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Advanced Polymer Materials: Synthesis, Structure, and Properties

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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: 31 July 2025 | Viewed by 8886

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Dr. Edina Rusen

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Faculty of Chemical Engineering and Biotechnologies, University of Bucharest, 1–7 Gh. Polizu Street, 011061 Bucharest, Romania
Interests: polymers; nanoparticles
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Special Issue Information

Dear Colleagues,

The present collection proposes to cover a large domain regarding the synthesis of polymer materials and the structure–properties correlation. The synthesis strategy could involve controlled radical polymerizations (CRP), ionic polymerization, polycondensation, radical polymerization, etc. The type of synthesis strategy influences the structure of the final polymers, which dictates the properties of the material. It is important to highlight the relationship between the synthesis strategy, structure, morphology, and properties. Obviously, the correlation could be made starting from the final properties of the polymers. Thus, considering these aspects, the structure can be deduced and associated with the synthesis strategy. Another important factor is the polymer synthesis technology, respectively, the processability, in attaining the desired applicability areas.

Reviews and research papers covering aspects of current trends in the development of polymer-based materials are desired.

Dr. Edina Rusen
Guest Editor

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Keywords

controlled radical polymerizations (CRP)
ionic polymerization
polycondensation
radical polymerization
Polymer structure and properties

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Published Papers (9 papers)

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Research

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24 pages, 3118 KiB

Open AccessArticle

Sago-Starch-Derived Sodium Starch Glycolate: An Effective Superdisintegrant to Enhance Formulation Performance

by Okta Nama Putra, Ida Musfiroh, Derina Paramitasari, Karjawan Pudjianto, Emmy Hainida Khairul Ikram, Chaidir Chaidir and Muchtaridi Muchtaridi

Polymers 2025, 17(9), 1208; https://doi.org/10.3390/polym17091208 - 28 Apr 2025

Viewed by 117

Abstract

This study focused on optimizing sago-starch-derived sodium starch glycolate (SSG) as a superdisintegrant using a Response Surface Methodology (RSM). The aim was to enhance the formulation performance by achieving an optimal degree of substitution (DS) in the synthesis of SSG from sago starch and evaluating its performance in mefenamic acid tablet formulation. The SSG was synthesized using an organic solvent slurry method, which involves crosslinking starch with sodium trimetaphosphate (STMP) and substituting it with sodium monochloroacetate (SMCA). The reaction conditions, including the temperature, SMCA ratio, and reaction time, were optimized using the RSM. The optimal conditions were identified as a temperature range of 45–55 °C, an SMCA ratio of 0.75–1.5, and a reaction time of 120–240 min. The maximum predicted DS value was 0.24, with a validated DS value of 0.246 ± 0.021. The SSG-containing mefenamic acid formulation met USP standards and showed a superior disintegration time compared to the existing SSG. The optimized SSG derived from sago starch can be effectively used as a superdisintegrant in pharmaceutical formulations, offering a sustainable and economically viable alternative source of SSG. This contributes to the development of more effective drug delivery systems and promotes sustainable agriculture in Indonesia. Full article

(This article belongs to the Special Issue Advanced Polymer Materials: Synthesis, Structure, and Properties)

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17 pages, 18798 KiB

Open AccessArticle

Molecular Entanglement Facilitated Improvement of Thermal Stability of Cellulose Diacetate

by Yang Liu, Yin Hu, Jianyu Chen, Zongkai Yan, Lin Zhao, Falu Zhan, Junjie Wang and Yagang Zhang

Polymers 2025, 17(7), 835; https://doi.org/10.3390/polym17070835 - 21 Mar 2025

Viewed by 300

Abstract

As a renewable and degradable biomass material, cellulose diacetate (CDA) has significant development potential and has gained widespread interest from researchers. However, its poor thermal stability at high temperatures limits its practical use in the extrusion process and restricts its applications in other fields, such as high-heat airflow filters, battery separators and special textile materials. To enhance the thermal stability of CDA, three heat-resistance additives, i.e., polyphenylene sulfide (PPS), polycarbonate (PC) and polyimide (PI), were introduced to synthesize PPS/CDA, PC/CDA and PI/CDA composite materials through melt extrusion. The incorporation of three heat-resistant additives increased the glass transition temperature (T_g), initial melting temperature (T_mⁱ) and final melting temperature (T_m^f) of the composites, and it reduced the heat loss at 195 °C. After conducting the isothermal thermogravimetry test for 3 h at 215 °C in an air atmosphere, the weight loss of PPS/CDA, PC/CDA and PI/CDA composites was 4.6%, 4.1% and 3.7%, respectively, which was 5.1% lower than that of pure CDA. Morphology characterization tests using a 3D digital microscope and a field emission scanning electron microscope (FESEM) revealed the compatibility order with CDA as the following: PC > PPS > PI. Additionally, Fourier transform infrared spectroscopy (FT–IR) disclosed that hydrogen bonds were formed between heat-resistant additives and CDA molecules, and the carbonyl groups in CDA showed conjugation and hyperconjugation effects with the benzene rings in the additives. Therefore, the enhanced thermal stability of CDA composites can be attributed to the molecular entanglement and crosslinking between additives and CDA molecules. Full article

