Pub Date : 2025-01-09DOI: 10.1016/j.reactfunctpolym.2025.106152
Jingjing Gao, Yadong Wang, Li Ma, Hui Ge, Guoping Zhu, Xuebao Lin, Long Zheng, Luoxin Wang, Zongmin Zhu
The green, environmentally friendly, and high-performance production of flame-retardant polymers has always been a huge challenge. In this paper, a bio-based flame retardant (PT) with high flame retardancy is synthesized from phytic acid (PA) and 2-aminothiazole (AT) using a green and simple method and is used in polylactic acid (PLA). When 4 wt% of PT is added into PLA, the LOI of PLA composite increases from 19 % to 24.6 % and vertical combustion reaches UL-94 V-0 grade, with a peak heat release rate (pHRR) reduced by 18 %. PT can take away heat in vertical combustion testing by promoting the dripping of molten droplets. On the other hand, in the cone calorimeter test (CCT), PT has the capability to facilitate the development of a compact char layer and achieve the effect of suppressing heat. In addition, the crystallinity of PLA composites has also been improved, with a maximum increase of 74.1 %. PLA/PT composites show a ∼ 50.3 % improvement on the impact performance thanks to plasticizing effect of PT. This work provides a green, environmentally friendly, and simple method for preparing highly efficient flame retardants.
{"title":"A bio-based phosphorus-containing flame retardant towards highly flame retardancy, improved crystallization and impact toughness of PLA","authors":"Jingjing Gao, Yadong Wang, Li Ma, Hui Ge, Guoping Zhu, Xuebao Lin, Long Zheng, Luoxin Wang, Zongmin Zhu","doi":"10.1016/j.reactfunctpolym.2025.106152","DOIUrl":"10.1016/j.reactfunctpolym.2025.106152","url":null,"abstract":"<div><div>The green, environmentally friendly, and high-performance production of flame-retardant polymers has always been a huge challenge. In this paper, a bio-based flame retardant (PT) with high flame retardancy is synthesized from phytic acid (PA) and 2-aminothiazole (AT) using a green and simple method and is used in polylactic acid (PLA). When 4 wt% of PT is added into PLA, the LOI of PLA composite increases from 19 % to 24.6 % and vertical combustion reaches UL-94 V-0 grade, with a peak heat release rate (pHRR) reduced by 18 %. PT can take away heat in vertical combustion testing by promoting the dripping of molten droplets. On the other hand, in the cone calorimeter test (CCT), PT has the capability to facilitate the development of a compact char layer and achieve the effect of suppressing heat. In addition, the crystallinity of PLA composites has also been improved, with a maximum increase of 74.1 %. PLA/PT composites show a ∼ 50.3 % improvement on the impact performance thanks to plasticizing effect of PT. This work provides a green, environmentally friendly, and simple method for preparing highly efficient flame retardants.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106152"},"PeriodicalIF":4.5,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143157580","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-08DOI: 10.1016/j.reactfunctpolym.2025.106150
Jianhui Chen , Feng Ma , Yan Qin , Junying Li , Pengfei Yang
With the rapid development of industry, dye wastewater increasingly damaged the ecological environment and human health. Therefore, the treatment of wastewater became an urgent environmental issue. In this paper, sodium lignosulfonate was modified with the Reimer-Tiemann reaction and then cross-linked with chitosan hydrochloride to prepare modified sodium lignosulfonate-chitosan hydrochloride (MSL-CHC) composite materials, which were characterized by infrared spectra (FT-IR), scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) surface area, and X-ray photoelectron spectroscopy (XPS). Then, the adsorption performance of MSL-CHC for Congo red (CR) was investigated under different conditions, including adsorbent dosage, adsorption time, inorganic salt ion species, ionic strength and adsorption temperature. The results showed that the adsorption was consistent with the pseudo-second-order kinetic model, indicating that chemical adsorption was dominant. The adsorption isotherm could be fitted as the Langmuir model, indicating monolayer chemical adsorption. Thermodynamics studies showed that the adsorption of CR was a spontaneous endothermic process. The maximum adsorption capacity for CR was 804.32 mg·g−1. Furthermore, the adsorption capacity of different dyes, as well as the adsorption process in various inorganic salt solution, indicated that MSL-CHC composites had good universality, anti-interference ability and recyclability. The composite materials were environmentally friendly, pollution-free, and easy to obtain, which were ideal bio-based adsorption materials for removing dyes from water.
