Polymers of the Future

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

Deadline for manuscript submissions: closed (20 September 2023) | Viewed by 13100

Special Issue Editor


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Guest Editor
A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 28 Vavilova St., GSP-1, V-334, 119991 Moscow, Russia
Interests: new polymeric forms; structure–properties relationship; supramolecular organization; organosilicon compounds; hybrid organic-inorganic structures; active media concept; organoalkoxysilanes; chlorine-free technology; functional metallosiloxanes; dendrimers; hyperbranched polymers; highly crosslinked nanogels; multiarm stars; macromolecular brushes
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Special Issue Information

Dear Colleagues,

The 100 year anniversary of the renowned Hermann Staudinger’s discovery of the chain structure of polymers was recently celebrated, drawing attention to the ever-growing importance of this phenomenon—one that was not the beginning of polymers as such, but rather paved the way to their study. The key conclusion of this process spanning more than 100 years is the realization that life on Earth is polymeric, and the most important planetary processes (e.g., the circular flow of carbon and oxygen) happens primarily using polymeric matter.

On such a grand scale, the achievements of polymer science in the development of new polymer systems may not look overly impressive. This is despite the fact that artificial and synthetic polymers have completely changed our lives—indeed, we can no longer imagine living without all-season fruits and vegetables; easily available electricity, from vacuum cleaners to electric kettles; advancements in medicine; modern construction work; and transport, from spaceships to electric scooters.

The present-day human society takes these achievements for granted and has no desire to thank the scientists for them. On the contrary, society reproaches us for polymer waste that has filled our seas and oceans as wandering islands, poisoning sea life. This waste is not an inevitable byproduct of polymer science progress, but rather a reflection of this very society’s level of self-organization as well as its readiness to use the benefits of polymers and polymer technologies smartly and responsibly.

Society is beginning to tackle the problem of polymer waste by barring the use of polymers in some applications and returning to traditional materials such as paper, glass, and metal, not realizing that paper and some glasses are polymer materials and that the manufacture of these materials as well as metals is far more damaging to the environment than polymers.

The polymer community is trying to adapt to the demands of an insufficiently educated lay society and to substitute “bad” polymers for “good” ones. However, there are no criteria for measuring a polymer’s “goodness,” and those that one may have heard of are still liable to be proven false. For example, the biodegradable systems craze does not guarantee the solution of the polymer waste problem, as it creates new ones that are just as complex and potentially more dangerous. This raises the question, what should polymers of the future be?

Obviously, while seeking an answer to that question, we are not ready to denounce any of the huge variety of polymers created by the talent of numerous generations of scientists, engineers, and workers of the gargantuan polymer industry. That said, we must bring the existing polymers to such a state that they will no longer present any danger to the environment. It is also clear that we cannot wait until society catches up to the level of consciousness required to use polymers responsibly.

The idea for this Special Issue is quite simple yet important. I am inviting experts from different areas of polymer science to share their ideas regarding approaches to resolving the global issue of the safe development of polymers, polymer materials, and polymer technologies as an alternative to ineffective and energy-intensive methods that are currently in use in various countries, as none of them bring us any closer to finding a global-scale resolution of the problem. I welcome the submission of articles on original approaches to designing new systems that decrease the expenses in every stage of a polymer’s life cycle, from the synthesis of monomers to all phases of recycling, to the finishing point where materials are safely disposed of. Submissions could include overviews with constructive criticism of current polymer synthesis and recycling technologies or highlights suggesting new original approaches to all stages of a polymer’s life cycle that require a concerted effort from the scientific and engineering communities to bring them to life.

Prof. Dr. Aziz Mansurovich Muzafarov
Guest Editor

Manuscript Submission Information

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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 materials
  • eco-friendly polymer
  • polymer technologies
  • polymer’s life cycle
  • polymer synthesis
  • polymer degradation
  • polymer applications

Published Papers (8 papers)