(This article belongs to the Special Issue Advanced Polymer Materials: Synthesis, Structure, and Properties)

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17 pages, 2789 KiB

Open AccessArticle

Effects of Degassing Treatment on the Dielectric Properties of XLPE Insulation Used in High-Voltage DC Power Cables

by Man Ding, Qingfeng Zheng, Jiahe Wang, Weifeng He, Chao Dai and Dingjun Wen

Polymers 2025, 17(3), 431; https://doi.org/10.3390/polym17030431 - 6 Feb 2025

Cited by 1 | Viewed by 977

Abstract

Cross-linked polyethylene power cables are widely used in high-voltage DC transmission lines, owing to their good dielectric and physical–chemical properties. However, the production process of XLPE involves cross-linking and degassing, in which the cross-linking process produces a variety of cross-linking by-products, and the changes in the properties of the cable insulation caused by the degassing process are not well understood. XLPE samples were degassed at 90 °C for 7 and 14 days in this paper, and the main by-products were found to be α-methylstyrene, acetophenone, and cumyl alcohol, the contents of which all declined after the degassing treatment. The results show that the space charge density, the leakage current under a high electric field at different temperatures, and the breakdown strength of the XLPE samples all decreased after the degassing treatment. On the other hand, the XLPE sample after 7 days’ degassing had the lowest conductivity and the highest conductance activation, and the space charge density and the charge decay rate as well as the breakdown strength after 7 days’ degassing differed little from the 14-day treated sample, demonstrating that the 7-day degassing treatment at 90 °C would be enough to achieve superior performance. Full article

(This article belongs to the Special Issue Advanced Polymer Materials: Synthesis, Structure, and Properties)

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21 pages, 3502 KiB

Open AccessArticle

Study on the Characterization of Physical, Mechanical, and Creep Properties of Masson Pine and Chinese Fir Wood Flour-Reinforced High-Density Polyethylene Composites

by Hailong Xu, Xueshan Hua, Yan Cao, Lifen Li, Baoyu Liu, Xiaohui Yang and Hua Gao

Polymers 2024, 16(24), 3507; https://doi.org/10.3390/polym16243507 - 17 Dec 2024

Viewed by 707

Abstract

Improving the physical, mechanical, and creep properties of wood fiber-reinforced polymer composites is crucial for broadening their application prospect. In this research, seven types of high-density polyethylene (HDPE) composites reinforced with different mass ratios of Masson pine (Pinus massoniana Lamb.) and Chinese fir [Cunninghamia lanceolata (Lamb.) Hook.] were prepared by a two-step extrusion molding method. The mass ratios of the two fibers were 60:0, 50:10, 40:20, 30:30, 20:40, 10:50, and 0:60, respectively. The surface color, density, dimension stability, bending, tensile, impact properties, dynamic mechanical properties, and 24 h creep properties at a 10% stress level of the seven composites were investigated. Additionally, the Rule of Mixtures (ROM), the Inverse Rule of Mixtures (IROM), the Hirsch models, and the improved model were employed to simulate the mechanical properties, while the Findley index model, the two-parameter index model, and the modified ExpAssoc model were employed to simulate the creep performance of the composites. This study revealed that as the proportion of Chinese fir wood flour increased, the mechanical properties of the composites gradually improved, the storage modulus showed an increasing trend, while the loss modulus decreased, and the overall creep strain of the composites increased. Among the various models, the modified model simulated the mechanical properties of the composites the best, while the modified ExpAssoc model simulated the creep behavior most effectively. Full article

(This article belongs to the Special Issue Advanced Polymer Materials: Synthesis, Structure, and Properties)

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16 pages, 2512 KiB

Open AccessArticle

The Design of a Controlled-Release Polymer of a Phytopharmaceutical Agent: A Study on the Release in Different PH Environments Using the Ultrafiltration Technique

by Oscar G. Marambio, Alejandro Muñoz, Rudy Martin-Trasancos, Julio Sánchez and Guadalupe del C. Pizarro

