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Polymers
Special Issues
Polymer Functionalization and Cross-Linking: Methodologies and Applications
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Polymer Functionalization and Cross-Linking: Methodologies and Applications

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

Deadline for manuscript submissions: closed (30 April 2022) | Viewed by 7415

Special Issue Editor

Dr. Luca Vaghi

E-Mail Website
Guest Editor
Department of Material Science, University of Milano-Bicocca, via Cozzi 55, 20125 Milano, Italy
Interests: organic synthesis; stereochemistry; polymers functionalization; bioactive compounds; micellar chemistry; surface chemistry; sensors

Special Issue Information

Dear Colleagues,

Polymeric materials are of great importance in modern world and are present in almost all fields of science and industry. In addition to new polymers and polymerization techniques, the last few decades have shown an exponential increase of methodologies aimed at functionalizing known polymers, whether they are of synthetic origin (e.g., plastics, synthetic rubbers, conductive polymers) or bio derived ones (i.e., polypeptides, polysaccharides and polynucleotides), in order to improve their mechanical, thermal, electronic or optical properties, as well as to introduce selected functionalities needed for advanced applications. Among the functionalization strategies deserving mention are those geared towards polymers cross-linking. Often, a successful procedure used for a single-site attack can inspire the design of a reagent that exploits the same reactivity in a bifunctional way, allowing the connection of two sites of the polymer chain, as well as two different chains. However, cross-linking can also be achieved by the single-site introduction of functionalities able to interact with each other by non-covalent interactions.

This Special Issue will focus on recent advances in methodologies for polymer functionalization and cross‑linking, as well as new applications of functionalised and cross-linked polymers. Both original research papers and reviews covering this topic are welcome.

Dr. Luca Vaghi
Guest Editor

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 functionalization
  • Polymer cross-linking
  • Functional polymers
  • Post-polymerization modification
  • Functionalized polymers applications
  • Cross-linked polymers applications

Published Papers (4 papers)

