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19 pages, 2708 KiB

Open AccessArticle

Effect of Amino-Functionalized Polyhedral Oligomeric Silsesquioxanes on Structure-Property Relationships of Thermostable Hybrid Cyanate Ester Resin Based Nanocomposites

by Olga Grigoryeva, Alexander Fainleib, Olga Starostenko, Diana Shulzhenko, Agustin Rios de Anda, Fabrice Gouanve, Eliane Espuche and Daniel Grande

Polymers 2023, 15(24), 4654; https://doi.org/10.3390/polym15244654 - 9 Dec 2023

Cited by 2 | Viewed by 818

Abstract

Nanocomposites of cyanate ester resin (CER) filled with three different reactive amino-functionalized polyhedral oligomeric silsesquioxane (POSS) were synthesized and characterized. The addition of a small quantity (0.1 wt.%) of amino-POSS chemically grafted to the CER network led to the increasing thermal stability of [...] Read more.

Nanocomposites of cyanate ester resin (CER) filled with three different reactive amino-functionalized polyhedral oligomeric silsesquioxane (POSS) were synthesized and characterized. The addition of a small quantity (0.1 wt.%) of amino-POSS chemically grafted to the CER network led to the increasing thermal stability of the CER matrix by 12–15 °C, depending on the type of amino-POSS. A significant increase of the glass transition temperature, T_g (DSC data), and the temperature of α relaxation, T_α (DMTA data), by 45–55 °C of the CER matrix with loading of nanofillers was evidenced. CER/POSS films exhibited a higher storage modulus than that of neat CER in the temperature range investigated. It was evidenced that CER/aminopropylisobutyl (APIB)-POSS, CER/N-phenylaminopropyl (NPAP)-POSS, and CER/aminoethyl aminopropylisobutyl (AEAPIB)-POSS nanocomposites induced a more homogenous α relaxation phenomenon with higher T_α values and an enhanced nanocomposite elastic behavior. The value of the storage modulus, E′, at 25 °C increased from 2.72 GPa for the pure CER matrix to 2.99–3.24 GPa for the nanocomposites with amino-functionalized POSS nanoparticles. Furthermore, CER/amino-POSS nanocomposites possessed a higher specific surface area, gas permeability (CO₂, He), and diffusion coefficients (CO₂) values than those for neat CER, due to an increasing free volume of the nanocomposites studied that is very important for their gas transport properties. Permeability grew by about 2 (He) and 3.5–4 times (CO₂), respectively, and the diffusion coefficient of CO₂ increased approximately twice for CER/amino-POSS nanocomposites in comparison with the neat CER network. The efficiency of amino-functionalized POSS in improving the thermal and transport properties of the CER/amino-POSS nanocomposites increased in a raw of reactive POSS containing one primary (APIB-POSS) < eight secondary (NPAP-POSS) < one secondary and one primary (AEAPIB-POSS) amino groups. APIB-POSS had the least strongly pronounced effect, since it could form covalent bonds with the CER network only by a reaction of one -NH₂ group, while AEAPIB-POSS displayed the most highly marked effect, since it could easily be incorporated into the CER network via a reaction of –NH₂ and –NH– groups with –O–C≡N groups from CER. Full article

(This article belongs to the Special Issue Porous Polymeric Materials: Design and Applications)

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12 pages, 3980 KiB

Open AccessArticle

RAFT Polymerisation and Hypercrosslinking Improve Crosslink Homogeneity and Surface Area of Styrene Based PolyHIPEs

by Amadeja Koler, Jiři Brus and Peter Krajnc

Polymers 2023, 15(10), 2255; https://doi.org/10.3390/polym15102255 - 10 May 2023

Cited by 2 | Viewed by 1350

Abstract

The influence of a polymerisation mechanism (reversible addition–fragmentation chain transfer; RAFT vs. free radical polymerisation; FRP) on the porous structure of highly porous poly(styrene-co-divinylbenzene) polymers was investigated. The highly porous polymers were synthesised via high internal phase emulsion templating (polymerizing the continuous phase [...] Read more.