Polymers 2024, 16(24), 3492; https://doi.org/10.3390/polym16243492 - 14 Dec 2024

Cited by 1 | Viewed by 869

Abstract

A series of hydrophilic copolymers were prepared using 2-hydroxyethyl methacrylate (HEMA) and itaconic acid (IA) from free radical polymerization at different feed monomer ratios using ammonium persulfate (APS) initiators in water at 70 °C. The herbicide 2,4-dichlorophenoxy acetic acid (2,4-D) was grafted to Poly(HEMA-co-IA) by a condensation reaction. The hydrolysis of the polymeric release system, Poly(HEMA-co-IA)-2,4-D, demonstrated that the release of the herbicide in an aqueous phase depends on the polymeric system’s pH value and hydrophilic character. In addition, the swelling behavior (Wt%) was studied at different pH values using Liquid-phase Polymer Retention (LPR) in an ultrafiltration system. The acid hydrolysis of the herbicide from the conjugates follows a first-order kinetic, showing higher kinetic constants as the pH increases. The base-catalyzed hydrolysis reaction of the herbicide follows a zero-order kinetic, where the basic medium acts as a catalyst, accelerating the release rate of the herbicide and showing higher kinetic constants as the pH increases. The differences in the release rates found for the hydrogel herbicide at different pH values can be correlated with the difference in their swelling capacity, where the release rate generally increases with an increase in the swelling capacity from water solution at higher pH values. The study of the release process revealed that all samples in distilled water at a pH of 10 are representative of agricultural systems. It showed first-order swelling kinetics and an absorption capacity that conforms to the parameters for hydrogels for agricultural applications, which supports their potential for these purposes. Full article

(This article belongs to the Special Issue Advanced Polymer Materials: Synthesis, Structure, and Properties)

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22 pages, 19199 KiB

Open AccessArticle

Impact of Hexyl Branch Content on the Mechanical Properties and Deformation Mechanisms of Amorphous Ethylene/1-Octene Copolymers: A Molecular Dynamics Study

by Ruijun Zhang, Qiqi He, Hongbo Yu, Junhua Li, Yuexin Hu and Jianhua Qian

Polymers 2024, 16(23), 3236; https://doi.org/10.3390/polym16233236 - 21 Nov 2024

Viewed by 931

Abstract

Ethylene/1-octene copolymers exhibit enhanced flexibility and impact resistance compared to polyethylene, which makes them well suited for applications in advanced plastics and elastomers. United-atom molecular dynamics (MD) simulations were conducted to explore the mechanical behavior and deformation mechanisms of ethylene/1-octene copolymers under uniaxial tensile loading. This study systematically examined the influence of temperature, polymer chain length, chain quantity, and strain rate, with a specific focus on how hexyl branch content impacts the mechanical properties of amorphous ethylene/1-octene copolymers. The simulation results indicate that as the branch content increases, the yield strength and elastic modulus decrease, suggesting a trade-off between flexibility and mechanical strength. Energy decomposition analysis reveals that copolymers with more branched chains undergo greater changes in van der Waals energy. Additionally, as the branch content increases, the reduction in dihedral angle energy in the strain hardening region becomes more gradual, and the rate and the extent of the transition of dihedral angles from gauche to trans conformation decrease under deformation. Ethylene/1-octene copolymers exhibit higher chain entanglement parameters compared to linear polyethylene, with these parameters increasing as the branch content rises. Moreover, increasing the branch content results in a less pronounced increase in chain orientation along the loading direction. Full article

(This article belongs to the Special Issue Advanced Polymer Materials: Synthesis, Structure, and Properties)

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21 pages, 6481 KiB

Open AccessArticle

In Situ Formation of Acidic Comonomer during Thermal Treatment of Copolymers of Acrylonitrile and Its Influence on the Cyclization Reaction

by Roman V. Toms, Daniil A. Ismaylov, Alexander Yu. Gervald, Nickolay I. Prokopov, Anna V. Plutalova and Elena V. Chernikova

