Polymers

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16 pages, 4872 KiB

Open AccessArticle

Active Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) Films Containing Phenolic Compounds with Different Molecular Structures

by Carla Ivonne La Fuente Arias, Chelo González-Martínez and Amparo Chiralt

Polymers 2024, 16(11), 1574; https://doi.org/10.3390/polym16111574 (registering DOI) - 2 Jun 2024

Abstract

To obtain more sustainable and active food packaging materials, PHBV films containing 5% wt. of phenolic compounds with different molecular structures (ferulic acid, vanillin, and catechin) and proved antioxidant and antimicrobial properties were obtained by melt blending and compression molding. These were characterized [...] Read more.

To obtain more sustainable and active food packaging materials, PHBV films containing 5% wt. of phenolic compounds with different molecular structures (ferulic acid, vanillin, and catechin) and proved antioxidant and antimicrobial properties were obtained by melt blending and compression molding. These were characterized by their structural, mechanical, barrier, and optical properties, as well as the polymer crystallization, thermal stability, and component migration in different food simulants. Phenolic compounds were homogenously integrated within the polymer matrix, affecting the film properties differently. Ferulic acid, and mainly catechin, had an anti-plasticizing effect (increasing the polymer glass transition temperature), decreasing the film extensibility and the resistance to breaking, with slight changes in the elastic modulus. In contrast, vanillin provoked a plasticizing effect, decreasing the elastic modulus without notable changes in the film extensibility while increasing the water vapor permeability. All phenolic compounds, mainly catechin, improved the oxygen barrier capacity of PHBV films and interfered with the polymer crystallization, reducing the melting point and crystallinity degree. The thermal stability of the material was little affected by the incorporation of phenols. The migration of passive components of the different PHBV films was lower than the overall migration limit in every simulant. Phenolic compounds were released to a different extent depending on their thermo-sensitivity, which affected their final content in the film, their bonding forces in the polymer matrix, and the simulant polarity. Their effective release in real foods will determine their active action for food preservation. Catechin was the best preserved, while ferulic acid was the most released. Full article

(This article belongs to the Special Issue Functional Polymers: Interaction, Surface, Processing and Applications II)

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19 pages, 2105 KiB

Open AccessArticle

Fabrication of Waterborne Silicone-Modified Polyurethane Nanofibers for Nonfluorine Elastic Waterproof and Breathable Membranes

by Fang Li, Kai Weng, Toshihisa Tanaka, Jianxin He, Haimin Zheng, Daisuke Noda, Shinji Irifune and Hiromasa Sato

Polymers 2024, 16(11), 1505; https://doi.org/10.3390/polym16111505 - 25 May 2024

Viewed by 261

Abstract

Waterproof and breathable membranes have a huge market demand in areas, such as textiles and medical protection. However, existing fluorinated nanofibrous membranes, while possessing good waterproof and breathable properties, pose health and environmental hazards. Consequently, fabricating fluorine-free, eco-friendly waterborne membranes by integrating outstanding [...] Read more.

Waterproof and breathable membranes have a huge market demand in areas, such as textiles and medical protection. However, existing fluorinated nanofibrous membranes, while possessing good waterproof and breathable properties, pose health and environmental hazards. Consequently, fabricating fluorine-free, eco-friendly waterborne membranes by integrating outstanding waterproofing, breathability, and robust mechanical performance remains a significant challenge. Herein, we successfully prepared waterborne silicone-modified polyurethane nanofibrous membranes with excellent elasticity, waterproofing, and breathability properties through waterborne electrospinning, using a small quantity of poly(ethylene oxide) as a template polymer and in situ doping of the poly(carbodiimide) crosslinking agent, followed by a simple hot-pressing treatment. The silicone imparted the nanofibrous membrane with high hydrophobicity, and the crosslinking agent enabled its stable porous structure. The hot-pressing treatment (120 °C) further reduced the pore size and improved the water resistance. This environmentally friendly nanofibrous membrane showed a high elongation at break of 428%, an ultra-high elasticity of 67.5% (160 cycles under 400% tensile strain), an air transmission of 13.2 mm s⁻¹, a water vapor transmission rate of 5476 g m⁻² d⁻¹, a hydrostatic pressure of 51.5 kPa, and a static water contact angle of 137.9°. The successful fabrication of these environmentally friendly, highly elastic membranes provides an important reference for applications in healthcare, protective textiles, and water purification. Full article

(This article belongs to the Special Issue Functional Polymers: Interaction, Surface, Processing and Applications II)

15 pages, 6052 KiB

Open AccessArticle

DIW-Printed Thermal Management PDMS Composites with 3D Structural Thermal Conductive Network of h-BN Platelets and Al₂O₃ Nanoparticles

by Hongyi Zhu, Shunxia Wu, Rui Tang, Yang Li, Gang Chen, Bingxue Huang and Biyou Peng

Polymers 2024, 16(11), 1491; https://doi.org/10.3390/polym16111491 - 24 May 2024

Viewed by 297

Abstract

Electronic devices play an increasingly vital role in modern society, and heat accumulation is a major concern during device development, which causes strong market demand for thermal conductivity materials and components. In this paper, a novel thermal conductive material consisting of polydimethylsiloxane (PDMS) [...] Read more.

