antibacterial hydrogel artificial blood vessel material shows low hemolysis rates, excellent anticoagulant properties, and reduced platelet adhesion. Therefore, the strategy of combining MLT with DMMA may effectively enhance the hemocompatibility and responsive antibacterial performance of artificial blood vessel materials.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113554"},"PeriodicalIF":5.8,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662680","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}
Investigating the solvatochromism of stimuli-chromic compounds such as oxazolidine in polymer matrices with various polarities or functionalities is a unique approach to developing advanced materials for anticounterfeiting, sensor, optoelectronic, and displayers. In a novel strategy, multi-functionalized copolymer nanoparticles were synthesized by copolymerization of methyl methacrylate (MMA) with various functional comonomers in emulsion media for post-polymerization modification with oxazolidine and investigation of its solvatochromism in both colloidal solution and solid phase. The particle size and morphology of nanoparticles were influenced significantly by the polarity of functional groups, and the morphology evolution from sphere to anisotropic shapes was observed by increasing the polarity of functional groups. Investigation of oxazolidine solvatochromism in colloidal solution and solid polymer powders indicated different mechanisms for solvatochromism, in which the polarity of media is the main effective parameter in colloidal solution and the polarity of functional groups in the polymer structure is the main effective parameter in solid polymer phase. The solvatochromism of oxazolidine was confirmed by observed red shift and blue shift in UV–Vis and fluorescence spectra, in which the intensity of absorbance and emission peaks was changed as a function of the polarity of functional groups. Solvatochromic photoluminescent polymer nanoparticles were used for several advanced applications such as solid anticounterfeiting inks to information encryption, dual-mode visualization of latent fingerprints, and also development of organic light-emitting diodes (OLEDs). For the first time, the results indicate a significant effect of polymer chain local polarity induced by functional groups on the tuning of optical properties of the oxazolidine by the solid-state solvatochromic phenomenon. Solvatochromism of oxazolidine in functionalized polymer nanoparticles is an interesting approach to developing novel intelligent materials that have advanced applications in different fields such as anticounterfeiting and information encryption, optoelectronic, polarity sensor, and visualization of latent fingerprints.
{"title":"Solid-state solvatochromism of oxazolidine in multi-functionalized copolymer nanoparticles: Development of advanced materials with multi-color fluorescence","authors":"Amin Abdollahi , Younes Habibi , Bita Ghasemi , Zahra Mohamadnia","doi":"10.1016/j.eurpolymj.2024.113555","DOIUrl":"10.1016/j.eurpolymj.2024.113555","url":null,"abstract":"<div><div>Investigating the solvatochromism of stimuli-chromic compounds such as oxazolidine in polymer matrices with various polarities or functionalities is a unique approach to developing advanced materials for anticounterfeiting, sensor, optoelectronic, and displayers. In a novel strategy, multi-functionalized copolymer nanoparticles were synthesized by copolymerization of methyl methacrylate (MMA) with various functional comonomers in emulsion media for post-polymerization modification with oxazolidine and investigation of its solvatochromism in both colloidal solution and solid phase. The particle size and morphology of nanoparticles were influenced significantly by the polarity of functional groups, and the morphology evolution from sphere to anisotropic shapes was observed by increasing the polarity of functional groups. Investigation of oxazolidine solvatochromism in colloidal solution and solid polymer powders indicated different mechanisms for solvatochromism, in which the polarity of media is the main effective parameter in colloidal solution and the polarity of functional groups in the polymer structure is the main effective parameter in solid polymer phase. The solvatochromism of oxazolidine was confirmed by observed red shift and blue shift in UV–Vis and fluorescence spectra, in which the intensity of absorbance and emission peaks was changed as a