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Keywords = norbornene cellulose

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15 pages, 2239 KB  
Article
Elastomeric Compositions of Ethylene–Norbornene Copolymer Containing Biofillers Based on Coffee and Tea Waste
by Aneta Malicka, Kamila Rułka, Malgorzata Latos-Brozio and Anna Masek
Materials 2024, 17(16), 4160; https://doi.org/10.3390/ma17164160 - 22 Aug 2024
Cited by 2 | Viewed by 1469
Abstract
The development of eco-friendly elastomeric materials has become an important issue in recent years. In this work, thermoplastic elastomer samples of an ethylene–norbornene copolymer (EN) with coffee and tea biofillers mixed with typical fillers such as montmorillonite (MMT), silica (SiO2), and [...] Read more.
The development of eco-friendly elastomeric materials has become an important issue in recent years. In this work, thermoplastic elastomer samples of an ethylene–norbornene copolymer (EN) with coffee and tea biofillers mixed with typical fillers such as montmorillonite (MMT), silica (SiO2), and cellulose were investigated. The aim of this research was to determine the effect of fillers on the properties of the materials and to assess their degradability after two ultraviolet (UV) aging cycles (200, 400 h). The scientific novelty of this work is the assessment of the anti-aging effect of simultaneous biofillers–stabilizers based on coffee and tea waste. The surfaces of the obtained polymer compositions were examined using infrared spectroscopy (FTIR-ATR). Contact angles were determined, and surface energy was calculated. The mechanical properties were tested, and the influence of plant fillers and aging on the color change in the materials was analyzed. The combination of coffee with silica, MMT, and cellulose fillers limited the migration of fatty acids and other compounds from the biofiller to the EN surface (FTIR analysis). Based on the aging coefficients K, it was shown that all coffee- and tea-based fillers stabilized the polymer compositions during UV aging (400 h). The results allowed the authors to determine the importance and impact of waste plant fillers on the degradability of the synthetic EN. Full article
(This article belongs to the Special Issue New Advances in Elastomer Materials and Its Composites)
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19 pages, 7234 KB  
Article
Facile Fabrication of NIR-Responsive Alginate/CMC Hydrogels Derived through IEDDA Click Chemistry for Photothermal–Photodynamic Anti-Tumor Therapy
by Ali Rizwan, Israr Ali, Sung-Han Jo, Trung Thang Vu, Yeong-Soon Gal, Yong Hyun Kim, Sang-Hyug Park and Kwon Taek Lim
Gels 2023, 9(12), 961; https://doi.org/10.3390/gels9120961 - 7 Dec 2023
Cited by 17 | Viewed by 3400
Abstract
Novel chemically cross-linked hydrogels derived from carboxymethyl cellulose (CMC) and alginate (Alg) were prepared through the utilization of the norbornene (Nb)–methyl tetrazine (mTz) click reaction. The hydrogels were designed to generate reactive oxygen species (ROS) from an NIR dye, indocyanine green (ICG), for [...] Read more.
Novel chemically cross-linked hydrogels derived from carboxymethyl cellulose (CMC) and alginate (Alg) were prepared through the utilization of the norbornene (Nb)–methyl tetrazine (mTz) click reaction. The hydrogels were designed to generate reactive oxygen species (ROS) from an NIR dye, indocyanine green (ICG), for combined photothermal and photodynamic therapy (PTT/PDT). The cross-linking reaction between Nb and mTz moieties occurred via an inverse electron-demand Diels–Alder chemistry under physiological conditions avoiding the need for a catalyst. The resulting hydrogels exhibited viscoelastic properties (G′ ~ 492–270 Pa) and high porosity. The hydrogels were found to be injectable with tunable mechanical characteristics. The ROS production from the ICG-encapsulated hydrogels was confirmed by DPBF assays, indicating a photodynamic effect (with NIR irradiation at 1–2 W for 5–15 min). The temperature of the ICG-loaded hydrogels also increased upon the NIR irradiation to eradicate tumor cells photothermally. In vitro cytocompatibility assessments revealed the non-toxic nature of CMC–Nb and Alg–mTz towards HEK-293 cells. Furthermore, the ICG-loaded hydrogels effectively inhibited the metabolic activity of Hela cells after NIR exposure. Full article
(This article belongs to the Special Issue Advances in Cellulose-Based Hydrogels (2nd Edition))
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12 pages, 4350 KB  
Article
Highly Norbornylated Cellulose and Its “Click” Modification by an Inverse-Electron Demand Diels–Alder (iEDDA) Reaction
by Christina Wappl, Viktor Schallert, Christian Slugovc, Astrid-Caroline Knall and Stefan Spirk
Molecules 2021, 26(5), 1358; https://doi.org/10.3390/molecules26051358 - 4 Mar 2021
Cited by 6 | Viewed by 3286
Abstract
A facile, catalyst-free synthesis of a norbornylated cellulosic material (NC) with a high degree of substitution (2.9) is presented by direct reaction of trimethylsilyl cellulose with norbornene acid chloride. The resulting NC is highly soluble in organic solvents and its reactive double bonds [...] Read more.