Electronic devices play an increasingly vital role in modern society, and heat accumulation is a major concern during device development, which causes strong market demand for thermal conductivity materials and components. In this paper, a novel thermal conductive material consisting of polydimethylsiloxane (PDMS) and a binary filler system of h-BN platelets and Al₂O₃ nanoparticles was successfully fabricated using direct ink writing (DIW) 3D printing technology. The addictive manufacturing process not only endows the DIW-printed composites with various geometries but also promotes the construction of a 3D structural thermal conductive network through the shearing force during the printing process. Moreover, the integrity of the thermal conductive network can be optimized by filling the gaps between the BN platelets with Al₂O₃ particles. Resultingly, the configuration of the binary fillers is arranged by the shearing force during the DIW process, fabricating the thermal conductive network of oriented fillers. The DIW-printed BN/Al₂O₃/PDMS with 45 wt% thermal conductive binary filler can reach a thermal conductivity of 0.98 W/(m·K), higher than the 0.62 W/(m·K) of the control sample. In this study, a novel strategy for the thermal conductive performance improvement of composites based on DIW technology is successfully verified, paving a new way for thermal management. Full article

(This article belongs to the Special Issue Functional Polymers: Interaction, Surface, Processing and Applications II)

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19 pages, 5235 KiB

Open AccessArticle

Inherited Structure Properties of Larch Arabinogalactan Affected via the TEMPO/NaBr/NaOCl Oxidative System

by Vladislav A. Ionin, Yuriy N. Malyar, Valentina S. Borovkova, Dmitriy V. Zimonin, Roksana M. Gulieva and Olga Yu. Fetisova

Polymers 2024, 16(11), 1458; https://doi.org/10.3390/polym16111458 - 22 May 2024

Viewed by 305

Abstract

Arabinogalactan (AG), extracted from larch wood, is a β-1,3-galactan backbone and β-1,6-galactan side chains with attached α-1-arabinofuranosyl and β-1-arabinopyranosyl residues. Although the structural characteristics of arabinogalactan II type have already been studied, its functionalization using 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) oxidation remains a promising avenue. In [...] Read more.

Arabinogalactan (AG), extracted from larch wood, is a β-1,3-galactan backbone and β-1,6-galactan side chains with attached α-1-arabinofuranosyl and β-1-arabinopyranosyl residues. Although the structural characteristics of arabinogalactan II type have already been studied, its functionalization using 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) oxidation remains a promising avenue. In this study, the oxidation of AG, a neutral polysaccharide, was carried out using the TEMPO/NaBr/NaOCl system, resulting in polyuronides with improved functional properties. The oxidation of AG was controlled by analyzing portions of the reaction mixture using spectrophotometric and titration methods. To determine the effect of the TEMPO/NaBr/NaOCl system, air-dried samples of native and oxidized AG were studied by Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy, as well as by gel permeation chromatography. Compounds that model free (1,1-diphenyl-2-picrylhydrazyl (DPPH)) and hydroxyl radicals (iron(II) sulfate, hydrogen peroxide, and salicylic acid) were used to study the antioxidant properties. It was found that, in oxidized forms of AG, the content of carboxyl groups increases by 0.61 mmol compared to native AG. The transformation of oxidized AG into the H⁺ form using a strong acid cation exchanger leads to an increase in the number of active carboxyl groups to 0.76 mmol. Using FTIR spectroscopy, characteristic absorption bands (1742, 1639, and 1403 cm⁻¹) were established, indicating the occurrence of oxidative processes with a subsequent reduction in the carboxyl group. The functionality of AG was also confirmed by gel permeation chromatography (GPC), which is reflected in an increase in molecular weights (up to 15,700 g/mol). A study of the antioxidant properties of the oxidized and protonated forms of AG show that the obtained antioxidant activity (AOA) values are generally characteristic of polyuronic acids. Therefore, the TEMPO oxidation of AG and other neutral polysaccharides can be considered a promising approach for obtaining compounds with the necessary controlled characteristics. Full article

