Special Issue "Microporous Organic Polymers: Synthesis, Characterization and Applications"

A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: closed (25 November 2018).

Special Issue Editors

Dr. Mariolino Carta
E-Mail Website
Guest Editor
Department of Chemistry, Swansea University, Singleton Park, Swansea SA2 8PP, UK
Interests: organic chemistry; material chemistry; polymers of intrinsic microporosity; gas separation
Dr. Johannes Carolus (John) Jansen
E-Mail Website1 Website2
Guest Editor
Institute on Membrane Technology, ITM-CNR, Via P. Bucci, Cubo 17/C, 87036 Rende (CS), Italy
Interests: polymeric and hybrid membranes for gas and vapour separation; principles of gas and vapour transport in membranes by sorption and permeation experiments; structural, mechanical and thermal properties of polymers, polymer blends and hybrid materials; membrane preparation by phase inversion techniques; polymers of intrinsic microporosity; perfluoropolymers; ionic liquids; carbon dioxide capture
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Special Issue Information

Dear Colleagues,

Microporous organic polymers represent a rapidly-expanding class of amorphous porous materials, composed of fully covalently bound organic building blocks. Depending on the appropriate choice of monomers, functionality and polymerisation method, they can be prepared both as solution processable or as insoluble networked materials. Typical features of microporous organic polymers are pore diameters of less than 2 nm, high internal surface areas and elevated thermal stability, which allow them to be exploited for a broad range of technologically important applications, such as gas storage and separation, heterogeneous catalysis, sensors and electrochemistry, just to name a few.

This Special Issue of Polymers aims to report full research papers, communications and review articles based on the latest advances in the field of synthesis, characterisation and applications of organic microporous polymers. Fields that will be covered are, but are not limited to:

  • Synthesis (Polymers of intrinsic microporosity, thermally rearrangeable polymers, porous organic networks)
  • Structural characterization
  • Modelling
  • Applications (i.e., gas sorption and storage, gas permeation, catalysis, heavy metal sorption, energy storage)

Dr. Mariolino Carta
Dr. Johannes Carolus Jansen
Guest Editors

Manuscript Submission Information

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 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

  • Microporous polymers
  • Polymer synthesis
  • Gas sorption and storage
  • Gas separation membranes
  • High Surface Area
  • Internal free volume
  • Carbon capture
  • Heterogeneous catalysis
  • Liquid phase sorption
  • Modelling

Published Papers (12 papers)

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Editorial

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Open AccessEditorial
Microporous Organic Polymers: Synthesis, Characterization, and Applications
Polymers 2019, 11(5), 844; https://doi.org/10.3390/polym11050844 - 10 May 2019
Cited by 1
Abstract
The presence of a certain degree of porosity in polymers is a feature that provides them with unique properties and with opportunities to be exploited in a number of technologically important applications [...] Full article

