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Polymers
Special Issues
Functional Polymeric Materials: Synthesis, Characterization and Applications
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Functional Polymeric Materials: Synthesis, Characterization and Applications

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

Deadline for manuscript submissions: 15 July 2024 | Viewed by 11043

Special Issue Editors

Dr. Sumant Dwivedi

E-Mail Website
Guest Editor
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

E-Mail Website
Guest Editor
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
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Placido Mineo

E-Mail Website
Guest Editor
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
Special Issues, Collections and Topics in MDPI journals

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

Manuscript Submission Information

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

Published Papers (6 papers)

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Research

15 pages, 2876 KiB  
Article
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 1 | Viewed by 918
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 [...] Read more.
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 (Mn 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  
Article
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
Viewed by 873
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 [...] Read more.
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 (Mn) 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  
Article
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 1268
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 [...] Read more.
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  
Article
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 - 02 Nov 2022
Cited by 1 | Viewed by 3382
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 [...] Read more.
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  
Article
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
Viewed by 1991
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 [...] Read more.
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  
Article
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 - 03 Sep 2022
Cited by 3 | Viewed by 1542
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 [...] Read more.
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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