The influence of a polymerisation mechanism (reversible addition–fragmentation chain transfer; RAFT vs. free radical polymerisation; FRP) on the porous structure of highly porous poly(styrene-co-divinylbenzene) polymers was investigated. The highly porous polymers were synthesised via high internal phase emulsion templating (polymerizing the continuous phase of a high internal phase emulsion), utilising either FRP or RAFT processes. Furthermore, residual vinyl groups in the polymer chains were used for the subsequent crosslinking (hypercrosslinking) applying di-tert-butyl peroxide as the source of radicals. A significant difference in the specific surface area of polymers prepared by FRP (between 20 and 35 m²/g) and samples prepared by RAFT polymerisation (between 60 and 150 m²/g) was found. Based on the results from gas adsorption and solid state NMR, it could be concluded that the RAFT polymerisation affects the homogeneous distribution of the crosslinks in the highly crosslinked styrene-co-divinylbenzene polymer network. During the initial crosslinking, RAFT polymerisation leads to the increase in mesopores with diameters between 2 and 20 nm, resulting in good accessibility of polymer chains during the hypercrosslinking reaction, which is reflected in increased microporosity. The fraction of micropores created during the hypercrosslinking of polymers prepared via RAFT is around 10% of the total pore volume, which is up to 10 times more than for polymers prepared by FRP. Specific surface area, mesopore surface area, and total pore volume after hypercrosslinking reach almost the same values, regardless of the initial crosslinking. The degree of hypercrosslinking was confirmed by determination of the remaining double bonds by solid-state NMR analysis. Full article

(This article belongs to the Special Issue Porous Polymeric Materials: Design and Applications)

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16 pages, 7416 KiB

Open AccessArticle

Polymer Supercritical CO₂ Foaming under Peculiar Conditions: Laser and Ultrasound Implementation

by Jennifer Andrea Villamil Jiménez, Margaux Haurat, Rayan Berriche, Fabien Baillon, Martial Sauceau, Mattéo Chaussat, Jean-Marc Tallon, Andrzej Kusiak and Michel Dumon

Polymers 2023, 15(8), 1968; https://doi.org/10.3390/polym15081968 - 21 Apr 2023

Viewed by 1262

Abstract

The two-step batch foaming process of solid-state assisted by supercritical CO₂ is a versatile technique for the foaming of polymers. In this work, it was assisted by an out-of-autoclave technology: either using lasers or ultrasound (US). Laser-aided foaming was only tested in [...] Read more.

The two-step batch foaming process of solid-state assisted by supercritical CO₂ is a versatile technique for the foaming of polymers. In this work, it was assisted by an out-of-autoclave technology: either using lasers or ultrasound (US). Laser-aided foaming was only tested in the preliminary experiments; most of the work involved US. Foaming was carried out on bulk thick samples (PMMA). The effect of ultrasound on the cellular morphology was a function of the foaming temperature. Thanks to US, cell size was slightly decreased, cell density was increased, and interestingly, thermal conductivity was shown to decrease. The effect on the porosity was more remarkable at high temperatures. Both techniques provided micro porosity. This first investigation of these two potential methods for the assistance of supercritical CO₂ batch foaming opens the door to new investigations. The different properties of the ultrasound method and its effects will be studied in an upcoming publication. Full article

(This article belongs to the Special Issue Porous Polymeric Materials: Design and Applications)

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14 pages, 2749 KiB

Open AccessArticle

Effect of Crystallinity on Young’s Modulus of Porous Materials Composed of Polyethylene Terephthalate Fibers in the Presence of Carbon Dioxide

by Takafumi Aizawa

Polymers 2022, 14(18), 3724; https://doi.org/10.3390/polym14183724 - 6 Sep 2022

Cited by 2 | Viewed by 1413

Abstract

Carbon dioxide (CO₂)-assisted polymer compression method is used for plasticizing polymers with subcritical CO₂ and then crimping the polymer fibers. Given that this method is based on crimping after plasticization by CO₂, it is very important to know [...] Read more.