Research

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Open AccessArticle
Polyvinylnorbornene Gas Separation Membranes
Polymers 2019, 11(4), 704; https://doi.org/10.3390/polym11040704 - 17 Apr 2019
Cited by 3
Abstract
Polynorbornenes are already used in a wide range of applications. They are also considered materials for polymer gas separation membranes because of their favorable thermal and chemical resistance, rigid backbone and varied chemistry. In this study, the use of 5-vinyl-2-norbornene (VNB), a new [...] Read more.
Polynorbornenes are already used in a wide range of applications. They are also considered materials for polymer gas separation membranes because of their favorable thermal and chemical resistance, rigid backbone and varied chemistry. In this study, the use of 5-vinyl-2-norbornene (VNB), a new monomer in the field of gas separations, is investigated by synthesizing two series of polymers via a vinyl-addition polymerization. The first series investigates the influence of the VNB content on gas separation in a series of homo and copolymers with norbornene. The second series explores the influence of the crosslinking of polyvinylnorbornene (pVNB) on gas separation. The results indicate that while crosslinking had little effect, the gas separation performance could be fine-tuned by controlling the VNB content. As such, this work demonstrates an interesting way to significantly extend the fine-tuning possibilities of polynorbornenes for gas separations. Full article
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Open AccessArticle
Synthesis and Gas-Permeation Characterization of a Novel High-Surface Area Polyamide Derived from 1,3,6,8-Tetramethyl-2,7-diaminotriptycene: Towards Polyamides of Intrinsic Microporosity (PIM-PAs)
Polymers 2019, 11(2), 361; https://doi.org/10.3390/polym11020361 - 19 Feb 2019
Cited by 2
Abstract
A triptycene-based diamine, 1,3,6,8-tetramethyl-2,7-diamino-triptycene (TMDAT), was used for the synthesis of a novel solution-processable polyamide obtained via polycondensation reaction with 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) (6FBBA). Molecular simulations confirmed that the tetrasubstitution with ortho-methyl groups in the triptycene building block reduced rotations around the C–N [...] Read more.
A triptycene-based diamine, 1,3,6,8-tetramethyl-2,7-diamino-triptycene (TMDAT), was used for the synthesis of a novel solution-processable polyamide obtained via polycondensation reaction with 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) (6FBBA). Molecular simulations confirmed that the tetrasubstitution with ortho-methyl groups in the triptycene building block reduced rotations around the C–N bond of the amide group leading to enhanced fractional free volume. Based on N2 sorption at 77 K, 6FBBA-TMDAT revealed microporosity with a Brunauer–Emmett–Teller (BET) surface area of 396 m2 g−1; to date, this is the highest value reported for a linear polyamide. The aged 6FBBA-TMDAT sample showed moderate pure-gas permeabilities (e.g., 198 barrer for H2, ~109 for CO2, and ~25 for O2) and permselectivities (e.g., αH2/CH4 of ~50) that position this polyamide close to the 2008 H2/CH4 and H2/N2 upper bounds. CO2–CH4 mixed-gas permeability experiments at 35 °C demonstrated poor plasticization resistance; mixed-gas permselectivity negatively deviated from the pure-gas values likely, due to the enhancement of CH4 diffusion induced by mixing effects. Full article
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Open AccessArticle
Preparation of Porous Polymeric Membranes Based on a Pyridine Containing Aromatic Polyether Sulfone
Polymers 2019, 11(1), 59; https://doi.org/10.3390/polym11010059 - 02 Jan 2019
Cited by 1
Abstract
Polymeric membranes, based on a polysulfone-type aromatic polyether matrix, were successfully developed via the non-solvent induced phase separation (NIPS) method. The polyethersulfone type polymer poly[2-(4-(diphenylsulfonyl)-phenoxy)-6-(4-phenoxy) pyridine] (PDSPP) was used as the membrane matrix, and mixed with its sulfonated derivative (SPDSPP) and a polymeric [...] Read more.
Polymeric membranes, based on a polysulfone-type aromatic polyether matrix, were successfully developed via the non-solvent induced phase separation (NIPS) method. The polyethersulfone type polymer poly[2-(4-(diphenylsulfonyl)-phenoxy)-6-(4-phenoxy) pyridine] (PDSPP) was used as the membrane matrix, and mixed with its sulfonated derivative (SPDSPP) and a polymeric porogen. The SPDPPP was added to impart hydrophilicity, while at the same time maintaining the interactions with the non-sulfonated aromatic polyether forming the membrane matrix. Different techniques were used for the membranes’ properties characterization. The results revealed that the use of the non-sulfonated and sulfonated polymers of the same polymeric backbone, at certain compositions, can lead to membranes with controllable porosity and hydrophilicity. Full article
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Open AccessArticle
Highly Permeable Matrimid®/PIM-EA(H2)-TB Blend Membrane for Gas Separation
Polymers 2019, 11(1), 46; https://doi.org/10.3390/polym11010046 - 30 Dec 2018
Cited by 2
Abstract
The effect on the gas transport properties of Matrimid®5218 of blending with the polymer of intrinsic microporosity PIM-EA(H2)-TB was studied by pure and mixed gas permeation measurements. Membranes of the two neat polymers and their 50/50 wt % blend [...] Read more.