function of the polarity of functional groups. Solvatochromic photoluminescent polymer nanoparticles were used for several advanced applications such as solid anticounterfeiting inks to information encryption, dual-mode visualization of latent fingerprints, and also development of organic light-emitting diodes (OLEDs). For the first time, the results indicate a significant effect of polymer chain local polarity induced by functional groups on the tuning of optical properties of the oxazolidine by the solid-state solvatochromic phenomenon. Solvatochromism of oxazolidine in functionalized polymer nanoparticles is an interesting approach to developing novel intelligent materials that have advanced applications in different fields such as anticounterfeiting and information encryption, optoelectronic, polarity sensor, and visualization of latent fingerprints.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113555"},"PeriodicalIF":5.8,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662927","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}
Pub Date : 2024-11-05DOI: 10.1016/j.eurpolymj.2024.113552
Amirhossein Enayati-Gerdroodbar , Amirreza Khayati , Mostafa Ahmadi , Behzad Pourabbas , M. Ali Aboudzadeh , Mehdi Salami-Kalajahi
In recent years, three-dimensional (3D) printing has emerged as an outstanding technique for creating intricate 3D structures with complex geometries. Additionally, four-dimensional (4D) printing technology has attracted attention due to its ability to reshape of 3D printed structures under external stimuli over time. The application of this technique in various fields such as polymer recycling, coating, energy storage systems, medical tools, and hydrogels is due to recent advances in functional materials. Vat photopolymerization-based 3D (VP-based 3D) printing relies on photopolymerization reactions, which are commonly used in techniques such as digital light processing (DLP) and stereolithography (SLA). These techniques are associated with critical parameters such as curing kinetics, printing speed, and resolution. Photoinitiators (PIs) as one of the components of the formulation of photo-resins and photo-inks can be very effective in optimizing these parameters. There are challenges in using common photoinitiators, such as yellowing effect, migration to the surface, toxicity, and bio-incompatibility. To address these challenges, recent researches have been directed towards the synthesis of new photoinitiators based on bio-inspired compounds, inorganic particles, aliphatic structures, transition metals, fluorescent compounds, photo-sensitizers, and macro-structure-based photoinitiators. This review article aims to explore recent studies on the synthesis of new photoinitiators in the application of 3D and 4D printing. Also, it examines various chemistries in the design of photoinitiators and describes the relationship between the curing kinetic, type of monomers, and printing speed. Moreover, it highlights the potential of synthesized photoinitiators in addressing challenges with mechanical properties, resolution, and transparency of the printed part. Furthermore, this article effectively categorizes various types of photoinitiators based on organic and inorganic compounds. Finally, the article aims to generate interest and stimulate more research in the use of new photoinitiators in industrial applications and formulation towards sustainable 3D and 4D printed structures.
近年来，三维（3D）打印技术已成为制造复杂几何形状的三维结构的杰出技术。此外，四维（4D）打印技术因其能够在外部刺激下随时间重塑三维打印结构而备受关注。这种技术在聚合物回收、涂层、储能系统、医疗工具和水凝胶等多个领域的应用，得益于功能材料的最新进展。基于大桶光聚合的三维打印（VP-based 3D ）依赖于光聚合反应，而光聚合反应通常用于数字光处理（DLP）和立体光刻（SLA）等技术中。这些技术与固化动力学、打印速度和分辨率等关键参数有关。光引发剂（PI）作为光树脂和光墨水配方的成分之一，可以非常有效地优化这些参数。在使用普通光引发剂的过程中存在一些挑战，如黄化效应、向表面迁移、毒性和生物相容性。为了应对这些挑战，最近的研究方向是合成基于生物启发的化合物、无机颗粒、脂肪族结构、过渡金属、荧光化合物、光敏剂和基于宏观结构的光引发剂。这篇综述文章旨在探讨在三维和四维打印应用中合成新型光引发剂的最新研究。此外，文章还探讨了光引发剂设计中的各种化学成分，并描述了固化动力学、单体类型和打印速度之间的关系。此外，文章还强调了合成光引发剂在应对打印部件的机械性能、分辨率和透明度等挑战方面的潜力。此外，本文还根据有机和无机化合物对各类光引发剂进行了有效分类。最后，文章旨在激发人们对新型光引发剂在工业应用和配方中的使用的兴趣，并推动更多研究，以实现可持续的三维和四维打印结构。