{"title":"Preparation and characterization of sodium lignosulfonate-chitosan hydrochloride composite materials for dye adsorption","authors":"Jianhui Chen , Feng Ma , Yan Qin , Junying Li , Pengfei Yang","doi":"10.1016/j.reactfunctpolym.2025.106150","DOIUrl":"10.1016/j.reactfunctpolym.2025.106150","url":null,"abstract":"<div><div>With the rapid development of industry, dye wastewater increasingly damaged the ecological environment and human health. Therefore, the treatment of wastewater became an urgent environmental issue. In this paper, sodium lignosulfonate was modified with the Reimer-Tiemann reaction and then cross-linked with chitosan hydrochloride to prepare modified sodium lignosulfonate-chitosan hydrochloride (MSL-CHC) composite materials, which were characterized by infrared spectra (FT-IR), scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) surface area, and X-ray photoelectron spectroscopy (XPS). Then, the adsorption performance of MSL-CHC for Congo red (CR) was investigated under different conditions, including adsorbent dosage, adsorption time, inorganic salt ion species, ionic strength and adsorption temperature. The results showed that the adsorption was consistent with the pseudo-second-order kinetic model, indicating that chemical adsorption was dominant. The adsorption isotherm could be fitted as the Langmuir model, indicating monolayer chemical adsorption. Thermodynamics studies showed that the adsorption of CR was a spontaneous endothermic process. The maximum adsorption capacity for CR was 804.32 mg·g<sup>−1</sup>. Furthermore, the adsorption capacity of different dyes, as well as the adsorption process in various inorganic salt solution, indicated that MSL-CHC composites had good universality, anti-interference ability and recyclability. The composite materials were environmentally friendly, pollution-free, and easy to obtain, which were ideal bio-based adsorption materials for removing dyes from water.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106150"},"PeriodicalIF":4.5,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143157579","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-06DOI: 10.1016/j.reactfunctpolym.2025.106153
Wenqian Yu , Tengfei Han , Shufen Zhang, Benzhi Ju
This study reports the efficient preparation of carboxymethyl cellulose (CMC) that can be used for the adsorption of heavy metals in water by a mechanical force-assisted method with the advantage of green sustainability by replacing solvents and catalysts with mechanical force throughout the preparation process. The mechanical force mechanism of the reaction conditions on the chemical structure and properties of CMC was investigated by FT-IR, 1H NMR, chemical titration, TGA and SEM. The experimental results of copper ion adsorption by CMC show that the adsorption process obeyed the quasi-secondary adsorption kinetic model and conformed to the multimolecular layer adsorption mechanism. When the initial concentration of copper ions was 850 mg/L, the adsorption capacity of CMC could reach 397.1 mg/g and the copper ions removal rate was 93.4 %. This work develops a green and environmentally friendly preparation method for biomass adsorbents which is expected to provide new ideas for solving heavy metal pollution.