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Research

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16 pages, 8475 KiB  
Article
Structure and Mechanical Response of Polybutylcarbosilane Dendrimers Confined in a Flat Slit: Effect of Molecular Architecture and Generation Number
by Andrey O. Kurbatov, Nikolay K. Balabaev, Kirill A. Litvin and Elena Yu. Kramarenko
Polymers 2023, 15(20), 4040; https://doi.org/10.3390/polym15204040 - 10 Oct 2023
Viewed by 697
Abstract
Due to the absence of specific interactions, carbosilane dendrimers are ideal models to study the effect of a hyperbranched regular structure on the molecular response to external influences. In this work, we have studied the conformational behavior of single polybutylcarbosilane dendrimers under confinement [...] Read more.
Due to the absence of specific interactions, carbosilane dendrimers are ideal models to study the effect of a hyperbranched regular structure on the molecular response to external influences. In this work, we have studied the conformational behavior of single polybutylcarbosilane dendrimers under confinement between impermeable flat surfaces using atomistic molecular dynamics simulations. Dendrimers of different generations belonging to two homologous series with a tetra-functional core and three- and four-functional branches were simulated. The analysis of the dependence of the internal energy of the dendrimers on the wall distance allowed us to determine the critical degree of compression at which the dendrimers are able to change their shape without energy loss. The effects of generation number and branching functionality on the number of wall contacts, density distribution and shape changes were elucidated. It was found that for high generation dendrimers, the inner layers are not accessible for external interaction. It was shown that the excess stresses occurring at high compressions are concentrated in the structural center of the dendrimer. The nature of the elastic response, which is strongly nonlinear, was analyzed at different compressions depending on the dendrimer architecture and generation. We believe that our results are useful for further studies of dendrimer films under compression and can also serve as a basis for developing model concepts to describe the dynamics of dendrimer melts. Full article
(This article belongs to the Special Issue Polymers of the Future)
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13 pages, 7142 KiB  
Article
The Relationships between the Structure and Properties of PA56 and PA66 and Their Fibers
by Keming Luo, Jiaxin Liu, Kieth Abbay, Yangjie Mei, Xiaowei Guo, Yunhe Song, Qingbao Guan and Zhengwei You
Polymers 2023, 15(13), 2877; https://doi.org/10.3390/polym15132877 - 29 Jun 2023
Cited by 1 | Viewed by 1561
Abstract
Bio-based polymers can reduce dependence on nonrenewable petrochemical resources and will be beneficial for future sustainable developments due to their low carbon footprint. In this work, the feasibility of bio-based polyamide 56 (PA56) substituting petroleum-based PA66 is systematically investigated. The crystallization, melting, and [...] Read more.
Bio-based polymers can reduce dependence on nonrenewable petrochemical resources and will be beneficial for future sustainable developments due to their low carbon footprint. In this work, the feasibility of bio-based polyamide 56 (PA56) substituting petroleum-based PA66 is systematically investigated. The crystallization, melting, and decomposition temperature of PA56 were all lower than that of PA66. PA56 formed a γ crystal type with larger grain size and took a longer amount of time to complete the crystallization process since its crystallization rate was lower than that of PA66. Compared with PA66, PA56 exhibited a higher tensile strength of 71.3 ± 1.9 MPa and specific strength of 64.8 ± 2.0 MPa but lower notched impact strength. More importantly, the limited oxygen index and vertical combustion measurement results indicated that the flame retardancy of PA56 was better than PA66, and the LOI values and the UL94 result of PA56 were 27.6% ± 0.9% and V-2. It is worth noting that the PA56 fiber had superior biodegradability compared to the PA66 fiber. PA56 showed significant biodegradation from the eighth week, whereas PA66 remained clean until the sixteenth week (without obvious biodegradation taking place). Eventually, PA56 did not show significant differences compared to PA66 in terms of thermal and mechanical properties. However, PA56 had great advantages in flame retardancy and biodegradability, indicating that the bio-based PA56 could potentially replace petroleum-based PA66 in many fields. Full article
(This article belongs to the Special Issue Polymers of the Future)
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12 pages, 2084 KiB  
Article
Polar-Functionalized Polyethylenes Enabled by Palladium-Catalyzed Copolymerization of Ethylene and Butadiene/Bio-Based Alcohol-Derived Monomers
by Yanlin Zong, Chaoqun Wang, Yixin Zhang and Zhongbao Jian
Polymers 2023, 15(4), 1044; https://doi.org/10.3390/polym15041044 - 19 Feb 2023
Cited by 3 | Viewed by 1793
Abstract
Polar-functionalized polyolefins are high-value materials with improved properties. However, their feedstocks generally come from non-renewable fossil products; thus, it requires the development of renewable bio-based monomers to produce functionalized polyolefins. In this contribution, via the Pd-catalyzed telomerization of 1,3-butadiene and three types of [...] Read more.
Polar-functionalized polyolefins are high-value materials with improved properties. However, their feedstocks generally come from non-renewable fossil products; thus, it requires the development of renewable bio-based monomers to produce functionalized polyolefins. In this contribution, via the Pd-catalyzed telomerization of 1,3-butadiene and three types of bio-based alcohols (furfuryl alcohol, tetrahydrofurfuryl alcohol, and solketal), 2,7-octadienyl ether monomers including OC8-FUR, OC8-THF, and OC8-SOL were synthesized and characterized, respectively. The copolymerization of these monomers with ethylene catalyzed by phosphine–sulfonate palladium catalysts was further investigated. Microstructures of the resultant copolymers were analyzed by NMR and ATR-IR spectroscopy, revealing linear structures with incorporations of difunctionalized side chains bearing both allyl ether units and polar cyclic groups. Mechanical property studies exhibited better strain-at-break of these copolymers compared to the non-polar polyethylene, among which the copolymer E-FUR with the incorporation of 0.3 mol% displayed the highest strain-at-break and stress-at-break values of 940% and 35.9 MPa, respectively. Full article
(This article belongs to the Special Issue Polymers of the Future)
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13 pages, 5279 KiB  
Article