The effect on the gas transport properties of Matrimid®5218 of blending with the polymer of intrinsic microporosity PIM-EA(H2)-TB was studied by pure and mixed gas permeation measurements. Membranes of the two neat polymers and their 50/50 wt % blend were prepared by solution casting from a dilute solution in dichloromethane. The pure gas permeability and diffusion coefficients of H2, He, O2, N2, CO2 and CH4 were determined by the time lag method in a traditional fixed volume gas permeation setup. Mixed gas permeability measurements with a 35/65 vol % CO2/CH4 mixture and a 15/85 vol % CO2/N2 mixture were performed on a novel variable volume setup with on-line mass spectrometric analysis of the permeate composition, with the unique feature that it is also able to determine the mixed gas diffusion coefficients. It was found that the permeability of Matrimid increased approximately 20-fold with the addition of 50 wt % PIM-EA(H2)-TB. Mixed gas permeation measurements showed a slightly stronger pressure dependence for selectivity of separation of the CO2/CH4 mixture as compared to the CO2/N2 mixture, particularly for both the blended membrane and the pure PIM. The mixed gas selectivity was slightly higher than for pure gases, and although N2 and CH4 diffusion coefficients strongly increase in the presence of CO2, their solubility is dramatically reduced as a result of competitive sorption. A full analysis is provided of the difference between the pure and mixed gas transport parameters of PIM-EA(H2)-TB, Matrimid®5218 and their 50:50 wt % blend, including unique mixed gas diffusion coefficients. Full article
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Open AccessArticle
Analysis of Sustained Release Behavior of Drug-Containing Tablet Prepared by CO2-Assisted Polymer Compression
Polymers 2018, 10(12), 1405; https://doi.org/10.3390/polym10121405 - 18 Dec 2018
Cited by 4
Abstract
A controlled-release system for drug delivery allows the continuous supply of a drug to the target region at a predetermined rate for a specified period of time. Herein, the sustained release behavior of a drug-containing tablet fabricated through CO2-assisted polymer compression [...] Read more.
A controlled-release system for drug delivery allows the continuous supply of a drug to the target region at a predetermined rate for a specified period of time. Herein, the sustained release behavior of a drug-containing tablet fabricated through CO2-assisted polymer compression (CAPC) was investigated. CAPC involves placing the drug in the center of a nonwoven fabric, sandwiching this fabric between an integer number of nonwoven fabrics, and applying pressure bonding. An elution test, in which the drug-carrying tablet was immersed in water, showed that sustained-release performance can be controlled by the number of nonwoven fabrics covering the top and bottom of the drug-loaded fabric and compression conditions. A model of sustained drug release was formulated to estimate the effective diffusion coefficient in the porous material. Comparative analysis of the bulk diffusion coefficient revealed that the change in diffusion volume due to change in porosity predominates. The tortuosity of the diffusion path was 3–4, and tended to remain almost constant or increase only slightly when the compression rate was increased. These findings show that sustained drug release can be controlled by incorporating the drug into a nonwoven fabric and using the same raw material to encapsulate it. Full article
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Open AccessArticle
Microporous Materials Based on Norbornadiene-Based Cross-Linked Polymers
Polymers 2018, 10(12), 1382; https://doi.org/10.3390/polym10121382 - 13 Dec 2018
Cited by 6
Abstract
New microporous homopolymers were readily prepared from norbornadiene-2,5, its dimer and trimer by addition (vinyl) polymerization of the corresponding monomers with 60–98% yields. As a catalyst Pd-N-heterocyclic carbene complex or Ni(II) 2-ethylhexanoate activated with Na+[B(3,5-(CF3)2C [...] Read more.
New microporous homopolymers were readily prepared from norbornadiene-2,5, its dimer and trimer by addition (vinyl) polymerization of the corresponding monomers with 60–98% yields. As a catalyst Pd-N-heterocyclic carbene complex or Ni(II) 2-ethylhexanoate activated with Na+[B(3,5-(CF3)2C6H3)4] or methylaluminoxane was used. The synthesized polynorbornenes are cross-linked and insoluble. They are glassy and amorphous polymers. Depending on the nature of the catalyst applied, BET surface areas were in the range of 420–970 m2/g. The polymers with the highest surface area were obtained in the presence of Pd-catalysts from the trimer of norbornadiene-2,5. The total pore volume of the polymers varies from 0.39 to 0.79 cm3/g, while the true volume of micropores was 0.14–0.16 cm3/g according to t-plot. These polymers gave CO2 uptake from 1.2 to 1.9 mmol/g at 273 K and 1 atm. The porous structure of new polymers was also studied by means of wide-angle X-ray diffraction and positron annihilation lifetime spectroscopy. Full article
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Open AccessArticle
Feasibility Study on the Design and Synthesis of Functional Porous Organic Polymers with Tunable Pore Structure as Metallocene Catalyst Supports
Polymers 2018, 10(9), 944; https://doi.org/10.3390/polym10090944 - 24 Aug 2018
Cited by 1
Abstract
Porous organic polymers (POPs) are highly versatile materials that find applications in adsorption, separation, and catalysis. Herein, a feasibility study on the design and synthesis of POP supports with a tunable pore structure and high ethylene-polymerization activity was conducted by the selection of [...] Read more.