{"title":"Green and efficient preparation of carboxymethyl cellulose by the mechanical force assist method and its copper ion adsorption","authors":"Wenqian Yu , Tengfei Han , Shufen Zhang, Benzhi Ju","doi":"10.1016/j.reactfunctpolym.2025.106153","DOIUrl":"10.1016/j.reactfunctpolym.2025.106153","url":null,"abstract":"<div><div>This study reports the efficient preparation of carboxymethyl cellulose (CMC) that can be used for the adsorption of heavy metals in water by a mechanical force-assisted method with the advantage of green sustainability by replacing solvents and catalysts with mechanical force throughout the preparation process. The mechanical force mechanism of the reaction conditions on the chemical structure and properties of CMC was investigated by FT-IR, <sup>1</sup>H NMR, chemical titration, TGA and SEM. The experimental results of copper ion adsorption by CMC show that the adsorption process obeyed the quasi-secondary adsorption kinetic model and conformed to the multimolecular layer adsorption mechanism. When the initial concentration of copper ions was 850 mg/L, the adsorption capacity of CMC could reach 397.1 mg/g and the copper ions removal rate was 93.4 %. This work develops a green and environmentally friendly preparation method for biomass adsorbents which is expected to provide new ideas for solving heavy metal pollution.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106153"},"PeriodicalIF":4.5,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143157575","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-05DOI: 10.1016/j.reactfunctpolym.2025.106155
Emanuel Hernández , Guillermina Capiel , Norma E. Marcovich , Mirna A. Mosiewicki
This article reports the obtaining of materials based on fatty acids as well as their physical, thermal, and mechanical performance. Bio-based polymers are manufactured by radical polymerization of methacrylated maleated ricinoleic acid (MMRA) and methacrylated oleic acid (MOA) combined in different proportions. Differential scanning calorimetry in isothermal experiments reveals polymerization enthalpies between −210 and − 290 J/g for all formulations. The cured materials are hydrophobic, highly translucent, and, even though they are insoluble in common solvents, their gel contents are between 71.4 and 90.3 %. They exhibit very wide loss tangent peaks, with maxima between 51.5 °C and 61.5 °C, demonstrating elastomeric behavior at room temperature with storage modulus up to 216.5 MPa for 100 % MMRA. Their properties depend on the cross-linking degree, the shape of the precursors, the number of pendant chains and on the existence of phase separation. Thus, a larger content of the high-functional MMRA leads to more rigid polymers with enhanced thermostability. Preliminary tests demonstrated vitrimer behavior, with most of the samples displaying stress relaxations higher than 50 % at 190 °C, and the system obtained from the same mass of the two polymeric precursors (50MOA-50MMRA) exhibiting total relaxation of stress at 200 °C, in less than 40 min.
{"title":"Ricinoleic and oleic acid based precursors as the sole constituents of thermosetting bioderived polymers","authors":"Emanuel Hernández , Guillermina Capiel , Norma E. Marcovich , Mirna A. Mosiewicki","doi":"10.1016/j.reactfunctpolym.2025.106155","DOIUrl":"10.1016/j.reactfunctpolym.2025.106155","url":null,"abstract":"<div><div>This article reports the obtaining of materials based on fatty acids as well as their physical, thermal, and mechanical performance. Bio-based polymers are manufactured by radical polymerization of methacrylated maleated ricinoleic acid (MMRA) and methacrylated oleic acid (MOA) combined in different proportions. Differential scanning calorimetry in isothermal experiments reveals polymerization enthalpies between −210 and − 290 J/g for all formulations. The cured materials are hydrophobic, highly translucent, and, even though they are insoluble in common solvents, their gel contents are between 71.4 and 90.3 %. They exhibit very wide loss tangent peaks, with maxima between 51.5 °C and 61.5 °C, demonstrating elastomeric behavior at room temperature with storage modulus up to 216.5 MPa for 100 % MMRA. Their properties depend on the cross-linking degree, the shape of the precursors, the number of pendant chains and on the existence of phase separation. Thus, a larger content of the high-functional MMRA leads to more rigid polymers with enhanced thermostability. Preliminary tests demonstrated vitrimer behavior, with most of the samples displaying stress relaxations higher than 50 % at 190 °C, and the system obtained from the same mass of the two polymeric precursors (50MOA-50MMRA) exhibiting total relaxation of stress at 200 °C, in less than 40 min.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106155"},"PeriodicalIF":4.5,"publicationDate":"2025-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143157578","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-03DOI: 10.1016/j.reactfunctpolym.2025.106151
Jie Ma , Liping Zhen , Huijun Yao , Dan Mo , Youmei Sun , Zhengguo Hu , Jie Liu , Jinglai Duan
Hydrophilicity is an important property for membranes as it influences the application scope and effectiveness of separation process, and various surface modification methods have been developed targeting to an enhanced hydrophilicity. However, few work focuses on hydrophilicity tunability, and many researches can only obtain limited wettability improvement. Here, a novel surface modification method is reported. In this method, surface functional groups on polyethylene terephthalate membrane are activated and hydrophilic polyethylenimine chains can be grafted to the membrane in a layer-by-layer manner. The membrane hydrophilicity is thus tunable in a wide range through adjusting the number of grafting steps, and a water contact angle decrease of 54o that exceeds most of other grafting modification methods is achieved. Optimal membrane hydrophilicity corresponding to a contact angle of 60o is found through the screening for the highest water permeability, and a water permeability improvement of ∼29 % is observed for modified PET track-etched membranes with different parameters.
