Topical Collection "Silicon-Containing Polymeric Materials"

A topical collection in Polymers (ISSN 2073-4360). This collection belongs to the section "Polymer Chemistry".

Editor

Prof. Dr. Ignazio Blanco
Website SciProfiles
Collection Editor
Department of Civil Engineering and Architecture, University of Catania, Edificio 10, Viale A. Doria 6, 95125 Catania, Italy
Interests: thermal stability; thermogravimetric analysis; differential scanning calorimetry; nanocomposites; kinetics of degradation; lifetime prediction; POSS; POSS-Based polymers
Special Issues and Collections in MDPI journals

Topical Collection Information

Dear Colleagues,

When thinking about a chemical element that has contributed to the technological progress over the last two centuries, carbon and all carbon-based materials immediately come to mind. By the way, especially during the last century, Silicon and its related materials follow very closely. The versatility of silicon-based materials and silicon’s abundance in the earth's crust make us sure that it will continue to play, in the years to come, a vital role in everyday life. In addition to silicones, or polysiloxanes, which have been known and manufactured for many years, silica-reinforced polymers, silsesquioxaness, and POSS-based polymers also offer a multitude of very useful consumer products. The combination of silicon and oxygen atoms with organic groups has lead to the generation of new and modified silicon-containing polymeric materials, thus providing an exciting mixture of properties and offering a wide spectrum of practical applications. We are interested in articles that explore silicon-containing polymeric materials and their applications.

Prof. Dr. Ignazio Blanco
Collection Editor

Related Special Issues

Published Papers (111 papers)

2020

Jump to: 2019, 2018, 2017, 2016, 2015

Open AccessArticle
High Refractive-Index Hybrids Consisting of Water-Soluble Matrices with Bipyridine-Modified Polyhedral Oligomeric Silsesquioxane and Lanthanoid Cations
Polymers 2020, 12(7), 1560; https://doi.org/10.3390/polym12071560 - 14 Jul 2020
Abstract
We report high refractive-index (RI) films composed of polyhedral oligomeric silsesquioxane (SSQ) matrices and various lanthanoid cations. The SSQ matrices were constructed from octaammonium SSQ by connecting with bipyridine dicarboxylic acid, which is expected to capture cations. By modulating the feed ratio between [...] Read more.
We report high refractive-index (RI) films composed of polyhedral oligomeric silsesquioxane (SSQ) matrices and various lanthanoid cations. The SSQ matrices were constructed from octaammonium SSQ by connecting with bipyridine dicarboxylic acid, which is expected to capture cations. By modulating the feed ratio between SSQ and dicarboxylic acid, the series of the SSQ matrices were obtained with variable cross-linking ratios among the SSQ units. Thin transparent films were able to be prepared through the drop-casting method with the aqueous mixtures containing SSQ matrices and various kinds of lanthanoid salts up to 40 wt %. From RI measurements, it was revealed that the increase of the amount of the metal ion can significantly lift up the RI values. In particular, critical losses of Abbe numbers, which theoretically have the trade-off relationship toward increases in RI values, were hardly detected. This effect could be obtained by cation assembly in local spots that are assisted by SSQ. Full article
Show Figures

Figure 1

Open AccessArticle
Preparation of Tri(alkenyl)functional Open-Cage Silsesquioxanes as Specific Polymer Modifiers
Polymers 2020, 12(5), 1063; https://doi.org/10.3390/polym12051063 - 06 May 2020
Abstract
The scientific reports on polyhedral oligomeric silsesquioxanes are mostly focused on the formation of completely condensed T8 cubic type structures and recently so-called double-decker derivatives. Herein, we report on efficient synthetic routes leading to trifunctionalized, open-cage silsesquioxanes with alkenyl groups of varying [...] Read more.
The scientific reports on polyhedral oligomeric silsesquioxanes are mostly focused on the formation of completely condensed T8 cubic type structures and recently so-called double-decker derivatives. Herein, we report on efficient synthetic routes leading to trifunctionalized, open-cage silsesquioxanes with alkenyl groups of varying chain lengths from -vinyl to -dec-9-enyl and two types of inert groups (iBu, Ph) at the silsesquioxane core. The presented methodology was focused on hydrolytic condensation reaction and it enabled obtaining titled compounds with high yields and purity. A parallel synthetic methodology that was based on the hydrosilylation reaction was also studied. Additionally, a thorough characterization of the obtained compounds was performed, also in terms of their thermal stability, melting and crystallization temperatures (TGA and DSC) in order to show the changes in the abovementioned parameters dependent on the type of reactive as well as inert groups at Si-O-Si core. The presence of unsaturated alkenyl groups has a profound impact on the application potential of these systems, i.e., as modifiers or comonomers for copolymerization reaction. Full article
Show Figures