Polymers 2024, 16(19), 2833; https://doi.org/10.3390/polym16192833 - 7 Oct 2024

Viewed by 1166

Abstract

Binary and ternary copolymers of acrylonitrile (AN), tert-butyl acrylate (TBA), and n-butyl acrylate (BA) are synthesized through conventional radical polymerization in DMSO in the presence of 2-mercaptoethanol. The thermal behavior of binary and ternary copolymers is studied under argon atmosphere and in air. It is demonstrated that the copolymers of AN contain 1–10 mol.% of TBA split isobutylene upon heating above 160 °C, resulting in the formation of the units of acrylic acid in the chain. The carboxylic groups formed in situ are responsible for the ionic mechanism of cyclization, which starts at lower temperatures compared with pure polyacrylonitrile (PAN) or AN copolymer with BA. The activation energy of cyclization through ionic and radical mechanisms depends on copolymer composition. For the ionic mechanism, the activation energy lies in the range ca. 100–130 kJ/mole, while for the radical mechanism, it lies in the range ca. 150–190 kJ/mole. The increase in the TBA molar part in the copolymer is followed by faster consumption of nitrile groups and the evolution of a ladder structure in both binary and ternary copolymers. Thus, the incorporation of a certain amount of TBA in PAN or its copolymer with BA allows tuning the temperature range of cyclization. This feature seems attractive for applications in the production of melt-spun PAN by choosing the appropriate copolymer composition and heating mode. Full article

(This article belongs to the Special Issue Advanced Polymer Materials: Synthesis, Structure, and Properties)

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23 pages, 16371 KiB

Open AccessArticle

Experimental Investigations on Shear Thickening Fluids as “Liquid Body Armors”: Non-Conventional Formulations for Ballistic Protection

by Florentina Alexe, Ciprian Sau, Ovidiu Iorga, Gabriela Toader, Aurel Diacon, Edina Rusen, Claudiu Lazaroaie, Raluca Elena Ginghina, Tudor Viorel Tiganescu, Mircea Teodorescu and Arcadie Sobetkii

Polymers 2024, 16(16), 2305; https://doi.org/10.3390/polym16162305 - 15 Aug 2024

Cited by 2 | Viewed by 2669

Abstract

Shear thickening fluids (STFs) have garnered attention as potential enhancers of protective capabilities and for the optimization of Kevlar^® armor design. To assess the possible shear thickening properties and potential application in ballistic protection, ten formulations were developed by employing polyethylene glycol (PEG) or polypropylene glycol (PPG), along with fumed silica or Aerosil HDK^®. Rheological characterization facilitated the identification of formulations displaying shear thickening behavior. The potential integration of the selected shear thickening fluids (STFs) into Kevlar^®-based composites was investigated by studying the impact resistance of Kevlar^® soft armor structures. Also, high-velocity impact testing revealed that the distance between aramid layers plays a crucial role in the impact resistance effectiveness of Kevlar^®–STF composite structures and that there is a very narrow domain between optimal and undesired scenarios in which STF could facilitate the penetration of Kevlar. The introduction of STF between the Kevlar sheets disrupted this packing and the energy absorption capacity of the material was not improved. Only one formulation (PEG400, Aerosil 27 wt.%) led to a less profound traumatic imprint and stopped the bullet when it was placed between layers no.1 and no.2 from a total of 11 layers of Kevlar XP. These experimental findings align with the modeling and simulation of Kevlar^®–STF composites using Ansys simulation software (Ansys® AutoDyn 2022 R2). Full article

(This article belongs to the Special Issue Advanced Polymer Materials: Synthesis, Structure, and Properties)

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Review

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30 pages, 34143 KiB

Open AccessReview

Incorporation of Carbocyclic Moieties into Polymer Structure: A Powerful Way to Polymers with Increased Microporosity

by Maxim A. Zotkin, Kirill V. Zaitsev and Dmitry A. Alentiev

Polymers 2025, 17(8), 1100; https://doi.org/10.3390/polym17081100 - 18 Apr 2025

Viewed by 253

Abstract

Microporous soluble polymers attract great attention as materials for membrane gas separation, gas storage and transportation, as sorbents, supports for catalysts, and matrices for mixed matrix membranes. The key problems in the development of this area of polymer chemistry include the search for methods of controlling the porous structure parameters and ensuring the stability of their properties over time. In this connection, a fruitful approach is to introduce bulky and rigid, often framework carbocyclic moieties into the polymer backbones and side chains. This review discusses the effect of carbocyclic moieties on gas transport properties, BET surface area, and FFV of glassy polymers, such as polyacetylenes, polynorbornenes, polyimides, and ladder and partially ladder polymers. In the majority of cases, the incorporation of carbocyclic moieties makes it possible to controllably increase these three parameters. Carbocyclic moieties can also improve CO₂/gas separation selectivity, which is displayed for ladder polymers and polynorbornenes. Full article

(This article belongs to the Special Issue Advanced Polymer Materials: Synthesis, Structure, and Properties)

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