{"title":"Tunable hydrophilic modification of polyethylene terephthalate membrane via layer-by-layer polyethylenimine grafting","authors":"Jie Ma , Liping Zhen , Huijun Yao , Dan Mo , Youmei Sun , Zhengguo Hu , Jie Liu , Jinglai Duan","doi":"10.1016/j.reactfunctpolym.2025.106151","DOIUrl":"10.1016/j.reactfunctpolym.2025.106151","url":null,"abstract":"<div><div>Hydrophilicity is an important property for membranes as it influences the application scope and effectiveness of separation process, and various surface modification methods have been developed targeting to an enhanced hydrophilicity. However, few work focuses on hydrophilicity tunability, and many researches can only obtain limited wettability improvement. Here, a novel surface modification method is reported. In this method, surface functional groups on polyethylene terephthalate membrane are activated and hydrophilic polyethylenimine chains can be grafted to the membrane in a layer-by-layer manner. The membrane hydrophilicity is thus tunable in a wide range through adjusting the number of grafting steps, and a water contact angle decrease of 54<sup>o</sup> that exceeds most of other grafting modification methods is achieved. Optimal membrane hydrophilicity corresponding to a contact angle of 60<sup>o</sup> is found through the screening for the highest water permeability, and a water permeability improvement of ∼29 % is observed for modified PET track-etched membranes with different parameters.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106151"},"PeriodicalIF":4.5,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143157577","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-31DOI: 10.1016/j.reactfunctpolym.2024.106147
Zitong Xu , Guixuan Ma , Dipak Rana , Takeshi Matsuura , Christopher Q. Lan
Alkaline treatment is a cost-effective and easy-to-operate method that can effectively alter the hydrophilicity of polyvinylidene fluoride (PVDF) membranes. It makes the surface of PVDF membranes chemically active by introducing hydrophilic groups, e.g., hydroxyl and carboxyl groups, and therefore could be used as an effective pretreatment for membrane surface engineering including the grafting of other target chemical molecules onto to membrane surface. This treatment enhances the hydrophilicity of the membrane surface and could therefore also improve membrane permeability and reduce fouling. In this research, we systematically studied the alkaline treatment using KOH/alcohol/water ternaries at different conditions. Results indicate that the inclusion of alcohol in the reaction system could impact the efficiency of membrane surface modification through altering the chemical reaction mechanism as well as affecting the reacting mixture's properties such as OH− activity, polarity, reactivity, and membrane wettability. The effectiveness of different alcohols was in the order of methanol > ethanol > isopropanol in terms of increasing the surface hydrophilicity, which is in accordance with the orders of their polarity and reactivity. In the meantime, the coloration of treated membranes followed a reversed order. It is evident that increasing treatment temperature, duration, OH− activity, reactivity and polarity in the tested range would lead to the increase of both the surface hydrophilicity and membrane color. On the other hand, increasing a ternary's ability to wet the PVDF membrane had none or little impact on membrane hydrophilicity but strong impact on membrane color. Results suggest that coloration reactions did not contribute to the improvement of surface hydrophilicity and should therefore be minimized.
