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Heterophase Polymerization and Functional Polymer Microspheres/Microcapsules
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Heterophase Polymerization and Functional Polymer Microspheres/Microcapsules

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: 30 November 2025 | Viewed by 4255

Special Issue Editors

Prof. Dr. Chengyou Kan

E-Mail Website1 Website2
Guest Editor
Institute of Polymer Materials Science & Engineering, Department of Chemical Engineering, Tsinghua University, Beijing, China
Interests: emulsion polymerization; polymer microspheres; silicone; waterborne system
Dr. Wei Deng

E-Mail Website
Guest Editor
School of Materials Science and Chemical Engineering, Harbin University of Science and Technology, Harbin, China
Interests: functional polymer microspheres; polymer nanocomposite; dielectrics for energy storage

Special Issue Information

Dear Colleagues,

Polymer microspheres are special materials with particle sizes ranging from nanometers to micrometers. Because their specific structure and morphology can provide them with unique functions that other materials do not have, polymer microspheres have been widely used in recent years, not only in traditional fields such as coatings, adhesives, and auxiliaries, but also in biomedicine, medical health, energy, environment, and other functional material fields.

There are many methods of preparing polymer microspheres, such as emulsion polymerization, mini-emulsion polymerization, dispersion polymerization, suspension polymerization, inverse emulsion polymerization, phase inversion emulsification techniques, etc. Microencapsulation is also one of the main methods of preparing polymer-based functional microspheres/ microcapsules. Different methods have different particle-forming mechanisms, and the resulting microspheres are also very different in size, performance, and application. To date, the precise control of the size and morphology of functional microspheres and the in-depth development of their applications have remained challenging. This issue will report the latest research progress in functional polymer microspheres/microcapsules from the aspects of synthesis, functionalization, characterization, properties, and applications. We believe that this Special Issue can inspire the development of functional polymer microspheres and benefit those involved in the field.

Prof. Dr. Chengyou Kan
Dr. Wei Deng
Guest Editors

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. Molecules 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

  • emulsion polymerization
  • mini emulsion polymerization
  • dispersion polymerization
  • suspension polymerization
  • encapsulation
  • functionalization
  • polymer microspheres
  • microcapsules
  • characterization
  • morphology control
  • structure–property relationship
  • polymer nanocomposite
  • application

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Published Papers (4 papers)