A facile, catalyst-free synthesis of a norbornylated cellulosic material (NC) with a high degree of substitution (2.9) is presented by direct reaction of trimethylsilyl cellulose with norbornene acid chloride. The resulting NC is highly soluble in organic solvents and its reactive double bonds were exploited for the copper-free inverse-electron demand Diels–Alder (iEDDA) “click” reaction with 3,6-di(pyridin-2-yl)-1,2,4,5-tetrazine. Reaction kinetics are comparable to the well-known Huisgen type 1,3-dipolar cycloaddition of azide with alkynes, while avoiding toxic catalysts. Full article
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18 pages, 2223 KB  
Article
Cellulose Modification for Improved Compatibility with the Polymer Matrix: Mechanical Characterization of the Composite Material
by Stefan Cichosz, Anna Masek and Adam Rylski
Materials 2020, 13(23), 5519; https://doi.org/10.3390/ma13235519 - 3 Dec 2020
Cited by 38 | Viewed by 4794
Abstract
The following article is the presentation attempt of cellulose hybrid chemical modification approach as a useful tool in improving the mechanical properties of plant fiber-filled polymer materials. The treatment process is a prolonged method of the cellulose maleinization and consists of two steps: [...] Read more.
The following article is the presentation attempt of cellulose hybrid chemical modification approach as a useful tool in improving the mechanical properties of plant fiber-filled polymer materials. The treatment process is a prolonged method of the cellulose maleinization and consists of two steps: 1. solvent exchange (altering fiber structure); 2. maleic anhydride (MA) chemical grafting (surface modification). Thanks to the incorporated treatment method, the created ethylene–norbornene copolymer composite specimen exhibited an improved performance, tensile strength at the level of (38.8 ± 0.8) MPa and (510 ± 20)% elongation at break, which is higher than for neat polymer matrix and could not be achieved in the case of regular MA treatment. Moreover, both the Payne effect and filler efficiency factor indicate a possibility of the fiber reinforcing nature that is not a common result. Additionally, the polymer matrix employed in this research is widely known for its excellent resistance to aqueous and polar organic media, good biocompatibility, and the ability to reproduce fine structures which makes it an interesting material regarding healthcare applications. Therefore, plant fiber-based polymer materials described in this research might be potentially applied in this area, e.g., medical devices, drug delivery, wearables, pharmaceutical blisters, and trays. Full article
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18 pages, 5425 KB  
Article
Superiority of Cellulose Non-Solvent Chemical Modification over Solvent-Involving Treatment: Application in Polymer Composite (part II)
by Stefan Cichosz and Anna Masek
Materials 2020, 13(13), 2901; https://doi.org/10.3390/ma13132901 - 28 Jun 2020
Cited by 22 | Viewed by 3756
Abstract
The following article debates on the properties of cellulose-filled ethylene-norbornene copolymer (EN) composites. Natural fibers employed in this study have been modified via two different approaches: solvent-involving (S) and newly developed non-solvent (NS). The second type of the treatment is fully eco-friendly and [...] Read more.
The following article debates on the properties of cellulose-filled ethylene-norbornene copolymer (EN) composites. Natural fibers employed in this study have been modified via two different approaches: solvent-involving (S) and newly developed non-solvent (NS). The second type of the treatment is fully eco-friendly and was carried out in the planetary mill without incorporation of any additional, waste-generating substances. Composite samples have been investigated with the use of spectroscopic methods (FT-IR), differential scanning calorimetry (DSC), static mechanical analysis, and surface-free energy measurements. It has been proved that the possible filler-polymer matrix interaction changes may occur due to the performed modifications. The highest reinforcement was evidenced for the composite sample filled with cellulose treated via a NS approach—TS = (34 ± 2) MPa, Eb = (380 ± 20)%. Additionally, a surface free energy polar part exhibited a significant increase for the same type of modification. Consequently, this could indicate easier wetting of the material which may contribute to the degradation process enhancement. Successfully developed cellulose-filled ethylene-norbornene copolymer composite compromises the rules of green chemistry and sustainable development by taking an advantage of renewable natural resources. This bio-inspired material may become an eco-friendly alternative for commonly used polymer blends. Full article
(This article belongs to the Special Issue Advances in Natural Fibers and Polymers)
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16 pages, 4003 KB  
Article
Thermal Behavior of Green Cellulose-Filled Thermoplastic Elastomer Polymer Blends
by Stefan Cichosz and Anna Masek
Molecules 2020, 25(6), 1279; https://doi.org/10.3390/molecules25061279 - 12 Mar 2020
Cited by 31 | Viewed by 4787
Abstract
A recently developed cellulose hybrid chemical treatment consists of two steps: solvent exchange (with ethanol or hexane) and chemical grafting of maleic anhydride (MA) on the surface of fibers. It induces a significant decrease in cellulose moisture content and causes some changes in [...] Read more.