{"title":"An overview on potential of novel photoinitiators for vat photopolymerization-based 3D/4D printing formulations","authors":"Amirhossein Enayati-Gerdroodbar , Amirreza Khayati , Mostafa Ahmadi , Behzad Pourabbas , M. Ali Aboudzadeh , Mehdi Salami-Kalajahi","doi":"10.1016/j.eurpolymj.2024.113552","DOIUrl":"10.1016/j.eurpolymj.2024.113552","url":null,"abstract":"<div><div>In recent years, three-dimensional (3D) printing has emerged as an outstanding technique for creating intricate 3D structures with complex geometries. Additionally, four-dimensional (4D) printing technology has attracted attention due to its ability to reshape of 3D printed structures under external stimuli over time. The application of this technique in various fields such as polymer recycling, coating, energy storage systems, medical tools, and hydrogels is due to recent advances in functional materials. Vat photopolymerization-based 3D (VP-based 3D) printing relies on photopolymerization reactions, which are commonly used in techniques such as digital light processing (DLP) and stereolithography (SLA). These techniques are associated with critical parameters such as curing kinetics, printing speed, and resolution. Photoinitiators (PIs) as one of the components of the formulation of photo-resins and photo-inks can be very effective in optimizing these parameters. There are challenges in using common photoinitiators, such as yellowing effect, migration to the surface, toxicity, and bio-incompatibility. To address these challenges, recent researches have been directed towards the synthesis of new photoinitiators based on bio-inspired compounds, inorganic particles, aliphatic structures, transition metals, fluorescent compounds, photo-sensitizers, and macro-structure-based photoinitiators. This review article aims to explore recent studies on the synthesis of new photoinitiators in the application of 3D and 4D printing. Also, it examines various chemistries in the design of photoinitiators and describes the relationship between the curing kinetic, type of monomers, and printing speed. Moreover, it highlights the potential of synthesized photoinitiators in addressing challenges with mechanical properties, resolution, and transparency of the printed part. Furthermore, this article effectively categorizes various types of photoinitiators based on organic and inorganic compounds. Finally, the article aims to generate interest and stimulate more research in the use of new photoinitiators in industrial applications and formulation towards sustainable 3D and 4D printed structures.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113552"},"PeriodicalIF":5.8,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142663009","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}
Pub Date : 2024-11-04DOI: 10.1016/j.eurpolymj.2024.113551
Luana Di Lisa , Mariangela Rea , Daniele Nuvoli , Maria Letizia Focarete , Cristiano Albonetti , Alberto Mariani
Low mechanical resistance represents one of the significant problems of hydrogels, limiting their applicability in many fields. One approach to overcome this issue is synthesizing interpenetrating polymeric networks. In this work, the frontal polymerization technique was used to synthesize two series of novel hydrogels: (i) poly(acrylamide) (PAAm)-based hydrogels copolymerized/crosslinked with methacrylate gelatin (GelMA) (AAm-GelMA copolymer networks), and (ii) semi-IPN made of AAm-GelMA copolymer networks and a physically crosslinked gelatin network. With the final objective of improving the rheological, mechanical, morphological, thermal, and swelling properties of PAAm hydrogels, GelMA with two different degrees of methacrylation (30 and 75 mol%) was used. Interactions between GelMA chains, which give rise to physical network formation (i.e., GelMA-GelMA interactions), resulted in very efficient crosslinking for PAAm-based hydrogels, requiring a significantly lower methacrylic group concentration (0.04 mol%) for hydrogel formation compared to N,N′-methylene-bis-acrylamide (1 mol%), which is the agent typically used as a crosslinker for PAAm. Furthermore, the degree of GelMA methacrylation markedly affected the properties of the hydrogels. For example, regarding the swelling degree, hydrogels containing 22 wt% of GELMA30 had an SR% of 2870, while those containing the same amount of GELMA75 swelled much less (870 %). The introduction of gelatin as a secondary network in semi-IPNs influenced the rheological and mechanical properties, resulting in increased hydrogel modulus and stiffness attributed to enhanced physical interactions within the network. Finally, dynamic rheological shear strain and cyclic loading compression tests demonstrated exceptional recovery capabilities in all hydrogel formulations: samples subjected to alternating low (0.1 %) and high (300 % or 10 %) shear strain demonstrated a complete and prompt recovery of G′ and G″ values.