{"title":"Modification of exterior and intraporous surfaces of polyvinylidene fluoride membranes using KOH/water/alcohol ternary: Effects of wettability, polarity, and OH− activity","authors":"Zitong Xu , Guixuan Ma , Dipak Rana , Takeshi Matsuura , Christopher Q. Lan","doi":"10.1016/j.reactfunctpolym.2024.106147","DOIUrl":"10.1016/j.reactfunctpolym.2024.106147","url":null,"abstract":"<div><div>Alkaline treatment is a cost-effective and easy-to-operate method that can effectively alter the hydrophilicity of polyvinylidene fluoride (PVDF) membranes. It makes the surface of PVDF membranes chemically active by introducing hydrophilic groups, e.g., hydroxyl and carboxyl groups, and therefore could be used as an effective pretreatment for membrane surface engineering including the grafting of other target chemical molecules onto to membrane surface. This treatment enhances the hydrophilicity of the membrane surface and could therefore also improve membrane permeability and reduce fouling. In this research, we systematically studied the alkaline treatment using KOH/alcohol/water ternaries at different conditions. Results indicate that the inclusion of alcohol in the reaction system could impact the efficiency of membrane surface modification through altering the chemical reaction mechanism as well as affecting the reacting mixture's properties such as OH<sup>−</sup> activity, polarity, reactivity, and membrane wettability. The effectiveness of different alcohols was in the order of methanol > ethanol > isopropanol in terms of increasing the surface hydrophilicity, which is in accordance with the orders of their polarity and reactivity. In the meantime, the coloration of treated membranes followed a reversed order. It is evident that increasing treatment temperature, duration, OH<sup>−</sup> activity, reactivity and polarity in the tested range would lead to the increase of both the surface hydrophilicity and membrane color. On the other hand, increasing a ternary's ability to wet the PVDF membrane had none or little impact on membrane hydrophilicity but strong impact on membrane color. Results suggest that coloration reactions did not contribute to the improvement of surface hydrophilicity and should therefore be minimized.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106147"},"PeriodicalIF":4.5,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143157606","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-31DOI: 10.1016/j.reactfunctpolym.2024.106146
Huan Liu , Xiao-jie Zhang , Yu-xin Ding , Shao-hui Xiong , Zi-en Fu
12-hydroxystearic acid (HSA) was introduced into the thermoset benzoxazine, we expected that the stable ordered structures could be introduced into the thermoset three-dimensional network through the self-assembly of HSA and the polymerization-induced phase separation of benzoxazine monomers. To better understand the structural effects attributed to the introduction of HSA, some model compounds possessing the chemical structure-like HSA were also involved into the study. HSA and benzoxazine (Ba-bz) mixed with different weight ratios, an isotropic solution could be formed after the mixture melted, indicating that HSA molecules in Ba-bz monomers could assemble into ordered structures like in other organic solvents. The study found that the HSA molecules did not aggregate together in the form of individual molecule which completely distinguished from the model compounds. A conjunction of observation of macroscopic structure picture and characterization of microstructure of the samples, the results showed that HSA molecules spontaneously assembled into the fibrillar networks (SAFINs) in Ba-bz. Nanometric spherical micelles consist of HSA could be formed in the molten isotropic solution of HSA and Ba-bz and aggregate into tubes upon cooling. Due to the high concentration of HSA, the nanometric spherical micelles were easier to self-assembly into the large scale fibrillar tubes. During the polymerization, the fibrillar tubes could be stacked further under the action of the polymerization-induced and the rapid formation of the cross-linking network of polybenzoxazine stabilized the tubes. The tubular structure of HSA aggregation was filled with the polybenzoxazine, contributing to the formation of the interpenetrating structure.
