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Functional Polymeric Materials: Synthesis, Characterization and Applications

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A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Chemistry".

Deadline for manuscript submissions: closed (5 January 2025) | Viewed by 22916

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Dr. Sumant Dwivedi

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School of Polymer Science and Engineering, The University of Southern Mississippi, Hattiesburg, MS 39406, USA
Interests: polymers; catalysts; materials synthesis; (nano) composites and molecular engineering

Prof. Dr. Mohamad Al-Sheikhly

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Laboratory for Radiation and Polymer Science, Department of Materials Science and Engineering, A. J. Clark School of Engineering, University of Maryland, College Park, MD 20742-2115, USA
Interests: polymers; biomaterials; radiation engineering; nuclear engineering; environmental effects
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Prof. Dr. Placido Mineo

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Department of Chemical Sciences, University of Catania, 95125 Catania, Italy
Interests: polymers synthesis; nanomaterials for depollution; functional polymers; polymer characterization; polymers for space; polymers for sensing
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Special Issue Information

Dear Colleagues,

Synthetic polymeric materials have greatly contributed to the development of novel, lighter, stronger and higher-thermostability materials. Along with new catalytic systems and processes, synthetic polymer chemistry is evolving rapidly towards the development of highly functional materials. New functional polymeric materials are produced through precise molecular engineering, surface engineering and/or composite preparation and other possible means for the betterment of the existing polymer technology and products.

In view of this goal, this Special Issue in Polymers, “Functional Polymeric Materials: Synthesis, Characterization and Applications”, will disseminate original ideas, concepts and developments in the field of polymer science and technology, including polymer synthesis with (multi)functional monomers, which impart specific chemical resistance/reactivity mechanisms and physical, chemical, structural, biological and/or therapeutic functions. Original articles, reviews, mini-reviews and short communications covering the latest advances in the synthesis, applications and characterization of functional polymers are welcome.

Dr. Sumant Dwivedi
Prof. Dr. Mohamad Al-Sheikhly
Prof. Dr. Placido Mineo
Guest Editors

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Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

polymer chemistry
polymer synthesis
polymerization kinetics
composites
hybrid materials
aerogels
hydrogels
surface engineering
molecular engineering
chiral polymers

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Published Papers (11 papers)

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Research

15 pages, 21157 KiB

Open AccessArticle

Assembling Carbon Nanotube and Graphene in Chitosan/Sodium Alginate Hydrogels for Ion Removal Applications

by Sajad Paryav, Nariman Rajabifar, Amir Rostami, Mohsen Abbasi and Mohammad Akrami

Polymers 2025, 17(3), 353; https://doi.org/10.3390/polym17030353 - 28 Jan 2025

Viewed by 972

Abstract

Hydrogels have emerged as a promising material for the removal of heavy metal ions from contaminated water owing to their high water absorption capacity and biocompatibility. Despite notable advancements in improving the adsorptive capacity of hydrogels, the demand for a more efficient structure persists. Here, we explore the ion adsorption performance of crosslinked hydrogels based on chitosan and sodium alginate with various ratios of carbon nanotubes (CNT) and graphene platelets (GNP). This study highlights the adsorption of chromium ions and the thermal stability of hydrogels for pure, single-particle, and hybrid nanocomposites. The results depict a uniform microstructure attained when CNT, GNP, or both are implemented into the hydrogel due to the strong interaction of functional moieties. The incorporation of CNT and GNP manipulates the crystalline structure of the hydrogels, lowering their crystallinity by around 28% and 13%, respectively. The synergistic effect of CNT and GNP in hybrid hydrogels raises the decomposition temperature by 16%, indicating a favorable interplay interaction between nanoparticles and polymers. Calculations of the adsorption capacity accentuate such a mutual effect between CNT and GNP in various loads of ion capture from aqueous solutions. Kinetic models fitted to the hydrogel nanocomposites reveal that the pseudo-second-order model aligns better with the experimental data in comparison to the pseudo-first-order and intraparticle diffusion models, addressing the adsorption mechanisms while capturing chromium ions. Full article