Carbon dioxide (CO₂)-assisted polymer compression method is used for plasticizing polymers with subcritical CO₂ and then crimping the polymer fibers. Given that this method is based on crimping after plasticization by CO₂, it is very important to know the degree of plasticization. In this study, heat treatment was gently applied on raw material fibers to obtain fibers with different degrees of crystallinity without changing the shape of the fibers. Simultaneously, two types of sheets were placed in a pressure vessel to compare the degree of compression and the degree of hardness. Furthermore, a model was used to derive the relative Young’s modulus of porous materials composed of polymer fibers with different degrees of crystallinity. In the model, the amount of strain was calculated according to the Young’s modulus as a function of porosity and reflected in compression. Young’s modulus of porous polymers in the presence of CO₂ has been shown to vary significantly with slight differences in crystallinity, indicating that extremely low crystallinity is significant for plasticizing the polymer by CO₂. Full article

(This article belongs to the Special Issue Porous Polymeric Materials: Design and Applications)

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18 pages, 4179 KiB

Open AccessArticle

Triazole-Functionalized Mesoporous Materials Based on Poly(styrene-block-lactic acid): A Morphology Study of Thin Films

by Melisa Trejo-Maldonado, Aisha Womiloju, Steffi Stumpf, Stephanie Hoeppener, Ulrich S. Schubert, Luis E. Elizalde and Carlos Guerrero-Sanchez

Polymers 2022, 14(11), 2231; https://doi.org/10.3390/polym14112231 - 31 May 2022

Cited by 2 | Viewed by 1500

Abstract

We report the synthesis of poly(styrene-block-lactic acid) (PS-b-PLA) copolymers with triazole rings as a junction between blocks. These materials were prepared via a ‘click’ strategy which involved the reaction between azide-terminated poly(styrene) (PS-N₃) and acetylene-terminated poly(D,L-lactic acid) [...] Read more.

We report the synthesis of poly(styrene-block-lactic acid) (PS-b-PLA) copolymers with triazole rings as a junction between blocks. These materials were prepared via a ‘click’ strategy which involved the reaction between azide-terminated poly(styrene) (PS-N₃) and acetylene-terminated poly(D,L-lactic acid) (PLA-Ac), accomplished by copper-catalyzed azide-alkyne cycloaddition reaction. This synthetic approach has demonstrated to be effective to obtain specific copolymer structures with targeted self-assembly properties. We observed the self-assembly behavior of the PS-b-PLA thin films as induced by solvent vapor annealing (SVA), thermal annealing (TA), and hydrolysis of the as-spun substrates and monitored their morphological changes by means of different microscopic techniques. Self-assembly via SVA and TA proved to be strongly dependent on the pretreatment of the substrates. Microphase segregation of the untreated films yielded a pore size of 125 nm after a 45-min SVA. After selectively removing the PLA microdomains, the as-spun substrates exhibited the formation of pores on the surface, which can be a good alternative to form an ordered pattern of triazole functionalized porous PS at the mesoscale. Finally, as revealed by scanning electron microscopy–energy dispersive X-ray spectroscopy, the obtained triazole-functionalized PS-porous film exhibited some affinity to copper (Cu) in solution. These materials are suitable candidates to further study its metal-caption properties. Full article

(This article belongs to the Special Issue Porous Polymeric Materials: Design and Applications)

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8 pages, 3411 KiB

Open AccessCommunication

Facile Synthesis of Microporous Ferrocenyl Polymers Photocatalyst for Degradation of Cationic Dye

by Bing Zhang, Zhiqiang Tan, Yinhu Zhang, Qingquan Liu, Qianxia Li and Gen Li

Polymers 2022, 14(9), 1900; https://doi.org/10.3390/polym14091900 - 6 May 2022

Cited by 2 | Viewed by 1703

Abstract

Microporous organic polymers (MOPs) were prepared by condensation reactions from substituent-group-free carbazole and pyrrole with 1,1′-ferrocenedicarboxaldehyde without adding any catalysts. The resultant MOPs were insoluble in common solvent and characterized by FTIR, XPS, TGA and SEM. An N₂ adsorption test showed that [...] Read more.