{"title":"HSA fibrillar networks assembled and stabilized in the condensed phase of thermoset polybenzoxazine","authors":"Huan Liu , Xiao-jie Zhang , Yu-xin Ding , Shao-hui Xiong , Zi-en Fu","doi":"10.1016/j.reactfunctpolym.2024.106146","DOIUrl":"10.1016/j.reactfunctpolym.2024.106146","url":null,"abstract":"<div><div>12-hydroxystearic acid (HSA) was introduced into the thermoset benzoxazine, we expected that the stable ordered structures could be introduced into the thermoset three-dimensional network through the self-assembly of HSA and the polymerization-induced phase separation of benzoxazine monomers. To better understand the structural effects attributed to the introduction of HSA, some model compounds possessing the chemical structure-like HSA were also involved into the study. HSA and benzoxazine (Ba-bz) mixed with different weight ratios, an isotropic solution could be formed after the mixture melted, indicating that HSA molecules in Ba-bz monomers could assemble into ordered structures like in other organic solvents. The study found that the HSA molecules did not aggregate together in the form of individual molecule which completely distinguished from the model compounds. A conjunction of observation of macroscopic structure picture and characterization of microstructure of the samples, the results showed that HSA molecules spontaneously assembled into the fibrillar networks (SAFINs) in Ba-bz. Nanometric spherical micelles consist of HSA could be formed in the molten isotropic solution of HSA and Ba-bz and aggregate into tubes upon cooling. Due to the high concentration of HSA, the nanometric spherical micelles were easier to self-assembly into the large scale fibrillar tubes. During the polymerization, the fibrillar tubes could be stacked further under the action of the polymerization-induced and the rapid formation of the cross-linking network of polybenzoxazine stabilized the tubes. The tubular structure of HSA aggregation was filled with the polybenzoxazine, contributing to the formation of the interpenetrating structure.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106146"},"PeriodicalIF":4.5,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143157607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-31DOI: 10.1016/j.reactfunctpolym.2024.106148
Mónica Stephen Correa-Durán , María Ortencia González-Díaz , Rita Sulub-Sulub , María Isabel de los Dolores Loria-Bastarrachea , José M. Cervantes-Uc , Humberto Vázquez-Torres , Manuel Aguilar-Vega
Three polymeric anion exchange membranes (AEMs) were synthesized via free radical copolymerization of vinyl acetate (VAc), with ionic liquid monomer 1-(4-vinylbenzyl)-3-butyl imidazolium tetrafluoroborate (VBIT) as the anion-exchange group. VBIT monomer and the copolymers PVAc-co-PVBIT chemical structure at different molar ratios (70:30, 64:36, and 60:40) were characterized by FTIR, 1H NMR and 13C NMR spectroscopy. DSC and TGA results showed that PVAc-co-PVBIT copolymers exhibit Tg, as well as thermal stability intermediate between the homopolymers. PVAc-co-PVBIT membranes showed high water absorption (165–631 %), ion exchange capacity between 2.11 and 2.52 meq g−1, and ionic conductivity between 1.9 and 5.0 × 10−2 mS cm−1. In most cases, ionic conductivity () and (IEC) values were equal to or higher than those reported for commercial or ionic liquid containing anionic membranes. After exposure to 3 M NaOH alkaline solution, PVAc-co-PVBIT membranes remain unchanged with a minimum weight loss. The ability to form membranes, thermal stability, ion exchange capacity and ionic conductivity values of PVAc-co-PVBIT copolymers situate them as promising material for anionic membrane preparation.