Graphical abstract

Open AccessArticle
A Novel Acetylene-Functional/Silicon-Containing Benzoxazine Resin: Preparation, Curing Kinetics and Thermal Properties
Polymers 2020, 12(5), 999; https://doi.org/10.3390/polym12050999 - 26 Apr 2020
Abstract
Benzoxazine resin has been paid more attention in the fields of aviation, electronics, automobiles and new energy industries because of its excellent comprehensive performance. Further application is limited, however, by shortcomings such as high brittleness and high curing temperature. Furthermore, higher thermal stability [...] Read more.
Benzoxazine resin has been paid more attention in the fields of aviation, electronics, automobiles and new energy industries because of its excellent comprehensive performance. Further application is limited, however, by shortcomings such as high brittleness and high curing temperature. Furthermore, higher thermal stability is imperiously demanded in special areas. Incorporating both an acetylene group and silicon into the benzoxazine monomer is a promising possible solution to improve the curing processability, thermal properties and toughness of benzoxazine. In this paper, an acetylene-functional/silicon-containing benzoxazine monomer was prepared by two-step synthesis, and acetylene-functional benzoxazine was also prepared as a comparison. FTIR and 1H NMR confirmed the molecular structure of acetylene-functional/silicon-containing benzoxazine. Differential scanning calorimetry (DSC) analysis showed that the initial and peak degradation temperatures of acetylene-functional/silicon-containing benzoxazine were decreased by 21 °C and 18 °C compared with acetylene-functional benzoxazine, respectively. The apparent activation energy of the curing reaction of acetylene-functional/silicon-containing benzoxazine was 83.1 kJ/mol, which was slightly lower than acetylene-functional benzoxazine (84.7 kJ/mol). TGA results showed that the acetylene-functional/silicon-containing benzoxazine had a higher thermal stability than acetylene-functional benzoxazine. The temperatures of 5% weight loss of acetylene-functional/silicon-containing benzoxazine were 380 °C in nitrogen and 485 °C in air, and the char yield at 1000 °C was 80% in nitrogen and 21% in air, respectively. The results of mechanical properties showed that the impact strength of acetylene-functional/silicon-containing benzoxazine was higher than acetylene-functional benzoxazine by 35.4%. The tensile and flexural strengths of acetylene-functional/silicon-containing benzoxazine were slightly higher than that of acetylene-functional benzoxazine. Full article
Show Figures

Figure 1

Open AccessArticle
Hyperbranched Poly(ether-siloxane)s Containing Ammonium Groups: Synthesis, Characterization and Catalytic Activity
Polymers 2020, 12(4), 856; https://doi.org/10.3390/polym12040856 - 07 Apr 2020
Abstract
In this article we report an easy synthetic route towards hyperbranched polyglycerols (Amm-HBPGs) containing trimethylammonium groups and siloxane or hydroxyl end-groups. Siloxane derivatives of Amm-HBPGs were synthesized in an efficient five-step procedure including an anionic ring opening copolymerization of the phthalimide-epoxy monomer with [...] Read more.
In this article we report an easy synthetic route towards hyperbranched polyglycerols (Amm-HBPGs) containing trimethylammonium groups and siloxane or hydroxyl end-groups. Siloxane derivatives of Amm-HBPGs were synthesized in an efficient five-step procedure including an anionic ring opening copolymerization of the phthalimide-epoxy monomer with glycidol, followed by reactions with allyl bromide, hydrosililation with hydrogenheptamethyltrisiloxane, hydrazinolysis of phthalimide groups and quaternization of resulting amine groups with methyl iodide. Hydroxyl derivatives were obtained by quaternization of previously reported aminated HBPG’s with methyl iodide. Polymeric products were characterized using various NMR techniques, FTIR, and elemental analysis. Both Amm-HBPGs were shown to be effective in catalysis of addition of CO2 to oxirane. The hydrophilic catalysts showed higher efficiency but synthesis of ethylene carbonate was accompanied by formation of small amounts of ethylene glycol. The siloxane-containing catalyst was easily separable from reaction mixture showing high potential in the process of converting carbon dioxide into valuable chemical raw materials. Full article
Show Figures