Microporous organic polymers (MOPs) were prepared by condensation reactions from substituent-group-free carbazole and pyrrole with 1,1′-ferrocenedicarboxaldehyde without adding any catalysts. The resultant MOPs were insoluble in common solvent and characterized by FTIR, XPS, TGA and SEM. An N₂ adsorption test showed that the obtained polymers PFcMOP and CFcMOP exhibited Brunauer–Emmett–Teller (BET) surface areas of 48 and 105 m² g⁻¹, respectively, and both polymers possessed abundant micropores. The MOPs with a nitrogen and ferrocene unit could be potentially applied in degrading dye with high efficiency. Full article

(This article belongs to the Special Issue Porous Polymeric Materials: Design and Applications)

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12 pages, 5363 KiB

Open AccessCommunication

Emulsion Templated Porous Poly(thiol-enes): Influence of Photopolymerisation, Emulsion Composition, and Phase Behaviour on the Porous Structure and Morphology

by Viola Hobiger, Muzafera Paljevac and Peter Krajnc

Polymers 2022, 14(7), 1338; https://doi.org/10.3390/polym14071338 - 25 Mar 2022

Cited by 7 | Viewed by 2387

Abstract

1,6-hexanediol diacrylate (HDDA) or divinyl adipate (DVA) and pentaerythritol tetrakis(3-mercaptopropionate) (TT) were polymerised via a thiol-ene radical initiated photopolymerisation using emulsions with a high volume fraction of internal droplet phase and monomers in the continuous phase as precursors. The porous structure derived from [...] Read more.

1,6-hexanediol diacrylate (HDDA) or divinyl adipate (DVA) and pentaerythritol tetrakis(3-mercaptopropionate) (TT) were polymerised via a thiol-ene radical initiated photopolymerisation using emulsions with a high volume fraction of internal droplet phase and monomers in the continuous phase as precursors. The porous structure derived from the high internal phase emulsions (HIPEs) followed the precursor emulsion setup resulting in an open porous cellularly structured polymer. Changing the emulsion composition and polymerisation conditions influenced the resulting morphological structure significantly. The investigated factors influencing the polymer monolith morphology were the emulsion phase ratio and surfactant concentration, leading to either interconnected cellular type morphology, bicontinuous porous morphology or a hollow sphere inverted structure of the polymerised monoliths. The samples with interconnected cellular morphology had pore diameters between 4 µm and 10 µm with approx. 1 µm sized interconnecting channels while samples with bicontinuous morphology featured approx. 5 µm wide pores between the polymer domains. The appropriate choice of emulsion composition enabled the preparation of highly porous poly(thiol-enes) with either polyHIPE or bicontinuous morphology. The porosities of the prepared samples followed the emulsion droplet phase share and could reach up to 88%. Full article

(This article belongs to the Special Issue Porous Polymeric Materials: Design and Applications)

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Review

Jump to: Research

22 pages, 4397 KiB

Open AccessReview

Metallic Nanoparticles Adsorbed at the Pore Surface of Polymers with Various Porous Morphologies: Toward Hybrid Materials Meant for Heterogeneous Supported Catalysis

by Benjamin Le Droumaguet, Romain Poupart, Mohamed Guerrouache, Benjamin Carbonnier and Daniel Grande

Polymers 2022, 14(21), 4706; https://doi.org/10.3390/polym14214706 - 3 Nov 2022

Cited by 2 | Viewed by 2041

Abstract

Hybrid materials consisting of metallic nanoparticles (NPs) adsorbed on porous polymeric supports have been the subject of intense research for many years. Such materials indeed gain from intrinsic properties, e.g., high specific surface area, catalytic properties, porous features, etc., of both components. Rational [...] Read more.

Hybrid materials consisting of metallic nanoparticles (NPs) adsorbed on porous polymeric supports have been the subject of intense research for many years. Such materials indeed gain from intrinsic properties, e.g., high specific surface area, catalytic properties, porous features, etc., of both components. Rational design of such materials is fundamental regarding the functionalization of the support surface and thus the interactions required for the metallic NPs to be strongly immobilized at the pore surface. Herein are presented some significant scientific contributions to this rapidly expanding research field. This contribution will notably focus on various examples of such hybrid systems prepared from porous polymers, whatever the morphology and size of the pores. Such porous polymeric supports can display pores with sizes ranging from a few nanometers to hundreds of microns while pore morphologies, such as spherical, tubular, etc., and/or open or closed, can be obtained. These systems have allowed some catalytic molecular reactions to be successfully undertaken, such as the reduction of nitroaromatic compounds or dyes, e.g., methylene blue and Eosin Y, boronic acid-based C–C homocoupling reactions, but also cascade reactions consisting of two catalytic reactions achieved in a row. Full article

(This article belongs to the Special Issue Porous Polymeric Materials: Design and Applications)

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