{"title":"Frontal polymerization of acrylamide/GelMA/gelatin hydrogels with controlled mechanical properties and inherent self-recovery","authors":"Luana Di Lisa , Mariangela Rea , Daniele Nuvoli , Maria Letizia Focarete , Cristiano Albonetti , Alberto Mariani","doi":"10.1016/j.eurpolymj.2024.113551","DOIUrl":"10.1016/j.eurpolymj.2024.113551","url":null,"abstract":"<div><div>Low mechanical resistance represents one of the significant problems of hydrogels, limiting their applicability in many fields. One approach to overcome this issue is synthesizing interpenetrating polymeric networks. In this work, the frontal polymerization technique was used to synthesize two series of novel hydrogels: (i) poly(acrylamide) (PAAm)-based hydrogels copolymerized/crosslinked with methacrylate gelatin (GelMA) (AAm-GelMA copolymer networks), and (ii) semi-IPN made of AAm-GelMA copolymer networks and a physically crosslinked gelatin network. With the final objective of improving the rheological, mechanical, morphological, thermal, and swelling properties of PAAm hydrogels, GelMA with two different degrees of methacrylation (30 and 75 mol%) was used. Interactions between GelMA chains, which give rise to physical network formation (i.e., GelMA-GelMA interactions), resulted in very efficient crosslinking for PAAm-based hydrogels, requiring a significantly lower methacrylic group concentration (0.04 mol%) for hydrogel formation compared to N,N′-methylene-bis-acrylamide (1 mol%), which is the agent typically used as a crosslinker for PAAm. Furthermore, the degree of GelMA methacrylation markedly affected the properties of the hydrogels. For example, regarding the swelling degree, hydrogels containing 22 wt% of GELMA30 had an SR% of 2870, while those containing the same amount of GELMA75 swelled much less (870 %). The introduction of gelatin as a secondary network in semi-IPNs influenced the rheological and mechanical properties, resulting in increased hydrogel modulus and stiffness attributed to enhanced physical interactions within the network. Finally, dynamic rheological shear strain and cyclic loading compression tests demonstrated exceptional recovery capabilities in all hydrogel formulations: samples subjected to alternating low (0.1 %) and high (300 % or 10 %) shear strain demonstrated a complete and prompt recovery of G′ and G″ values.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113551"},"PeriodicalIF":5.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142663017","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}
Pub Date : 2024-11-04DOI: 10.1016/j.eurpolymj.2024.113550
Zhiyi Guo, Qiufei Chen, Zhicheng Wang, Athar Ali Khan Gorar, Zhongcheng Pan, Jun Wang, Wenbin Liu
A bio-based bisphenol compound (DFA) was prepared using bisphenolic acid and furfurylamine in biomass as raw materials. Then, a bio-based amide phthalonitrile monomer (DFAP) was obtained in an environmentally friendly solvent. Nuclear magnetic resonance and Fourier transform infrared spectroscopy (FT-IR) proved the successful synthesis of DFA and DFAP. The curing behavior and curing kinetics of the polymer were studied using FT-IR and differential scanning calorimetry. Calculate the activation energy using the isoconversion method. The SB(m, n) autocatalytic reaction model describing the curing process of poly(DFAP) was modified and fitted by introducing the variable activation energy model. The thermal stability, thermomechanical properties and processing properties of the resin were studied using technologies such as thermogravimetric analyzer, dynamic mechanical analyzer and rheometer. The results show that the prepolymer has a wide processing window and a low melt viscosity. Poly(DFAP) has a high glass transition temperature and excellent thermal stability.