(This article belongs to the Special Issue Functional Polymeric Materials: Synthesis, Characterization and Applications)

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20 pages, 9784 KiB

Open AccessArticle

Transparent Poly(amide-imide)s with Low Coefficient of Thermal Expansion from Trifluoromethylated Trimellitic Anhydride

by Seong Jong Kim, SeongUk Jeong, Taejoon Byun, Jun Sung Kim, Haeshin Lee and Sang Youl Kim

Polymers 2025, 17(3), 309; https://doi.org/10.3390/polym17030309 - 24 Jan 2025

Viewed by 660

Abstract

Making transparent aromatic polymers with high T_g and low thermal expansion behavior, like glass, is challenging. We report transparent and soluble poly(amide-imide)s (PAIs) with high dimensional stability synthesized from the new monomer, trifluoromethylated trimellitic anhydride. Insertion of trifluoromethyl (CF₃) groups into polymer chains enhanced solubility and the optical properties of polymers without sacrificing high thermal stability. Model reactions were utilized to study how the CF₃ group in trimellitic anhydride affects the polymerization reaction with aromatic diamine monomers, and a series of new PAIs were synthesized. All the polymers were soluble in polar organic solvents and can be solution-cast into nearly colorless and flexible freestanding films. The obtained PAI films possessed high thermal stability (T_d5: 437–452 °C in N₂) and high transparency (84~87% transmittance at 550 nm). Interestingly, PAIs prepared in this study exhibited high thermodimensional stability with low CTE values from 9 to 26 ppm/°C. The transparent poly(amide-imide) film with low CTE value finds its application in display and optical devices that require flexible and transparent form factors. Full article

(This article belongs to the Special Issue Functional Polymeric Materials: Synthesis, Characterization and Applications)

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20 pages, 5978 KiB

Open AccessArticle

The Integration of Microwave-Synthesized Silver Colloidal Nanoparticles into Poly (Lactic Acid)-Based Textiles as Antimicrobial Agents via Pre- and Post-Electrospinning Processes

by Muhammad Omer Aijaz, Ibrahim A. Alnaser, Md Irfanul Haque Siddiqui and Mohammad Rezaul Karim

Polymers 2024, 16(24), 3613; https://doi.org/10.3390/polym16243613 - 23 Dec 2024

Viewed by 729

Abstract

This study introduces a novel method to enhance the antibacterial functionality of electrospun nanofibrous textiles by integrating silver nanoparticles (AgNPs) into poly (lactic acid) (PLA) fabrics through pre- and post-electrospinning techniques. AgNPs were incorporated into hydrophobic and modified hydrophilic PLA textiles via pre-solution blending and post-solution casting. A PEG-PPG-PEG tri-block copolymer was utilized to enhance hydrophilicity and water stability, while AgNPs served as antibacterial agents. Morphological analyses confirmed uniform, smooth, and beadless nanofibers with diameters between 435 and 823 nm. Energy-dispersive X-ray spectroscopy spectra and elemental analysis verified the successful incorporation of AgNPs, with higher Ag content in the post-electrospinning samples. Contact angle measurements showed an improved hydrophilicity of the modified PLA textiles, absorbing water droplets within 2 s. The X-ray crystallography patterns confirmed the amorphous structures of the PLA and PEG-PPG-PEG, with reduced crystallinity in the samples containing AgNPs. Thermal analysis indicated lower decomposition temperatures for the hydrophilic samples due to the plasticizing effects of PEG-PPG-PEG on PLA. Mechanical testing showed comparable tensile strengths but reduced elongation in the post-treated samples. The antibacterial efficacy was assessed against various bacterial strains, with post-electrospinning AgNP incorporation showing the most effective antibacterial properties. The results indicate that integrating electrospinning and nanofiber modification techniques expands the applications of PLA-based protective fabrics for disabled individuals. Full article