{"title":"Anionic membranes from vinyl acetate and ionic liquid vinyl-butyl imidazolium (PVAc-co-PVBIT) copolymers: Synthesis, characterization and ionic conductivity","authors":"Mónica Stephen Correa-Durán , María Ortencia González-Díaz , Rita Sulub-Sulub , María Isabel de los Dolores Loria-Bastarrachea , José M. Cervantes-Uc , Humberto Vázquez-Torres , Manuel Aguilar-Vega","doi":"10.1016/j.reactfunctpolym.2024.106148","DOIUrl":"10.1016/j.reactfunctpolym.2024.106148","url":null,"abstract":"<div><div>Three polymeric anion exchange membranes (AEMs) were synthesized via free radical copolymerization of vinyl acetate (VAc), with ionic liquid monomer 1-(4-vinylbenzyl)-3-butyl imidazolium tetrafluoroborate (VBIT) as the anion-exchange group. VBIT monomer and the copolymers PVAc-co-PVBIT chemical structure at different molar ratios (70:30, 64:36, and 60:40) were characterized by FTIR, <sup>1</sup>H NMR and <sup>13</sup>C NMR spectroscopy. DSC and TGA results showed that PVAc-co-PVBIT copolymers exhibit Tg, as well as thermal stability intermediate between the homopolymers. PVAc-<em>co</em>-PVBIT membranes showed high water absorption (165–631 %), ion exchange capacity between 2.11 and 2.52 meq g<sup>−1</sup>, and ionic conductivity between 1.9 and 5.0 × 10<sup>−2</sup> mS cm<sup>−1</sup>. In most cases, ionic conductivity (<span><math><mi>σ</mi></math></span>) and (<em>IEC)</em> values were equal to or higher than those reported for commercial or ionic liquid containing anionic membranes. After exposure to 3 M NaOH alkaline solution, PVAc-<em>co</em>-PVBIT membranes remain unchanged with a minimum weight loss. The ability to form membranes, thermal stability, ion exchange capacity and ionic conductivity values of PVAc-<em>co</em>-PVBIT copolymers situate them as promising material for anionic membrane preparation.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106148"},"PeriodicalIF":4.5,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143157605","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-30DOI: 10.1016/j.reactfunctpolym.2024.106145
Marta Piccioni, Alessio Varesano, Maria Laura Tummino, Cinzia Tonetti, Claudia Vineis
In this research work, cotton and polyamide 6,6 fabrics were coated with polypyrrole, an intrinsically electro-conductive polymer that showed antibacterial actions. The study first aims to measure the antibacterial efficacy of polypyrrole-coated fabrics at increasing pyrrole concentrations (2, 4, and 6 g/L) and consider contact times shorter than the standard 60 min between the fabrics and the bacteria. The results showed not trivial antibacterial performances obtained at different conditions on fabrics with hydrophilic (e.g., cotton) and hydrophobic (e.g., polyamide 6,6) characteristics, also evidencing the importance of polypyrrole particle distribution in the fabric. For instance, outstanding performances were revealed by both cotton and polyamide coated with 2 g/L in 30 min against the two tested bacterial strains, Staphylococcus aureus (Gram-positive) and Escherichia coli (Gram-negative). These findings will be valuable for choosing materials and processing conditions when a rapid and solid biocidal effect is needed. Additionally, from the evaluation of electrical features and photothermal activity, it was found that the electrical conductivity, like the antibacterial properties, was strongly affected by the polypyrrole de-doping consequent to washing, in contrast to photothermal features (particularly triggered by infrared radiation), that were not straightforwardly influenced by doping state and did not exert positive effects on the antibacterial properties.