Chains Stiffness Effect on the Vertical Segregation of Mixed Polymer Brushes in Selective Solvent
by Ivan V. Lukiev, Yana A. Mogelnitskaya, Ivan V. Mikhailov and Anatoly A. Darinskii
Polymers 2023, 15(3), 644; https://doi.org/10.3390/polym15030644 - 27 Jan 2023
Cited by 2 | Viewed by 1279
Abstract
The microstructure of the binary polymer brushes in the selective solvent was studied using the numerical lattice self-consisting field approach. The case was considered when the selectivity to the solvent (the Flory–Huggins parameter χ) was varied only for one type of chains [...] Read more.
The microstructure of the binary polymer brushes in the selective solvent was studied using the numerical lattice self-consisting field approach. The case was considered when the selectivity to the solvent (the Flory–Huggins parameter χ) was varied only for one type of chains (responsive chains) while the others (non-responsive chains) remained hydrophilic (χ = 0). In such a brush, with an increase in the hydrophobicity of the responsive chains, a transition occurs between two two-layer microstructures. In the initial state the ends of the longer responsive chains are located near the external surface of the brush and those of non-responsive chains are inside the brush. When the hydrophobicity of the responsive chains becomes high enough then the reversed two-layer microstructure is formed, when the ends of non-responsive chains are located near the brush surface and the responsive chains collapse on the brush bottom. In contrast to previous works, the stiffness parameter (Kuhn segment length p) for one or for both types of chains was varied and its effect on the mechanism and characteristics of the transition was studied. If the stiffness of only responsive chains increases, then the transition occurs with the formation of an intermediate three-layer microstructure, where a layer of responsive chains is located between layers formed by non-responsive ones. If both types of chains have the same p, then the transition occurs gradually without the formation of an intermediate three-layer microstructure. For both cases, the effect of p on the critical value of χ*, corresponding to the transition point and on the steepness of the transition was investigated. Full article
(This article belongs to the Special Issue Polymers of the Future)
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16 pages, 18243 KiB  
Article
True Molecular Composites: Unusual Structure and Properties of PDMS-MQ Resin Blends
by Artem V. Bakirov, Sergey V. Krasheninnikov, Maxim A. Shcherbina, Ivan B. Meshkov, Aleksandra A. Kalinina, Vadim V. Gorodov, Elena A. Tatarinova, Aziz M. Muzafarov and Sergey N. Chvalun
Polymers 2023, 15(1), 48; https://doi.org/10.3390/polym15010048 - 22 Dec 2022
Cited by 4 | Viewed by 1756
Abstract
Poly(dimethyl siloxane)-MQ rubber molecular composites are easy to prepare, as it does not require a heterophase mixing of ingredients. They are characterized by perfect homogeneity, so they are very promising as rubber materials with controllable functional characteristics. The manuscript reveals that MQ resin [...] Read more.
Poly(dimethyl siloxane)-MQ rubber molecular composites are easy to prepare, as it does not require a heterophase mixing of ingredients. They are characterized by perfect homogeneity, so they are very promising as rubber materials with controllable functional characteristics. The manuscript reveals that MQ resin particles can significantly, more than by two orders of magnitude, enhance the mechanical properties of poly(dimethyl siloxane), and, as fillers, they are not inferior to aerosils. In the produced materials, MQ particles play a role of the molecular entanglements, so rubber molecular weight and MQ filler concentration are the parameters determining the structure and properties of such composites. Moreover, a need for a saturation of the reactive groups and minimization of the surface energy of MQ particles also determine the size and distribution of the filler at different filler rates. An unusual correlation of the concentration of MQ component and the interparticle spacing was revealed. Based on the extraordinary mechanical properties and structure features, a model of the structure poly(dimethyl siloxane)-rubber molecular composites and of its evolution in the process of stretching, was proposed. Full article
(This article belongs to the Special Issue Polymers of the Future)
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17 pages, 3315 KiB  
Article
Salt-Induced Transformations of Hybrid Micelles Formed by Anionic Surfactant and Poly(4-vinylpyridine)
by Alexander L. Kwiatkowski, Vyacheslav S. Molchanov, Alexander I. Kuklin, Yuri M. Chesnokov and Olga E. Philippova
Polymers 2022, 14(23), 5086; https://doi.org/10.3390/polym14235086 - 23 Nov 2022
Cited by 2 | Viewed by 1536
Abstract
Salt-induced structural transformation of charged hybrid surfactant/polymer micelles formed by potassium oleate and poly(4-vinylpyridine) was investigated by cryo-TEM, SANS with contrast variation, DLS, and 2D NOESY. Cryo-TEM data show, that at small salt concentration beads-on-string aggregates on polymer chains are formed. KCl induces [...] Read more.
Salt-induced structural transformation of charged hybrid surfactant/polymer micelles formed by potassium oleate and poly(4-vinylpyridine) was investigated by cryo-TEM, SANS with contrast variation, DLS, and 2D NOESY. Cryo-TEM data show, that at small salt concentration beads-on-string aggregates on polymer chains are formed. KCl induces the transformation of those aggregates into rods, which is due to the screening of the electrostatic repulsion between similarly charged beads by added salt. In a certain range of salt concentration, the beads-on-string aggregates coexist with the rodlike ones. In the presence of polymer, the sphere-to-rod transition occurs at higher salt concentration than in pure surfactant system indicating that hydrophobic polymer favors the spherical packing of potassium oleate molecules. The size of micelles was estimated by DLS. The rods that are formed in the hybrid system are much shorter than those in polymer-free surfactant solution suggesting the stabilization of the semi-spherical endcaps of the rods by embedded polymer. 2D NOESY data evidence that in the spherical aggregates the polymer penetrates deep into the core, whereas in tighter packed rodlike aggregates it is located mainly at core/corona interface. According to SANS with contrast variation, inside the rodlike aggregates the polymer adopts more compact coil conformation than in the beads-on-string aggregates. Such adaptive self-assembled polymer-surfactant nanoparticles with water-insoluble polymer are very promising for various applications including drag reduction at transportation of fluids. Full article
(This article belongs to the Special Issue Polymers of the Future)
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Review