(This article belongs to the Special Issue Functional Polymeric Materials: Synthesis, Characterization and Applications)

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15 pages, 6889 KiB

Open AccessArticle

Quaternized and Hyperbranched Amidoxime-Modified Ultra-High-Molecular-Weight Polyethylene Fiber for Uranium Extraction from Seawater

by Lijun Hu, Hongwei Han, Xuanzhi Mao, Xinxin Feng, Yulong He, Jiangtao Hu and Guozhong Wu

Polymers 2024, 16(23), 3310; https://doi.org/10.3390/polym16233310 - 27 Nov 2024

Viewed by 807

Abstract

The most promising material for uranium extraction from saltwater is generally acknowledged to be fibrous adsorbents. An irradiation-modified anti-biofouling ultra-high-molecular-weight polyethylene (UHMWPE-g-PGAO) fibrous adsorbent with a hyperbranched structure was synthesized. It exhibited adsorption capacities of 314.8 mg-U/g-Ads in aqueous solution and 4.04 mg-U/g-Ads in simulated seawater over a 28-day period. The ultra-high-molecular-weight polyethylene (UHMWPE) fiber was functionalized by covalently linking hyperbranched polyethyleneimine (h-PEI) to facilitate the migration of uranyl ions within the fibers. Additionally, amidoxime and quaternary ammonium groups were immobilized on the fiber surface to enhance uranium affinity and provide defense against marine organisms. This three-dimensional design of amidoxime and h-PEI-modified UHMWPE fiber retained more than 91.0% of its maximum adsorption capacity after undergoing five adsorption-desorption cycles. The UHMWPE-g-PGAO adsorbent exhibits significant antibacterial activity against Escherichia coli and Staphylococcus aureus, achieving an inactivation efficiency of over 99.9%. It is proved to be an innovative fiber adsorbent for uranium extraction from seawater for its biofouling resistance, robustness, and reusability. Full article

(This article belongs to the Special Issue Functional Polymeric Materials: Synthesis, Characterization and Applications)

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12 pages, 2554 KiB

Open AccessArticle

Electromechanical Performances of Polyvinyl Chloride Gels Using (Polyvinyl Chloride-Co-Vinyl Acetate) (P(VC-VA)) Synergistic Plasticization

by Han Yan, Chang Wei, Zexing Wang, Lei Liu, Zicai Zhu, Junshi Zhang, Jihong Zhu and Weihong Zhang

Polymers 2024, 16(13), 1904; https://doi.org/10.3390/polym16131904 - 3 Jul 2024

Cited by 1 | Viewed by 1573

Abstract

The current polyvinyl chloride (PVC) gel flexible actuators are facing challenges of high input voltage and an insufficient elastic modulus. In this study, we conducted a detailed study on the properties of PVC gel prepared by introducing the modifier polyvinyl chloride-vinyl acetate (P(VC-VA)). We compared a modified PVC gel with the traditional one in terms of the relative dielectric constant, mechanical modulus, and electromechanical actuation performance. Experimental results demonstrated that the introduction of P(VC-VA) enhanced the dielectric constant and reduced the driving electric field strength of PVC gels. The dielectric constant increased from 4.77 to 7.3. The electromechanical actuation performance increased by 150%. We employed the Gent model to fit the experimental results, and the actual experimental data aligned well with the expectations of the Gent model. The research results show that this type of plasticizing method effectively balanced the mechanical and electrical performance of PVC gels. This study summarizes the experimental results and performance analysis of PVC gels prepared using innovative plasticization methods, revealing the potential engineering applications of polymeric gels. Full article

(This article belongs to the Special Issue Functional Polymeric Materials: Synthesis, Characterization and Applications)