{"title":"Effect of coating and testing conditions on the antibacterial efficacy of polypyrrole-treated fabrics","authors":"Marta Piccioni, Alessio Varesano, Maria Laura Tummino, Cinzia Tonetti, Claudia Vineis","doi":"10.1016/j.reactfunctpolym.2024.106145","DOIUrl":"10.1016/j.reactfunctpolym.2024.106145","url":null,"abstract":"<div><div>In this research work, cotton and polyamide 6,6 fabrics were coated with polypyrrole, an intrinsically electro-conductive polymer that showed antibacterial actions. The study first aims to measure the antibacterial efficacy of polypyrrole-coated fabrics at increasing pyrrole concentrations (2, 4, and 6 g/L) and consider contact times shorter than the standard 60 min between the fabrics and the bacteria. The results showed not trivial antibacterial performances obtained at different conditions on fabrics with hydrophilic (<em>e.g.</em>, cotton) and hydrophobic (<em>e.g.</em>, polyamide 6,6) characteristics, also evidencing the importance of polypyrrole particle distribution in the fabric. For instance, outstanding performances were revealed by both cotton and polyamide coated with 2 g/L in 30 min against the two tested bacterial strains, <em>Staphylococcus aureus</em> (Gram-positive) and <em>Escherichia coli</em> (Gram-negative). These findings will be valuable for choosing materials and processing conditions when a rapid and solid biocidal effect is needed. Additionally, from the evaluation of electrical features and photothermal activity, it was found that the electrical conductivity, like the antibacterial properties, was strongly affected by the polypyrrole de-doping consequent to washing, in contrast to photothermal features (particularly triggered by infrared radiation), that were not straightforwardly influenced by doping state and did not exert positive effects on the antibacterial properties.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106145"},"PeriodicalIF":4.5,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143157604","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-25DOI: 10.1016/j.reactfunctpolym.2024.106144
Agnes Kemmer, Thomas Heinze
Polysaccharides containing norbornene moieties are gaining importance in biomedical applications. This study presents the effective linkage of the norbornene moiety to the polysaccharide backbone using dextran phenyl and p-nitrophenyl carbonates as activated starting biopolymer derivatives. A novel norbornene-functionalized dextran with a degree of substitution of 1.0 predominantly modified at position 2 could be obtained by aminolysis of the dextran p-nitrophenyl carbonate. A highly norbornene-functionalized dextran derivative is derived from the reaction with dextran phenyl carbonate. The reactivity of these norbornene-functionalized derivatives was investigated, demonstrating a complete conversion of the norbornene moiety in radical thiol-ene reactions while maintaining the stability of the carbamate bond. The synthesis of mixed dextran derivatives containing reactive phenyl carbonate- and norbornene moieties is also described. The selectivity of reactions involving phenyl carbonates with amines and thiols was assessed, revealing a cleavage of phenyl carbonate moieties, which is influenced by the basicity of the amine rather than side reactions with thiols. NMR spectroscopy and elemental analysis were employed to accurately determine the degrees of substitution and confirm the structural integrity of the derivatives.
{"title":"Reactive norbornene- and phenyl carbonate-modified dextran derivatives: A new approach to selective functionalization","authors":"Agnes Kemmer, Thomas Heinze","doi":"10.1016/j.reactfunctpolym.2024.106144","DOIUrl":"10.1016/j.reactfunctpolym.2024.106144","url":null,"abstract":"<div><div>Polysaccharides containing norbornene moieties are gaining importance in biomedical applications. This study presents the effective linkage of the norbornene moiety to the polysaccharide backbone using dextran phenyl and <em>p</em>-nitrophenyl carbonates as activated starting biopolymer derivatives. A novel norbornene-functionalized dextran with a degree of substitution of 1.0 predominantly modified at position 2 could be obtained by aminolysis of the dextran <em>p</em>-nitrophenyl carbonate. A highly norbornene-functionalized dextran derivative is derived from the reaction with dextran phenyl carbonate. The reactivity of these norbornene-functionalized derivatives was investigated, demonstrating a complete conversion of the norbornene moiety in radical thiol-ene reactions while maintaining the stability of the carbamate bond. The synthesis of mixed dextran derivatives containing reactive phenyl carbonate- and norbornene moieties is also described. The selectivity of reactions involving phenyl carbonates with amines and thiols was assessed, revealing a cleavage of phenyl carbonate moieties, which is influenced by the basicity of the amine rather than side reactions with thiols. NMR spectroscopy and elemental analysis were employed to accurately determine the degrees of substitution and confirm the structural integrity of the derivatives.</div></div>","PeriodicalId":20916,"journal":{"name":"Reactive & Functional Polymers","volume":"208 ","pages":"Article 106144"},"PeriodicalIF":4.5,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143157576","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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