Porous organic polymers (POPs) are highly versatile materials that find applications in adsorption, separation, and catalysis. Herein, a feasibility study on the design and synthesis of POP supports with a tunable pore structure and high ethylene-polymerization activity was conducted by the selection of functional comonomers and template agents, and control of cross-linking degree of their frameworks. Functionalized POPs with a tunable pore structure were designed and synthesized by a dispersion polymerization strategy. The functional comonomers incorporated in the poly(divinylbenzene) (PDVB)-based matrix played a significant role in the porous structure and particle morphology of the prepared polymers, and a specific surface area (SSA) of 10–450 m2/g, pore volume (PV) of 0.05–0.5 cm3/g, bulk density with a range of 0.02–0.40 g/cm3 were obtained by the varied functional comonomers. Besides the important factors of thermodynamic compatibility of the selected solvent system, other factors that could be used to tune the pore structure and morphology of the POP particles have been also investigated. The Fe3O4 nanoaggregates as a template agent could help improve the porous structure and bulk density of the prepared POPs, and the highly cross-linking networks can dramatically increase the porous fabric of the prepared POPs. As for the immobilized metallocene catalysts, the pore structure of the prepared POPs had a significant influence on the loading amount of the Zr and Al of the active sites, and the typically highly porous structure of the POPs would contribute the immobilization of the active species. High ethylene-polymerization activity of 8033 kg PE/mol Zr h bar was achieved on the POPs-supported catalysts, especially when high Al/Zr ratios on the catalysts were obtained. The performance of the immobilized metallocene catalysts was highly related to the pore structure and functional group on the POP frameworks. Full article
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Open AccessCommunication
Controlling the Internal Structures of Polymeric Microspheres via the Introduction of a Water-Soluble Organic Solvent
Polymers 2018, 10(7), 789; https://doi.org/10.3390/polym10070789 - 18 Jul 2018
Cited by 2
Abstract
Polymeric microspheres with different internal structures have been widely used because of their characteristics in the structures. This paper reports a method of controlling the internal structures of polymeric microspheres via the introduction of a water-soluble organic solvent to the continuous phase in [...] Read more.
Polymeric microspheres with different internal structures have been widely used because of their characteristics in the structures. This paper reports a method of controlling the internal structures of polymeric microspheres via the introduction of a water-soluble organic solvent to the continuous phase in the foam phase preparation of porous polymeric microspheres. The introduction of a water-soluble organic solvent enables the control of polymeric microspheres’ internal structures, from porous to hollow. Because a water-soluble organic solvent is introduced, the organic solvent may be diffused toward the interface because of the affinity between the organic solvent and the oil droplets, resulting an accumulation of organic solvent molecules at the interface to form an organic solvent layer. The presence of this layer may decrease the evaporation rate of the internal organic solvent in an oil droplet, which extends the time for the mingling of porogen droplets to form a few large pores or even an extremely large single pore inside. This method is also capable of altering the thickness of hollow microspheres’ shells in a desired way, with improved efficiency, yield and the capacity for continuous use on an industrial scale. Full article
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Open AccessArticle
A Novel Glucose Biosensor Based on Hierarchically Porous Block Copolymer Film
Polymers 2018, 10(7), 723; https://doi.org/10.3390/polym10070723 - 02 Jul 2018
Cited by 2
Abstract
Enzymatic biosensors are widely used in clinical diagnostics, and electrode materials are essential for both the efficient immobilization of enzyme and the fast electron transfer between the active sites of enzyme and electrode surface. Electrode materials with a hierarchically porous structure can not [...] Read more.
Enzymatic biosensors are widely used in clinical diagnostics, and electrode materials are essential for both the efficient immobilization of enzyme and the fast electron transfer between the active sites of enzyme and electrode surface. Electrode materials with a hierarchically porous structure can not only increase the specific surface area but also promote the electron transfer, facilitating the catalysis reaction. Block copolymer is a good candidate for preparation of film with a hierarchically porous structure due to its unique characteristics of self-assembly and phase separation. In the current work, hierarchically porous block copolymer film containing both micropores and nanopores was prepared by spinodal decomposition induced phase separation. The resultant copolymer film was adopted as the electrode material to immobilize glucose oxidase (GOx) for construction of an enzyme biosensor. Scanning electron microscopy (SEM), contact angle (CA) measurements, and Fourier-transform infrared (FTIR) and electrochemical impendence spectroscopy (EIS) were adopted to investigate the microstructure of the as-developed biosensor. Results demonstrated that the hierarchically porous block copolymer film offered a favorable and biocompatible microenvironment for proteins. These as-prepared glucose biosensors possessed a wide linear range (10–4500 μM), a low detection limit (0.05 μM), quick response (2 s), excellent stability, and selectivity. This work demonstrates that hierarchically porous block copolymer film is a good matrix candidate for the immobilization of the enzyme and provides a potential electrode material to construct novel biosensors with excellent performance. Full article
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Review