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15 pages, 2876 KiB

Open AccessArticle

Vinyl-Addition Homopolymeization of Norbornenes with Bromoalkyl Groups

by Artyom O. Lunin, Fedor A. Andreyanov, Igor S. Makarov and Maxim V. Bermeshev

Polymers 2023, 15(22), 4444; https://doi.org/10.3390/polym15224444 - 17 Nov 2023

Cited by 2 | Viewed by 2026

Abstract

Vinyl-addition polynorbornenes are of great interest as versatile templates for the targeted design of polymer materials with desired properties. These polymers possess rigid and saturated backbones, which provide them with high thermal and chemical stability as well as high glass transition temperatures. Vinyl-addition polymers from norbornenes with bromoalkyl groups are widely used as precursors of anion exchange membranes; however, high-molecular-weight homopolymers from such monomers are often difficult to prepare. Herein, we report the systematic study of vinyl-addition polymerization of norbornenes with various bromoalkyl groups on Pd-catalysts bearing N-heterocyclic carbene ligands ((NHC)Pd-systems). Norbornenes with different lengths of hydrocarbon linker (one, two, and four CH₂ groups) between the bicyclic norbornene moiety and the bromine atom were used as model monomers, while single- and three-component (NHC)Pd-systems were applied as catalysts. In vinyl-addition polymerization, the reactivity of the investigated monomers varied substantially. The relative reactivity of these monomers was assessed in copolymerization experiments, which showed that the closer the bromine is to the norbornene double-bond, the lower the monomer’s reactivity. The most reactive monomer was the norbornene derivative with the largest substituent (with the longest linker). Tuning the catalyst’s nature and the conditions of polymerization, we succeeded in synthesizing high-molecular-weight homopolymers from norbornenes with bromoalkyl groups (M_n up to 1.4 × 10⁶). The basic physico-chemical properties of the prepared polymers were studied and considered together with the results of vinyl-addition polymerization. Full article

(This article belongs to the Special Issue Functional Polymeric Materials: Synthesis, Characterization and Applications)

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21 pages, 6764 KiB

Open AccessArticle

Straightforward Enzymatic Methacrylation of Poly(Glycerol Adipate) for Potential Applications as UV Curing Systems

by Víctor Hevilla, Águeda Sonseca and Marta Fernández-García

Polymers 2023, 15(14), 3050; https://doi.org/10.3390/polym15143050 - 14 Jul 2023

Cited by 1 | Viewed by 1639

Abstract

Enzymatic one-pot synthesis procedures in a one-step and two-step monomers addition were developed to obtain poly(glycerol adipate) macromers with methacrylate end-functional groups under the presence of 1 and 3 wt% of Candida antarctica lipase B (CALB). Glycerol, divinyl adipate, and vinyl methacrylate were enzymatically reacted (vinyl methacrylate was either present from the beginning in the monomers solution or slowly dropped after 6 h of reaction) in tetrahydrofuran (THF) at 40 °C over 48 h. Macromers with a methacrylate end groups fraction of ≈52% in a simple one-pot one-step procedure were obtained with molecular weights (M_n) of ≈7500–7900 g/mol. The obtained products under the one-pot one-step and two steps synthesis procedures carried out using 1 and 3 wt% of a CALB enzymatic catalyst were profusely characterized by NMR (¹H and ¹³C), MALDI-TOF MS, and SEC. The methacrylate functional macromers obtained with the different procedures and 1 wt% of CALB were combined with an Irgacure^® 369 initiator to undergo homopolymerization under UV irradiation for 10 and 30 min, in order to test their potential to obtain amorphous networks within minutes with similar properties to those typically obtained by complex acrylation/methacrylation procedures, which need multiple purification steps and harsh reagents such as acyl chlorides. To the best of our knowledge, this is the first time that it has been demonstrated that the obtention of methacrylate-functional predominantly linear macromers based on poly(glycerol adipate) is able to be UV crosslinked in a simple one-step procedure. Full article

(This article belongs to the Special Issue Functional Polymeric Materials: Synthesis, Characterization and Applications)

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24 pages, 6614 KiB

Open AccessArticle

Multivariate Analysis Applied to Microwave-Driven Cyanide Polymerization: A Statistical View of a Complex System

by Cristina Pérez-Fernández, Elena González-Toril, Eva Mateo-Martí and Marta Ruiz-Bermejo