(This article belongs to the Special Issue Functional Polymers: Interaction, Surface, Processing and Applications II)

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16 pages, 9463 KiB

Open AccessArticle

An Eco-Friendly Manner to Prepare Superwetting Melamine Sponges with Switchable Wettability for the Separation of Oil/Water Mixtures and Emulsions

by Guyita Berako Belachew, Chien-Chieh Hu, Yan-Yu Chang, Chih-Feng Wang, Wei-Song Hung, Jem-Kun Chen and Juin-Yih Lai

Polymers 2024, 16(5), 693; https://doi.org/10.3390/polym16050693 - 3 Mar 2024

Viewed by 1056

Abstract

Oil/water separation processes have garnered significant global attention due to the quick growth in industrial development, recurring chemical leakages, and oil spills. Hence, there is a significant demand for the development of inexpensive superwetting materials in an eco-friendly manner to separate oil/water mixtures [...] Read more.

Oil/water separation processes have garnered significant global attention due to the quick growth in industrial development, recurring chemical leakages, and oil spills. Hence, there is a significant demand for the development of inexpensive superwetting materials in an eco-friendly manner to separate oil/water mixtures and emulsions. In this study, a superwetting melamine sponge (SMS) with switchable wettabilities was prepared by modifying melamine sponge (MS) with sodium dodecanoate. The as-prepared SMS exhibited superhydrophobicity, superoleophilicity, underwater superoleophobicity, and underoil superhydrophobicity. The SMS can be utilized in treating both light and heavy oil/water mixtures through the prewetting process. It demonstrated fast permeation fluxes (reaching 108,600 L m⁻² h⁻¹ for a light oil/water mixture and 147,700 L m⁻² h⁻¹ for a heavy oil/water mixture) and exhibited good separation efficiency (exceeding 99.56%). The compressed SMS was employed in separating surfactant-stabilized water-in-oil emulsions (SWOEs), as well as surfactant-stabilized oil-in-water emulsions (SOWEs), giving high permeation fluxes (reaching 7210 and 5054 L m⁻² h⁻¹, respectively). The oil purity for SWOEs’ filtrates surpassed 99.98 wt% and the separation efficiencies of SOWEs exceeded 98.84%. Owing to their remarkable capability for separating oil/water mixtures and emulsions, eco-friendly fabrication method, and feasibility for large-scale production, our SMS has a promising potential for practical applications. Full article

(This article belongs to the Special Issue Functional Polymers: Interaction, Surface, Processing and Applications II)

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18 pages, 1257 KiB

Open AccessArticle

A Facile Surface Modification Scheme for Medical-Grade Titanium and Polypropylene Using a Novel Mussel-Inspired Biomimetic Polymer with Cationic Quaternary Ammonium Functionalities for Antibacterial Application

by Chi-Hui Cheng, Xiang-Zhen Zeng, Wen-Yuan Chiu and Jui-Che Lin

Polymers 2024, 16(4), 503; https://doi.org/10.3390/polym16040503 - 12 Feb 2024

Viewed by 887

Abstract

Medical device-associated infection remains a critical problem in the healthcare setting. Different clinical- or device-related methods have been attempted to reduce the infection rate. Among these approaches, creating a surface with bactericidal cationic functionality has been proposed. To do so, a sophisticated multi-step [...] Read more.

Medical device-associated infection remains a critical problem in the healthcare setting. Different clinical- or device-related methods have been attempted to reduce the infection rate. Among these approaches, creating a surface with bactericidal cationic functionality has been proposed. To do so, a sophisticated multi-step chemical procedure would be needed. Instead, a simple immersion approach was utilized in this investigation to render the titanium and polypropylene surface with the quaternary ammonium functionality by using a mussel-inspired novel lab-synthesized biomimetic catechol-terminated polymer, PQA-C8. The chemical oxidants, CuSO₄/H₂O₂, as well as dopamine, were added into the novel PQA-C8 polymer immersion solution for one-step surface modification. Additionally, a two-step immersion scheme, in which the polypropylene substrate was first immersed in the dopamine solution and then in the PQA-C8 solution, was also attempted. Surface analysis results indicated the surface characteristics of the modified substrates were affected by the immersion solution formulation as well as the procedure utilized. The antibacterial assay has shown the titanium substrates modified by the one-step dopamine + PQA-C8 mixtures with the oxidants added and the polypropylene modified by the two-step scheme exhibited bacterial reduction percentages greater than 90% against both Gram-positive S. aureus and Gram-negative E. coli and these antibacterial substrates were non-cytotoxic. Full article