Graphical abstract

Open AccessArticle
Study of POSS on the Properties of Novel Inorganic Dental Composite Resin
Polymers 2020, 12(2), 478; https://doi.org/10.3390/polym12020478 - 20 Feb 2020
Cited by 4
Abstract
Various amounts of methacryl polyhedral oligomeric silsesquioxane (POSS) were explored to be incorporated into novel nano SiO2 dental resin composites using light curing method. The scanning electron microscopy (SEM), optical microscopy, fourier transform infrared spectroscopy (FTIR), nanoindentation, nanoscratch and three-point flexure tests [...] Read more.
Various amounts of methacryl polyhedral oligomeric silsesquioxane (POSS) were explored to be incorporated into novel nano SiO2 dental resin composites using light curing method. The scanning electron microscopy (SEM), optical microscopy, fourier transform infrared spectroscopy (FTIR), nanoindentation, nanoscratch and three-point flexure tests were performed. The volumetric shrinkage and mechanical properties such as hardness, elastic modulus, resistance, flexural strength and fracture energy were analyzed. With the additions of POSS, the volume shrinkage decreased and the mechanical properties initially increased. The effects of POSS on these properties were studied to provide a reference for clinically selecting a composite resin with excellent properties. Full article
Show Figures

Figure 1

Open AccessArticle
Main Chain–Type Block Copolymers through Atom Transfer Radical Polymerization from Double-Decker–Shaped Polyhedral Oligomeric Silsesquioxane Hybrids
Polymers 2020, 12(2), 465; https://doi.org/10.3390/polym12020465 - 17 Feb 2020
Abstract
In this study, we synthesized two main chain–type block copolymers featuring hydrogen bond donor and acceptor segments through atom transfer radical polymerization (ATRP) using a bifunctionalized polyhedral oligomeric silsesquioxane (POSS) nanoparticle as the initiator. Hydrosilylation of vinylbenzyl chloride at the two corners of [...] Read more.
In this study, we synthesized two main chain–type block copolymers featuring hydrogen bond donor and acceptor segments through atom transfer radical polymerization (ATRP) using a bifunctionalized polyhedral oligomeric silsesquioxane (POSS) nanoparticle as the initiator. Hydrosilylation of vinylbenzyl chloride at the two corners of a double-decker silsesquioxane (DDSQ) provided the bifunctionalized benzyl chloride initiator VBC-DDSQ-VBC, which we applied as a platform to prepare a main chain–type polystyrene homopolymer (PS-DDSQ-PS), the diblock copolymer poly(styrene–b–4-vinylpyridine) (P4VP-b-PS-DDSQ-PS-b-P4VP), and the diblock copolymer poly(styrene–btert-butoxystyrene) (PtBuOS-b-PS-DDSQ-PS-b-PtBuOS) through sequential ATRP. Selective hydrolysis of the tert-butoxyl units of PtBuOS-b-PS-DDSQ-PS-b-PtBuOS yielded the strongly hydrogen bonding diblock copolymer poly (styrene-b-vinylphenol) (PVPh-b-PS-DDSQ-PS-b-PVPh). We used Fourier transfer infrared spectroscopy, nuclear magnetic resonance spectroscopy, size exclusion chromatography, differential scanning calorimetry, mass-analyzed laser desorption ionization mass spectrometry, and transmission electron microscopy to investigate the chemical structures, thermal behavior, and self-assembled nanostructures formed by these main chain–type block copolymers based on DDSQ. Full article
Show Figures

Graphical abstract

2019

Jump to: 2020, 2018, 2017, 2016, 2015

Open AccessArticle
Novel Siloxane-Modified Epoxy Resins as Promising Encapsulant for LEDs
Polymers 2020, 12(1), 21; https://doi.org/10.3390/polym12010021 - 20 Dec 2019
Cited by 1
Abstract
This study investigated a new category of transparent encapsulant materials for light-emitting diodes (LEDs). It comprised a phenyl group that contained siloxane-modified epoxy (SEP-Ph) hybridized with a cyclic tetrafunctional siloxane-modified epoxy (SEP-D4) with methylhexahydrophthalic anhydride (MHHPA) as a curing agent. The SEP-Ph/SEP-D4 = [...] Read more.
This study investigated a new category of transparent encapsulant materials for light-emitting diodes (LEDs). It comprised a phenyl group that contained siloxane-modified epoxy (SEP-Ph) hybridized with a cyclic tetrafunctional siloxane-modified epoxy (SEP-D4) with methylhexahydrophthalic anhydride (MHHPA) as a curing agent. The SEP-Ph/SEP-D4 = 0.5/0.5 (sample 3) and SEP-D4 (sample 4) could provide notably high optical transmittance (over 90% in the visible region), high-temperature discoloration resistance, low stress, and more crucially, noteworthy sulfurization resistance. The lumen flux retention of the SEP encapsulated surface mounted device LEDs remained between approximately 97% and 99% after a sulfurization test for 240 h. The obtained comprehensive optical, mechanical, and sulfurization resistance proved the validity and uniqueness of the present design concept with complementary physical and chemical characteristics. Full article
Show Figures