{"title":"A novel bio-based autocatalytic amide-type phthalonitrile monomer: Synthesis, curing kinetics and thermal properties","authors":"Zhiyi Guo, Qiufei Chen, Zhicheng Wang, Athar Ali Khan Gorar, Zhongcheng Pan, Jun Wang, Wenbin Liu","doi":"10.1016/j.eurpolymj.2024.113550","DOIUrl":"10.1016/j.eurpolymj.2024.113550","url":null,"abstract":"<div><div>A bio-based bisphenol compound (DFA) was prepared using bisphenolic acid and furfurylamine in biomass as raw materials. Then, a bio-based amide phthalonitrile monomer (DFAP) was obtained in an environmentally friendly solvent. Nuclear magnetic resonance and Fourier transform infrared spectroscopy (FT-IR) proved the successful synthesis of DFA and DFAP. The curing behavior and curing kinetics of the polymer were studied using FT-IR and differential scanning calorimetry. Calculate the activation energy using the isoconversion method. The SB(m, n) autocatalytic reaction model describing the curing process of poly(DFAP) was modified and fitted by introducing the variable activation energy model. The thermal stability, thermomechanical properties and processing properties of the resin were studied using technologies such as thermogravimetric analyzer, dynamic mechanical analyzer and rheometer. The results show that the prepolymer has a wide processing window and a low melt viscosity. Poly(DFAP) has a high glass transition temperature and excellent thermal stability.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113550"},"PeriodicalIF":5.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593975","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}
Pub Date : 2024-11-04DOI: 10.1016/j.eurpolymj.2024.113553
Dou Li , Bailiang Xue , Qinyu Zhao , Wenliang Wang , Xinping Li , Jialong Wen , Zhiwen Wang , Wei Zhao
Lignin-based non-isocyanate polyurethanes (LNIPUs) represent a class of polymers synthesized from lignin—an abundant, renewable polymer found in the cell walls of plants—without the use of toxic isocyanates. This makes LNIPUs an eco-friendly alternative to traditional petroleum-based polyurethanes. Despite their advantages, the synthesis of LNIPUs often entails complex processes, the use of additional catalysts, and highly polar solvents, which largely restrict their accessibility and practical applications. In this study, we present an higly efficient, catalyst-free, and solvent-free methodology for synthesizing LNIPUs. A series of novel LNIPUs were successfully prepared through a one-pot, catalyst-free and solvent-free polymerization reaction involving aminated fractionated lignin (ALFE) and bis(6-membered cyclic carbonate) (6CC). We systematically investigated the properties of the resulting LNIPUs, with a particular focus on the adhesion performance. The incorporation of ALFE significantly enhanced the adhesive properties of the resultant LNIPUs on aluminum, wood, and plastic substrates, achieving a maximum bonding strength of 3.09 MPa on aluminum. Furthermore, LNIPUs exhibit exceptional functionalities, including reusability, self-healing capabilities, and removability, along with improved thermal stability and photothermal properties.
{"title":"Green synthesis of lignin-based non-isocyanate polyurethanes as reusable, self-healable and removable adhesives","authors":"Dou Li , Bailiang Xue , Qinyu Zhao , Wenliang Wang , Xinping Li , Jialong Wen , Zhiwen Wang , Wei Zhao","doi":"10.1016/j.eurpolymj.2024.113553","DOIUrl":"10.1016/j.eurpolymj.2024.113553","url":null,"abstract":"<div><div>Lignin-based non-isocyanate polyurethanes (LNIPUs) represent a class of polymers synthesized from lignin—an abundant, renewable polymer found in the cell walls of plants—without the use of toxic isocyanates. This makes LNIPUs an eco-friendly alternative to traditional petroleum-based polyurethanes. Despite their advantages, the synthesis of LNIPUs often entails complex processes, the use of additional catalysts, and highly polar solvents, which largely restrict their accessibility and practical applications. In this study, we present an higly efficient, catalyst-free, and solvent-free methodology for synthesizing LNIPUs. A series of novel LNIPUs were successfully prepared through a one-pot, catalyst-free and solvent-free polymerization reaction involving aminated fractionated lignin (ALF<sub>E</sub>) and bis(6-membered cyclic carbonate) (6CC). We systematically investigated the properties of the resulting LNIPUs, with a particular focus on the adhesion performance. The incorporation of ALF<sub>E</sub> significantly enhanced the adhesive properties of the resultant LNIPUs on aluminum, wood, and plastic substrates, achieving a maximum bonding strength of 3.09 MPa on aluminum. Furthermore, LNIPUs exhibit exceptional functionalities, including reusability, self-healing capabilities, and removability, along with improved thermal stability and photothermal properties.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113553"},"PeriodicalIF":5.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142663008","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}