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18 pages, 5379 KiB  
Review
New Approaches to the Synthesis and Stabilization of Polymer Microspheres with a Narrow Size Distribution
by Inessa A. Gritskova, Nikolay I. Prokopov, Anna A. Ezhova, Anatoly E. Chalykh, Sergey A. Gusev, Sergey M. Levachev, Vitaly P. Zubov, Vitaly I. Gomzyak, Ivan V. Skopintsev, Alexander N. Stuzhuk, Ivan D. Kovtun, Anton M. Shulgin, Dmitry S. Ivashkevich, German A. Romanenko, Valentin G. Lakhtin and Sergei N. Chvalun
Polymers 2023, 15(11), 2464; https://doi.org/10.3390/polym15112464 - 26 May 2023
Cited by 1 | Viewed by 1235
Abstract
This article presents the results of investigations on heterophase polymerization of vinyl monomers in the presence of organosilicon compounds of different structures. On the basis of the detailed study of the kinetic and topochemical regularities of the heterophase polymerization of vinyl monomers, the [...] Read more.
This article presents the results of investigations on heterophase polymerization of vinyl monomers in the presence of organosilicon compounds of different structures. On the basis of the detailed study of the kinetic and topochemical regularities of the heterophase polymerization of vinyl monomers, the conditions for the synthesis of polymer suspensions with a narrow particle-size distribution using a one-step method have been determined. Full article
(This article belongs to the Special Issue Polymers of the Future)
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17 pages, 1099 KiB  
Review
Chemical Recycling of High-Molecular-Weight Organosilicon Compounds in Supercritical Fluids
by Igor V. Elmanovich, Victor E. Sizov, Vadim V. Zefirov, Alexandra A. Kalinina, Marat O. Gallyamov, Vladimir S. Papkov and Aziz M. Muzafarov
Polymers 2022, 14(23), 5170; https://doi.org/10.3390/polym14235170 - 28 Nov 2022
Cited by 2 | Viewed by 2009
Abstract
The main known patterns of thermal and/or catalytic destruction of high-molecular-weight organosilicon compounds are considered from the viewpoint of the prospects for processing their wastes. The advantages of using supercritical fluids in plastic recycling are outlined. They are related to a high diffusion [...] Read more.
The main known patterns of thermal and/or catalytic destruction of high-molecular-weight organosilicon compounds are considered from the viewpoint of the prospects for processing their wastes. The advantages of using supercritical fluids in plastic recycling are outlined. They are related to a high diffusion rate, efficient extraction of degradation products, the dependence of solvent properties on pressure and temperature, etc. A promising area for further research is described concerning the application of supercritical fluids for processing the wastes of organosilicon macromolecular compounds. Full article
(This article belongs to the Special Issue Polymers of the Future)
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