Polymers 2023, 15(2), 410; https://doi.org/10.3390/polym15020410 - 12 Jan 2023

Viewed by 1900

Abstract

For the first time, chemometrics was applied to the recently reported microwave-driven cyanide polymerization. Fast, easy, robust, low-cost, and green-solvent processes are characteristic of these types of reactions. These economic and environmental benefits, originally inspired by the constraints imposed by plausible prebiotic synthetic conditions, have taken advantage of the development of a new generation of HCN-derived multifunctional materials. HCN-derived polymers present tunable properties by temperature and reaction time. However, the apparently random behavior observed in the evolution of cyanide polymerizations, assisted by microwave radiation over time at different temperatures, leads us to study this highly complex system using multivariate analytical tools to have a proper view of the system. Two components are sufficient to explain between 84 and 98% of the total variance in the data in all principal component analyses. In addition, two components explain more than 91% of the total variance in the data in the case of principal component analysis for categorical data. These consistent statistical results indicate that microwave-driven polymerization is a more robust process than conventional thermal syntheses but also that plausible prebiotic chemistry in alkaline subaerial environments could be more complex than in the aerial part of these systems, presenting a clear example of the “messy chemistry” approach of interest in the research about the origins of life. In addition, the methodology discussed herein could be useful for the data analysis of extraterrestrial samples and for the design of soft materials, in a feedback view between prebiotic chemistry and materials science. Full article

(This article belongs to the Special Issue Functional Polymeric Materials: Synthesis, Characterization and Applications)

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10 pages, 2679 KiB

Open AccessArticle

Manufacturing of Soft Contact Lenses Using Reusable and Reliable Cyclic Olefin Copolymer Moulds

by Christopher Musgrave, Lorcan O’Toole, Tianyu Mao, Qing Li, Min Lai and Fengzhou Fang

Polymers 2022, 14(21), 4681; https://doi.org/10.3390/polym14214681 - 2 Nov 2022

Cited by 1 | Viewed by 5712

Abstract

We present experimental evidence of reusable, reliable cyclic olefin copolymer (COC) moulds in soft contact lens manufacturing. The moulds showed high performance surface roughness characteristics despite >20 kW exposure to 365 nm ultraviolet (UV) light from repeated use. Ultra-precision manufacturing techniques were used to fabricate transparent COC mould inserts and to produce soft contact lenses from liquid monomer compositions. Both polymer and silicone hydrogels were fabricated with more than 60 individual uses of the moulds. White light interferometry measured the surface roughness (Sa) of the COC moulds to be almost unchanged before and after repeated use (Sa 16.3 nm before vs. 16.6 nm after). The surface roughness of the prototyped lenses and that of commercially available soft contact lenses were then compared by white light interferometry. The surface roughness of the lenses was also nearly unchanged, despite undergoing more than 60 uses of the COC moulds (lens Sa 24.4 nm before vs. after Sa 26.5 nm). By comparison the roughness of the commercial lenses ranged from 9.3–28.5 nm, including conventional and silicone lenses, indicating that the reusable COC moulds produced competitive surface properties. In summary, COC moulds have potential as reusable and reliable mould inserts in the manufacturing of soft contact lenses, yet maintain high quality optical surfaces even after sustained exposure to UV light. Full article

(This article belongs to the Special Issue Functional Polymeric Materials: Synthesis, Characterization and Applications)

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19 pages, 3513 KiB

Open AccessArticle

A Multifunctional Conjugated Polymer Developed as an Efficient System for Differentiation of SH-SY5Y Tumour Cells

by Angelo Nicosia, Giuseppe La Perna, Lorena Maria Cucci, Cristina Satriano and Placido Mineo