Pub Date : 2024-11-04DOI: 10.1016/j.eurpolymj.2024.113558
Xiao Wu , Lijun Qian , Juan Li , Wang Xi , Yong Qiu
To explore the potential of a flame retardant molecular structure that simultaneously enhances the flame retardancy and physical properties of epoxy resin (EP), benzene-terminated linear phosphonate oligomers Bz-DQPC-n were synthesized. Compared with the previously prepared linear bisphenol phosphonate oligomers DQPC-n, the benzene-terminated effect of Bz-DQPC-n molecules endows EP composites with better flame retardancy and toughness. In the vertical combustion (UL 94) test, Bz-DQPC-n/EP reached a V-0 rating. For the Bz-DQPC-2 molecule, the results revealed that under the same phosphorus contents, the limiting oxygen index (LOI) value of the Bz-DQPC-2/EP reached 38.2 %, which was higher than that of DQPC-2/EP. Furthermore, the peak heat release rate (pk-HRR) and total heat release rate (THR) of Bz-DQPC-2/EP were 677 kW/m2 and 83 MJ/m2. These values decreased by 54.7 % and 27.2 % in comparison to pure EP, respectively. In addition, the incorporation of Bz-DQPC-n can enhance the glass transition temperature (Tg) of EP composites. The flame retardant mechanism research demonstrated that Bz-DQPC-n molecules produced phosphorus-containing free radicals and aromatic compound fragments during gas-phase pyrolysis. These phosphorus-containing free radicals can interrupt or inhibit the combustion chain reaction process. A proportion of the aggregated phosphaphenanthrene groups decomposed to produce aromatic compounds that remained in the condensed phase, thereby enhancing the quality of the char layer. The investigation of the impact of the end-capping effect within Bz-DQPC-n molecules on the flame retardant behavior of EP composites offers a valuable reference for designing phosphaphenanthrene compounds with high flame retardant efficiency.
为了探索同时提高环氧树脂（EP）阻燃性和物理性能的阻燃分子结构的潜力，合成了苯封端的线性膦酸盐低聚物 Bz-DQPC-n。与之前制备的线性双酚膦酸酯低聚物 DQPC-n 相比，Bz-DQPC-n 分子的苯端效应赋予 EP 复合材料更好的阻燃性和韧性。在垂直燃烧（UL 94）测试中，Bz-DQPC-n/EP 达到了 V-0 级。对于 Bz-DQPC-2 分子，研究结果表明，在磷含量相同的情况下，Bz-DQPC-2/EP 的极限氧指数（LOI）值达到 38.2%，高于 DQPC-2/EP。此外，Bz-DQPC-2/EP 的峰值放热率（pk-HRR）和总放热率（THR）分别为 677 kW/m2 和 83 MJ/m2。与纯 EP 相比，这些数值分别降低了 54.7% 和 27.2%。此外，Bz-DQPC-n 的加入还能提高 EP 复合材料的玻璃化转变温度（Tg）。阻燃机理研究表明，Bz-DQPC-n 分子在气相热解过程中会产生含磷自由基和芳香族化合物碎片。这些含磷自由基可打断或抑制燃烧链反应过程。一部分聚集的磷菲基团分解后产生的芳香族化合物留在凝结相中，从而提高了炭层的质量。研究 Bz-DQPC-n 分子内的端封效应对 EP 复合材料阻燃性能的影响，为设计具有高阻燃效率的磷菲化合物提供了宝贵的参考。
{"title":"The intramolecular aggregation of phosphaphenanthrene groups and benzene-terminated effect within linear phosphonate oligomers effectively enhanced the flame retardancy and toughness of epoxy resin","authors":"Xiao Wu , Lijun Qian , Juan Li , Wang Xi , Yong Qiu","doi":"10.1016/j.eurpolymj.2024.113558","DOIUrl":"10.1016/j.eurpolymj.2024.113558","url":null,"abstract":"<div><div>To explore the potential of a flame retardant molecular structure that simultaneously enhances the flame retardancy and physical properties of epoxy resin (EP), benzene-terminated linear phosphonate oligomers Bz-DQPC-n were synthesized. Compared with the previously prepared linear bisphenol phosphonate oligomers DQPC-n, the benzene-terminated effect of Bz-DQPC-n molecules endows EP composites with better flame retardancy and toughness. In the vertical combustion (UL 94) test, Bz-DQPC-n/EP reached a V-0 rating. For the Bz-DQPC-2 molecule, the results revealed that under the same phosphorus contents, the limiting oxygen index (LOI) value of the Bz-DQPC-2/EP reached 38.2 %, which was higher than that of DQPC-2/EP. Furthermore, the peak heat release rate (pk-HRR) and total heat release rate (THR) of Bz-DQPC-2/EP were 677 kW/m<sup>2</sup> and 83 MJ/m<sup>2</sup>. These values decreased by 54.7 % and 27.2 % in comparison to pure EP, respectively. In addition, the incorporation of Bz-DQPC-n can enhance the glass transition temperature (<em>T<sub>g</sub></em>) of EP composites. The flame