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Open AccessReview
Highly Porous Organic Polymers for Hydrogen Fuel Storage
Polymers 2019, 11(4), 690; https://doi.org/10.3390/polym11040690 - 16 Apr 2019
Cited by 1
Abstract
Hydrogen (H2) is one of the best candidates to replace current petroleum energy resources due to its rich abundance and clean combustion. However, the storage of H2 presents a major challenge. There are two methods for storing H2 fuel, [...] Read more.
Hydrogen (H2) is one of the best candidates to replace current petroleum energy resources due to its rich abundance and clean combustion. However, the storage of H2 presents a major challenge. There are two methods for storing H2 fuel, chemical and physical, both of which have some advantages and disadvantages. In physical storage, highly porous organic polymers are of particular interest, since they are low cost, easy to scale up, metal-free, and environmentally friendly. In this review, highly porous polymers for H2 fuel storage are examined from five perspectives: (a) brief comparison of H2 storage in highly porous polymers and other storage media; (b) theoretical considerations of the physical storage of H2 molecules in porous polymers; (c) H2 storage in different classes of highly porous organic polymers; (d) characterization of microporosity in these polymers; and (e) future developments for highly porous organic polymers for H2 fuel storage. These topics will provide an introductory overview of highly porous organic polymers in H2 fuel storage. Full article
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Open AccessReview
Recent Advancements in the Synthesis of Covalent Triazine Frameworks for Energy and Environmental Applications
Polymers 2019, 11(1), 31; https://doi.org/10.3390/polym11010031 - 26 Dec 2018
Cited by 8
Abstract
Covalent triazine frameworks (CTFs) are a unique type of porous materials, comprised of triazine units. Owing to the strong linkage of triazine, the most important advantage of CTFs lies in their high chemical and thermal stabilities and high nitrogen content as compared to [...] Read more.
Covalent triazine frameworks (CTFs) are a unique type of porous materials, comprised of triazine units. Owing to the strong linkage of triazine, the most important advantage of CTFs lies in their high chemical and thermal stabilities and high nitrogen content as compared to other porous organic polymers (POPs). Therefore, CTFs are one of the most promising materials for practical applications. Much research has been devoted to developing new methods to synthesize CTFs and explore their potential applications. Nowadays, energy and environmental issues have attracted enormous attention. CTFs are particular promising for energy- and environment-related applications, due to their nitrogen-rich scaffold and robust structure. Here, we selected some typical examples and reviewed recent advancements in the synthesis of CTFs and their applications in gas adsorption, separation, and catalysis in relation to environment and energy issues. Full article
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