A recently developed cellulose hybrid chemical treatment consists of two steps: solvent exchange (with ethanol or hexane) and chemical grafting of maleic anhydride (MA) on the surface of fibers. It induces a significant decrease in cellulose moisture content and causes some changes in the thermal resistance of analyzed blend samples, as well as surface properties. The thermal characteristics of ethylene-norbornene copolymer (TOPAS) blends filled with hybrid chemically modified cellulose fibers (UFC100) have been widely described on the basis of differential scanning calorimetry and thermogravimetric analysis. Higher thermal stability is observed for the materials filled with the fibers which were dried before any of the treatments carried out. Dried cellulose filled samples start to degrade at approximately 330 °C while undried UFC100 specimens begin to degrade around 320 °C. Interestingly, the most elevated thermal resistance was detected for samples filled with cellulose altered only with solvents (both ethanol and hexane). In order to support the supposed thermal resistance trends of prepared blend materials, apparent activation energies assigned to cellulose degradation (EA1) and polymer matrix decomposition (EA2) have been calculated and presented in the article. It may be evidenced that apparent activation energies assigned to the first decomposition step are higher in case of the systems filled with UFC100 dried prior to the modification process. Moreover, the results have been enriched using surface free energy analysis of the polymer blends. The surface free energy polar part (Ep) raises considering samples filled with not dried UFC100. On the other hand, when cellulose fibers are dried prior to the modification process, then the blend sample’s dispersive part of surface free energy is increased with respect to that containing unmodified fiber. As polymer blend Ep exhibits higher values reflecting enhanced material degradation potential, the cellulose fibers employment leads to more eco-friendly production and responsible waste management. This is in accordance with the rules of sustainable development. Full article
(This article belongs to the Special Issue Fibre Reinforced Composites: Interfacial Modifications and Property)
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18 pages, 4006 KB  
Article
Drying of the Natural Fibers as A Solvent-Free Way to Improve the Cellulose-Filled Polymer Composite Performance
by Stefan Cichosz and Anna Masek
Polymers 2020, 12(2), 484; https://doi.org/10.3390/polym12020484 - 21 Feb 2020
Cited by 25 | Viewed by 6350
Abstract
When considering cellulose (UFC100) modification, most of the processes employ various solvents in the role of the reaction environment. The following article addresses a solvent-free method, thermal drying, which causes a moisture content decrease in cellulose fibers. Herein, the moisture content in UFC100 [...] Read more.
When considering cellulose (UFC100) modification, most of the processes employ various solvents in the role of the reaction environment. The following article addresses a solvent-free method, thermal drying, which causes a moisture content decrease in cellulose fibers. Herein, the moisture content in UFC100 was analyzed with spectroscopic methods, thermogravimetric analysis, and differential scanning calorimetry. During water desorption, a moisture content drop from approximately 6% to 1% was evidenced. Moreover, drying may bring about a specific variation in cellulose’s chemical structure. These changes affected the cellulose-filled polymer composite’s properties, e.g., an increase in tensile strength from 17 MPa for the not-dried UFC100 to approximately 30 MPa (dried cellulose; 24 h, 100 °C) was observed. Furthermore, the obtained tensile test results were in good correspondence with Payne effect values, which changed from 0.82 MPa (not-dried UFC100) to 1.21 MPa (dried fibers). This raise proves the reinforcing nature of dried UFC100, as the Payne effect is dependent on the filler structure’s development within a polymer matrix. This finding paves new opportunities for natural fiber applications in polymer composites by enabling a solvent-free and efficient cellulose modification approach that fulfils the sustainable development rules. Full article
(This article belongs to the Special Issue Cellulose and Renewable Materials)
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