retardant mechanism research demonstrated that Bz-DQPC-n molecules produced phosphorus-containing free radicals and aromatic compound fragments during gas-phase pyrolysis. These phosphorus-containing free radicals can interrupt or inhibit the combustion chain reaction process. A proportion of the aggregated phosphaphenanthrene groups decomposed to produce aromatic compounds that remained in the condensed phase, thereby enhancing the quality of the char layer. The investigation of the impact of the end-capping effect within Bz-DQPC-n molecules on the flame retardant behavior of EP composites offers a valuable reference for designing phosphaphenanthrene compounds with high flame retardant efficiency.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113558"},"PeriodicalIF":5.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142663018","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}
A novel approach to the synthesis of miktoarm star-shaped poly(2-alkyl-2-oxazolines) with calix[8]arene core was developed using a combination of the “core first” (grafting from) and “grafting onto” methods. The star-shaped polymers of A8B8 type with grafted poly(2-ethyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline) arms were obtained using calix[8]arene based multifunctional branching center with sulfonyl chloride initiating moieties and as well as acyl hydrazide termination ones. The polymer structure has been confirmed by 1H NMR spectroscopy and UV spectroscopy. The molar mass characteristics of the samples were determined by size-exclusion chromatographic and light scattering. It was experimentally confirmed that all synthesized polymers had the target arm number, namely 8 or 16. The obtained miktoarm stars were characterized by narrow molar mass distributions, and the polymerization degree of the arms was 15. The synthesized stars had a high intramolecular density, which increased with the arm number. It is shown that the thermoresponsiveness of the studied stars depends on the number and structure of arms and on intramolecular density, while molecular mass is not a decisive factor determining their LCST behavior.
For miktoarm stars, phase separation temperatures do not depend on the grafting configuration of poly(2-ethyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline) on the upper or lower rim of calix[8]arene.
{"title":"Synthesis of miktoarm star-shaped polymers with polyoxazoline arms and macrocyclic calix[8]arene branching center","authors":"N.D. Kozina, T.U. Kirila, A.N. Blokhin, A.P. Filippov, A.V. Tenkovtsev","doi":"10.1016/j.eurpolymj.2024.113547","DOIUrl":"10.1016/j.eurpolymj.2024.113547","url":null,"abstract":"<div><div>A novel approach to the synthesis of miktoarm star-shaped poly(2-alkyl-2-oxazolines) with calix[8]arene core was developed using a combination of the “core first” (grafting from) and “grafting onto” methods. The star-shaped polymers of A<sub>8</sub>B<sub>8</sub> type with grafted poly(2-ethyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline) arms were obtained using calix[8]arene based multifunctional branching center with sulfonyl chloride initiating moieties and as well as acyl hydrazide termination ones. The polymer structure has been confirmed by <sup>1</sup>H NMR spectroscopy and UV spectroscopy. The molar mass characteristics of the samples were determined by size-exclusion chromatographic and light scattering. It was experimentally confirmed that all synthesized polymers had the target arm number, namely 8 or 16. The obtained miktoarm stars were characterized by narrow molar mass distributions, and the polymerization degree of the arms was 15. The synthesized stars had a high intramolecular density, which increased with the arm number. It is shown that the thermoresponsiveness of the studied stars depends on the number and structure of arms and on intramolecular density, while molecular mass is not a decisive factor determining their LCST behavior.</div><div>For miktoarm stars, phase separation temperatures do not depend on the grafting configuration of poly(2-ethyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline) on the upper or lower rim of calix[8]arene.</div></div>","PeriodicalId":315,"journal":{"name":"European Polymer Journal","volume":"221 ","pages":"Article 113547"},"PeriodicalIF":5.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593976","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}
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