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Research

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14 pages, 109001 KiB  
Article
Construction and Regulation of Polymer@Silica Microspheres with Double-Shell Hollow Structures
by Mingxiu Jiang, Yuanyuan Yang, Jiawei Feng, Zhaopan Wang and Wei Deng
Molecules 2025, 30(4), 954; https://doi.org/10.3390/molecules30040954 - 18 Feb 2025
Viewed by 538
Abstract
Microspheres with well-defined hollow structures have been attracting interest due to their unique morphology and fascinating properties. Herein, a strategy for morphology and size control of hollow polymer@silica microspheres is proposed. Multilayer core–shell polymer microspheres, containing substantial carboxyl groups inside, evolve into microspheres [...] Read more.
Microspheres with well-defined hollow structures have been attracting interest due to their unique morphology and fascinating properties. Herein, a strategy for morphology and size control of hollow polymer@silica microspheres is proposed. Multilayer core–shell polymer microspheres, containing substantial carboxyl groups inside, evolve into microspheres with a 304 nm hollow structure after alkali treatment, which are used to construct hollow polymer@silica microspheres by coating the inorganic layer using the layer-by-layer (LBL) and sol–gel methods, respectively. The inorganic shell thickness of hollow polymer@silica microspheres can be adjusted from 15 nm to 33 nm by the self-assembled layers in the LBL method and from 15 nm to 63 nm by the dosage of precursor in the sol–gel method. Compared to the LBL method, the hollow polymer@silica microspheres prepared via the sol–gel method have a uniform and dense inorganic shell, thus ensuring the complete spherical morphology of the microspheres after calcination, even if the inorganic shell thickness is only 15 nm. Moreover, the hollow polymer@silica microspheres prepared via the sol–gel method exhibit improved compression resistance and good opacity, remaining intact at 16,000 psi and providing the corresponding coating with transmittance lower than 35.1%. This work highlights the morphology regulation of microspheres prepared by different methods and provides useful insights for the design of composites microspheres with controllable structures. Full article
(This article belongs to the Special Issue Heterophase Polymerization and Functional Polymer Microspheres/Microcapsules)
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14 pages, 6655 KiB  
Article
Fabrication of Polyurethane–Polyacrylate Hybrid Latexes with High Organosilicon Content via Phase Inversion Emulsion Polymerization
by Junhao Zhou, Furui Luo, Liming Tang and Zhaoxia Guo
Molecules 2024, 29(24), 5870; https://doi.org/10.3390/molecules29245870 (registering DOI) - 12 Dec 2024
Viewed by 884
Abstract
Waterborne polyurethane, with a mechanical strength comparable to solvent-based types, is eco-friendly and safe, using water as a dispersion medium. Polyacrylate excels in film formation and weather resistance but suffers from “hot stickiness and cold brittleness”. Merging polyurethane and polyacrylate creates advanced hybrids, [...] Read more.
Waterborne polyurethane, with a mechanical strength comparable to solvent-based types, is eco-friendly and safe, using water as a dispersion medium. Polyacrylate excels in film formation and weather resistance but suffers from “hot stickiness and cold brittleness”. Merging polyurethane and polyacrylate creates advanced hybrids, while organosilicon enhances properties but is restricted due to hydrolytic crosslinking. In this paper, a series of polyurethane–polyacrylate hybrid latexes with high organosilicon content were prepared using phase inversion emulsion polymerization technology. Even when the monomer content of 3-(methacryloyloxy)propyltrimethoxysilane (MPS) was increased to 10%, the polymerization process was stable, without the formation of a gel precipitate. The resulting latexes could remain stable for at least 6 months without significant changes in the properties of their films. The effects of MPS content on the mechanical and thermal properties of latex films were systematically researched. The study showed that with an increase in MPS dosage, the hardness and elastic modulus of the latex films increased, while the elongation at break and water absorption decreased, together with the increased glass transition temperature and surface hydrophilicity. This work aims to provide new theoretical guidance for the preparation of silicone-modified hybrid latexes, enabling their safe and stable production and storage. Full article
(This article belongs to the Special Issue Heterophase Polymerization and Functional Polymer Microspheres/Microcapsules)
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14 pages, 8360 KiB  
Article
Preparation of Double-Networked Slow-Expanding Nanomicrospheres and Evaluation of Drive Modulation Performance
by Qiaolin Zuo, Zhenzhong Fan, Qingwang Liu, Yuanfeng Fu, Luoqi Cui and Junfeng Yang
Molecules 2024, 29(22), 5378; https://doi.org/10.3390/molecules29225378 - 14 Nov 2024
Viewed by 731
Abstract
Aiming at the problem of excessive swelling of conventional microspheres for oilfield use, a novel amphiphilic polymerizable crosslinker (AE) was synthesized by quaternary ammonium modification of an unstable crosslinker (AE) using acrylamide, 2-acrylamido-2-methylpropanesulfonic acid as the monomers, N,N′-methylene bisacrylamide as the stabilizing crosslinker, [...] Read more.
Aiming at the problem of excessive swelling of conventional microspheres for oilfield use, a novel amphiphilic polymerizable crosslinker (AE) was synthesized by quaternary ammonium modification of an unstable crosslinker (AE) using acrylamide, 2-acrylamido-2-methylpropanesulfonic acid as the monomers, N,N′-methylene bisacrylamide as the stabilizing crosslinker, ammonium peroxysulfate and sodium bisulfite as the initiator, and water as the solvent by using a reversed microemulsion method. Double-networked nanomicrospheres were prepared. The preparation conditions of the microspheres were optimized by the surface response method, focusing on the effects of the initiator addition and reaction temperature, and total crosslinker addition on the formation of nanomicrospheres. The samples were characterized by FTIR, TGA, laser particle sizer, and SEM to evaluate the retarded expansion performance and the modulation drive performance. The results showed that the optimal conditions for the preparation of microspheres were m(oil phase):m(water phase) = 3:2, stirring speed of 550 r/min, total crosslinking agent dosage of 0.6% (based on the total mass of monomers, hereinafter the same), initiator dosage of 0.30%, reaction temperature of 45 °C, and reaction time of 4 h. Compared with the conventional polymer microsphere PAM, PAE was slow-expanded for 45 d at 60 °C, and the expansion multiplier was about 16 times, with slow-expansion characteristics; the blocking rate of PAE reached 98.3%, the oil repulsion rate was 73.11%, and the increase in the recovery rate could be up to 11.23%. In this paper, a new type of nanomicrosphere material is investigated to realize the efficient implementation of oil field conditioning and driving. Full article
(This article belongs to the Special Issue Heterophase Polymerization and Functional Polymer Microspheres/Microcapsules)
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Review

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29 pages, 6394 KiB  
Review
Preparation of Colored Polymer Microspheres
by Lei Wang, Weiting Ma, Shuheng Zhang, Mengke He, Ping Song, Hongying Wang, Xianxiao Song and Botian Li
Molecules 2025, 30(2), 375; https://doi.org/10.3390/molecules30020375 - 17 Jan 2025
Viewed by 1297
Abstract
Colored polymer microspheres have attracted significant attention in both academia and industry due to their unique optical properties and extensive application potential. However, achieving a uniform distribution of dyes within these microspheres remains a challenge, particularly when heavy concentrations of dye are used, [...] Read more.
Colored polymer microspheres have attracted significant attention in both academia and industry due to their unique optical properties and extensive application potential. However, achieving a uniform distribution of dyes within these microspheres remains a challenge, particularly when heavy concentrations of dye are used, as this can lead to aggregation or delamination, adversely affecting their application. Additionally, many dyes are prone to degradation or fading when exposed to light, heat, or chemicals, which compromises the long-term color stability of the microspheres. Consequently, the preparation of colored polymer microspheres with high stability continues to be a significant challenge. This review offers a comprehensive overview of the preparation techniques for colored polymer microspheres and their dyeing mechanisms, introducing the fundamental concepts of these microspheres and their applications in various fields, such as biomedicine, optical devices, and electronic display technologies. It further presents a detailed discussion of the different preparation methods, including physical adsorption, chemical bonding, and copolymerization. The advantages, limitations, and potential improvements of each method are explored, along with an analysis of the interactions between dyes and the polymer matrix, and how these interactions influence the properties of the microspheres, including their color uniformity, stability, and durability. Finally, the review discusses future perspectives on the development of colored polymer microspheres, highlighting the advancement of novel materials, innovations in preparation technology, and the exploration of potential new application areas. Full article
(This article belongs to the Special Issue Heterophase Polymerization and Functional Polymer Microspheres/Microcapsules)
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