(This article belongs to the Special Issue Functional Polymers: Interaction, Surface, Processing and Applications II)

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17 pages, 11402 KiB

Open AccessArticle

Single-Component Hydrophilic Terpolymer Thin Film Systems for Imparting Surface Chemical Versatility on Various Substrates

by Yun Hee Ko, Hai Ha Tran Nguyen, Christopher R. Branstetter, Soeun Park, Jin-Kyun Lee, Jaesung Yang, Jangwook P. Jung and Myungwoong Kim

Polymers 2024, 16(1), 44; https://doi.org/10.3390/polym16010044 - 21 Dec 2023

Viewed by 956

Abstract

We demonstrate a single-component hydrophilic photocrosslinkable copolymer system that incorporates all critical functionalities into one chain. This design allows for the creation of uniform functional organic coatings on a variety of substrates. The copolymers were composed of a poly(ethylene oxide)-containing monomer, a monomer [...] Read more.

We demonstrate a single-component hydrophilic photocrosslinkable copolymer system that incorporates all critical functionalities into one chain. This design allows for the creation of uniform functional organic coatings on a variety of substrates. The copolymers were composed of a poly(ethylene oxide)-containing monomer, a monomer that can release a primary amine upon UV light, and a monomer with reactive epoxide or cyclic dithiocarbonate with a primary amine. These copolymers are easily incorporated into the solution-casting process using polar solvents. Furthermore, the resulting coating can be readily stabilized through UV light-induced crosslinking, providing an advantage for controlling the surface properties of various substrates. The photocrosslinking capability further enables us to photolithographically define stable polymer domains in a desirable region. The resulting copolymer coatings were chemically versatile in immobilizing complex molecules by (i) post-crosslinking functionalization with the reactive groups on the surface and (ii) the formation of a composite coating by mixing varying amounts of a protein of interest, i.e., fish skin gelatin, which can form a uniform dual crosslinked network. The number of functionalization sites in a thin film could be controlled by tuning the composition of the copolymers. In photocrosslinking and subsequent functionalizations, we assessed the reactivity of the epoxide and cyclic dithiocarbonate with the generated primary amine. Moreover, the orthogonality of the possible reactions of the presented reactive functionalities in the crosslinked thin films with complex molecules is assessed. The resulting copolymer coatings were further utilized to define a hydrophobic surface or an active surface for the adhesion of biological objects. Full article

(This article belongs to the Special Issue Functional Polymers: Interaction, Surface, Processing and Applications II)

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17 pages, 2469 KiB

Open AccessArticle

Interpenetration Networked Polyimide–Epoxy Copolymer under Kinetic and Thermodynamic Control for Anticorrosion Coating

by Dong-Sen Chen, Chun-Hua Chen, Wha-Tzong Whang and Chun-Wei Su

Polymers 2023, 15(1), 243; https://doi.org/10.3390/polym15010243 - 3 Jan 2023

Cited by 3 | Viewed by 1670

Abstract

Epoxy (EP) was copolymerized with polyamic acid (PAA, precursor of polyimide (PI)) with termanil monomers of (1) 4,4′-Oxydianiline (ODA) and (2) pyromellitic dianhydride (PMDA) individually to form (PI-O-EP) and (PI-P-EP) copolymers. The FTIR spectrum of PI-O-EP copolymerization intermediates shows that some amide-EP linkages [...] Read more.

Epoxy (EP) was copolymerized with polyamic acid (PAA, precursor of polyimide (PI)) with termanil monomers of (1) 4,4′-Oxydianiline (ODA) and (2) pyromellitic dianhydride (PMDA) individually to form (PI-O-EP) and (PI-P-EP) copolymers. The FTIR spectrum of PI-O-EP copolymerization intermediates shows that some amide-EP linkages were formed at low temperature and were broken at higher temperature; in additoin, the released amide was available for subsequent imidization to form PI. The curing and imidization of the amide groups on PAA were determined by reaction temperature (kinetic vs. thermodynamic control). In PI-P-EP, the released amide group was very short-lived (fast imidization) and was not observed on FTIR spectra. Formation and breakage of the amide-EP linkages is the key step for EP homopolymerization and formation of the interpenetration network. PI contributed in improving thermal durability and mechanical strength without compromising EP’s adhesion strength. Microphase separations were minimal at PI content less than 10 wt%. The copolymerization reaction in this study followed the “kinetic vs. thermodynamic control” principle. The copolymer has high potential for application in the field of higher-temperature anticorrosion. Full article

(This article belongs to the Special Issue Functional Polymers: Interaction, Surface, Processing and Applications II)

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