Polymers 2022, 14(20), 4329; https://doi.org/10.3390/polym14204329 - 14 Oct 2022

Cited by 1 | Viewed by 2781

Abstract

Polymer-based systems have been demonstrated in novel therapeutic and diagnostic (theranostic) treatments for cancer and other diseases. Polymers provide a useful scaffold to develop multifunctional nanosystems that combine various beneficial properties such as drug delivery, bioavailability, and photosensitivity. For example, to provide passive tumour targeting of small drug molecules, polymers have been used to modify and functionalise the surface of water-insoluble drugs. This approach also allows the reduction of adverse side effects, such as retinoids. However, multifunctional polymer conjugates containing several moieties with distinct features have not been investigated in depth. This report describes the development of a one-pot approach to produce a novel multifunctional polymer conjugate. As a proof of concept, we synthesised polyvinyl alcohol (PVA) covalently conjugated with rhodamine B (a tracking agent), folic acid (a targeting agent), and all-trans retinoic acid (ATRA, a drug). The obtained polymer (PVA@RhodFR) was characterised by MALDI-TOF mass spectrometry, gel permeation chromatography, thermal analysis, dynamic light-scattering, NMR, UV-Vis, and fluorescence spectroscopy. Finally, to evaluate the efficiency of the multifunctional polymer conjugate, cellular differentiation treatments were performed on the neuroblastoma SH-SY5Y cell line. In comparison with standard ATRA-based conditions used to promote cell differentiation, the results revealed the high capability of the new PVA@RhodFR to induce neuroblastoma cells differentiation, even with a short incubation time and low ATRA concentration. Full article

(This article belongs to the Special Issue Functional Polymeric Materials: Synthesis, Characterization and Applications)

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20 pages, 1295 KiB

Open AccessArticle

Tailoring the Hydroxyl Density of Glass Surface for Anionic Ring-Opening Polymerization of Polyamide 6 to Manufacture Thermoplastic Composites

by Achraf Belkhiri, Nick Virgilio, Valérie Nassiet, Hélène Welemane, France Chabert and Olivier De Almeida

Polymers 2022, 14(17), 3663; https://doi.org/10.3390/polym14173663 - 3 Sep 2022

Cited by 3 | Viewed by 2214

Abstract

Reactive thermoplastics matrices offer ease of processing using well-known molding techniques (such as Resin Transfer Molding) due to their initially low viscosity. For Polyamide 6 (PA6)/glass composites, the hydroxyl groups on the glass surface slow down the anionic ring-opening polymerization (AROP) reaction, and can ultimately inhibit it. This work aims to thoroughly control the hydroxyl groups and the surface chemistry of glass particulates to facilitate in situ AROP-an aspect that has been barely explored until now. A model system composed of a PA6 matrix synthesized by AROP is reinforced with calcinated and silanized glass microparticles. We systematically quantify, by TGA and FTIR, the complete particle surface modification sequence, from the dehydration, dehydroxylation and rehydroxylation processes, to the silanization step. Finally, the impact of the particle surface chemistry on the polymerization and crystallization of the PA6/glass composites was quantified by DSC. The results confirm that a careful balance is required between the dehydroxylation process, the simultaneous rehydroxylation and silane grafting, and the residual hydroxyl groups, in order to maintain fast polymerization and crystallization kinetics and to prevent reaction inhibition. Specifically, a hydroxyl concentration above 0.2 mmol OH·g⁻¹ leads to a slowdown of the PA6 polymerization reaction. This reaction can be completely inhibited when the hydroxyl concentration reaches 0.77 mmol OH·g⁻¹ as in the case of fully rehydroxylated particles or pristine raw particles. Furthermore, both the rehydroxylation and silanization processes can be realized simultaneously without any negative impact on the polymerization. This can be achieved with a silanization time of 2 h under the treatment conditions of the study. In this case, the silane agent gradually replaces the regenerated hydroxyls. This work provides a roadmap for the preparation of reinforced reactive thermoplastic materials. Full article

(This article belongs to the Special Issue Functional Polymeric Materials: Synthesis, Characterization and Applications)

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