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Research

12 pages, 3738 KiB  
Article
Thermally Activable Bistetrazoles for Elastomers Crosslinking
by Mauro Monti, Luca Giannini, Luciano Tadiello, Silvia Guerra, Antonio Papagni and Luca Vaghi
Polymers 2022, 14(14), 2919; https://doi.org/10.3390/polym14142919 - 19 Jul 2022
Cited by 2 | Viewed by 1420
Abstract
Sulfur vulcanization is the most used method for curing of natural and synthetic rubbers. The crosslinking degree achieved is usually controlled by adding proper quantities of accelerants, activators, co-activators, retardants, and inhibitors, and influences the hardness, elasticity, hysteresis of elastomers and, consequently, the [...] Read more.
Sulfur vulcanization is the most used method for curing of natural and synthetic rubbers. The crosslinking degree achieved is usually controlled by adding proper quantities of accelerants, activators, co-activators, retardants, and inhibitors, and influences the hardness, elasticity, hysteresis of elastomers and, consequently, the properties and behavior of the materials that incorporate them. Despite the fine tuning pursued over the years, sulfur crosslinking is still difficult to control both in terms of degree and homogeneity of cross-link. Addition of thermally activable bifunctional reagents able to crosslink the polymer matrix through covalent bonds could be a strategy to modulate and control finely the reticulation grade of elastomers. Tetrazoles can form highly reactive nitrilimines by thermal treatment at appropriate temperature, which can react with the vinyl double bonds present in the rubber. In this work a set of bis-tetrazoles were synthesized and those with the right activation temperatures were used for the curing of styrene-butadiene rubber, acting both as single crosslinkers and together with classic sulfur-based ones. The addition of bistetrazoles simplified and made more efficient the compounding process, allowing to prolong the mixing until optimum dispersion and homogeneity were obtained. Moreover, they led to an improvement in the hysteretic properties of the compound and to the reduction of the non-linearity of the dynamic behavior (Payne effect). Full article
(This article belongs to the Special Issue Polymer Functionalization and Cross-Linking: Methodologies and Applications)
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10 pages, 2706 KiB  
Article
Terahertz Spectral Properties of PEO-Based Anti-Adhesion Films Cross-Linked by Electron Beam Irradiation
by Hyeon Sang Bark, Inhee Maeng, Jin Un Kim, Kyoung Dong Kim, Jae Hun Na, Junki Min, Jungsup Byun, Yongkeun Song, Byung-youl Cha, Seung Jae Oh and Young Bin Ji
Polymers 2022, 14(10), 2008; https://doi.org/10.3390/polym14102008 - 13 May 2022
Cited by 4 | Viewed by 1999
Abstract
We investigated the spectral property changes in anti-adhesion films, which were cross-linked and surface-modified through electron beam irradiation, using terahertz time-domain spectroscopy (THz-TDS). Polyethylene oxide (PEO), which is a biocompatible and biodegradable polymer, was the main component of these anti-adhesion films being manufactured [...] Read more.
We investigated the spectral property changes in anti-adhesion films, which were cross-linked and surface-modified through electron beam irradiation, using terahertz time-domain spectroscopy (THz-TDS). Polyethylene oxide (PEO), which is a biocompatible and biodegradable polymer, was the main component of these anti-adhesion films being manufactured for testing. The terahertz characteristics of the films were affected by the porosity generated during the freeze-drying and compression processes of sample preparation, and this was confirmed using optical coherence tomography (OCT) imaging. An anti-adhesion polymer film made without porosity was measured by using the THz-TDS method, and it was confirmed that the refractive index and absorption coefficient were dependent on the crosslinking state. To our knowledge, this is the first experiment on the feasibility of monitoring cross-linking states using terahertz waves. The THz-TDS method has potential as a useful nondestructive technique for polymer inspection and analysis. Full article
(This article belongs to the Special Issue Polymer Functionalization and Cross-Linking: Methodologies and Applications)
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21 pages, 6030 KiB  
Article
Understanding the Molecular Dynamics of Dual Crosslinked Networks by Dielectric Spectroscopy
by Saul Utrera-Barrios, Reyes Verdugo Manzanares, Javier Araujo-Morera, Sergio González, Raquel Verdejo, Miguel Ángel López-Manchado and Marianella Hernández Santana
Polymers 2021, 13(19), 3234; https://doi.org/10.3390/polym13193234 - 24 Sep 2021
Cited by 19 | Viewed by 3821
Abstract
The combination of vulcanizing agents is an adequate strategy to develop multiple networks that consolidate the best of different systems. In this research, sulfur (S), and zinc oxide ( ZnO) were combined as vulcanizing agents in a matrix of carboxylated nitrile rubber (XNBR). [...] Read more.
The combination of vulcanizing agents is an adequate strategy to develop multiple networks that consolidate the best of different systems. In this research, sulfur (S), and zinc oxide ( ZnO) were combined as vulcanizing agents in a matrix of carboxylated nitrile rubber (XNBR). The resulting dual network improved the abrasion resistance of up to ~15% compared to a pure ionically crosslinked network, and up to ~115% compared to a pure sulfur-based covalent network. Additionally, the already good chemical resistance of XNBR in non-polar fluids, such as toluene and gasoline, was further improved with a reduction of up to ~26% of the solvent uptake. A comprehensive study of the molecular dynamics was performed by means of broadband dielectric spectroscopy (BDS) to complete the existing knowledge on dual networks in XNBR. Such analysis showed that the synergistic behavior that prevails over purely ionic vulcanization networks is related to the restricted motions of rubber chain segments, as well as of the trapped chains within the ionic clusters that converts the vulcanizate into a stiffer and less solvent-penetrable material, improving abrasion resistance and chemical resistance, respectively. This combined network strategy will enable the production of elastomeric materials with improved performance and properties on demand. Full article
(This article belongs to the Special Issue Polymer Functionalization and Cross-Linking: Methodologies and Applications)
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16 pages, 4096 KiB  
Article
New Star-Shaped Polyether-Pentols (PEPOs) for Fabrication of Crosslinked Polyurethanes—Synthesis and Characterization
by Justyna Jurek-Suliga, Zbigniew Grobelny, Sylwia Golba, Hubert Okła and Katarzyna Bednarczyk
Polymers 2021, 13(13), 2150; https://doi.org/10.3390/polym13132150 - 29 Jun 2021
Viewed by 1692
Abstract
Polyether-pentols (PEPOs) were synthesized from glycidyl ethers and butylene oxide with the application of tripotassium salts of 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol (HMCH) activated 18C6 for ring-opening polymerization (ROP). The construction of the applied initiator system reflects the ability of crown ether to influence the degree of [...] Read more.
Polyether-pentols (PEPOs) were synthesized from glycidyl ethers and butylene oxide with the application of tripotassium salts of 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol (HMCH) activated 18C6 for ring-opening polymerization (ROP). The construction of the applied initiator system reflects the ability of crown ether to influence the degree of ion-pair separation with an increased activating effect. As a result formation of bi- or trimodal polymers was observed with molar masses in the range of (Mn = 1200–6000). The observed multi-fraction composition is prescribed to the formation of ionic aggregates with different reactivities during polymerization. The mechanism of the studied processes is discussed. The obtained PEPOs served for a crosslinked PUR synthesis, for which the hydrogen bond index for coupling of hard segments was calculated. Additionally, the range of phase separation was calculated that was higher for PUR-containing aromatic rings as the substituent. Full article
(This article belongs to the Special Issue Polymer Functionalization and Cross-Linking: Methodologies and Applications)
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