Graphical abstract

Open AccessReview
Progress in the Synthesis of Bifunctionalized Polyhedral Oligomeric Silsesquioxane
Polymers 2019, 11(12), 2098; https://doi.org/10.3390/polym11122098 - 14 Dec 2019
Cited by 1
Abstract
Polyhedral oligomeric silsesquioxane (POSS) has been considered as one of the most promising nanofillers in academic and industrial research due to its unique multifunctional nanostructure, easy functionalization, hybrid nature, and high processability. The progress of POSS has been extensive, particularly applications based on [...] Read more.
Polyhedral oligomeric silsesquioxane (POSS) has been considered as one of the most promising nanofillers in academic and industrial research due to its unique multifunctional nanostructure, easy functionalization, hybrid nature, and high processability. The progress of POSS has been extensive, particularly applications based on single- or multiple-armed POSS. In polymer hybrids, in order to enhance the properties, bifunctional POSS has been incorporated into the backbone chain of the polymer. This review summarizes recent developments in the synthesis, modification, and application of bifunctional POSS-containing composite materials. This includes amino-POSS, hydroxyl-POSS, aromatic ring-POSS, ether-POSS, and vinyl groups-POSS and their applications, exemplified by polyurethanes (PUs) and polyimides (PIs). In addition, the review highlights the enhancement of thermal, mechanical, and optical properties of the composites. Full article
Show Figures

Graphical abstract

Open AccessArticle
Synthesis of Monoacryloxypropyl-POSS-based Hybrid Epoxyacrylate Copolymers and Their Application in Thermally Curable Structural Self-Adhesive Tapes
Polymers 2019, 11(12), 2058; https://doi.org/10.3390/polym11122058 - 11 Dec 2019
Cited by 2
Abstract
New organic-inorganic hybrid copolymers (EA-POSSs) based on butyl acrylate, glycidyl methacylate, hydroxybutyl acrylate, acryloiloxybenzophenone and acryloxypropyl-heptaisobutyl-POSS (A-POSS) were prepared via free-radical solution polymerization (FRP) and applied as a component of thermally curable structural self-adhesive tapes (SATs). The EA-POSS with 0.25, 0.5 or 1 [...] Read more.
New organic-inorganic hybrid copolymers (EA-POSSs) based on butyl acrylate, glycidyl methacylate, hydroxybutyl acrylate, acryloiloxybenzophenone and acryloxypropyl-heptaisobutyl-POSS (A-POSS) were prepared via free-radical solution polymerization (FRP) and applied as a component of thermally curable structural self-adhesive tapes (SATs). The EA-POSS with 0.25, 0.5 or 1 mol % of A-POSS exhibited significantly higher dynamic viscosity (ca. +104%), Mw (+61%) and polydispersity (+109%; measured using gel permeation chromatography) as well as lower Tg value (−16 °C) in relation to the A-POSS-free copolymer (EA-0). Differential scanning calorimetry (DSC) measurements (one glass transition process) confirmed statistic chain structure of the EA-POSS materials. Replacement of EA-0 by the EA-POSS copolymers in a SATs recipe caused simultaneous improvement of their self-adhesive features, i.e., adhesion (+70%), tack (+21%) and cohesion (+1590%). Moreover, the POSS-based copolymers improved the shear strength of thermally cured Al/SAT/Al overlap joints; the best mechanical resistance (before and after accelerated ageing tests) was observed for the sample containing 0.5 mol % of A-POSS (an increment range of 50–294% in relation to the A-POSS-free joints). Thermogravimetric analysis (TGA) revealed markedly improved thermal stability of the A-POSS-based SATs as well. Full article
Show Figures

Figure 1

Open AccessArticle
Synthesis and Characterization of Aminosilane Grafted Cellulose Nanocrystal Modified Formaldehyde-Free Decorative Paper and its CO2 Adsorption Capacity
Polymers 2019, 11(12), 2021; https://doi.org/10.3390/polym11122021 - 06 Dec 2019
Abstract
As one of the main consumables of interior decoration and furniture, decorative paper can be seen everywhere in the indoor space. However, because of its high content of formaldehyde, it has a certain threat to people’s health. Therefore, it is necessary to develop [...] Read more.
As one of the main consumables of interior decoration and furniture, decorative paper can be seen everywhere in the indoor space. However, because of its high content of formaldehyde, it has a certain threat to people’s health. Therefore, it is necessary to develop and study new formaldehyde-free decorative paper to meet the market demand. In this work, we have obtained formaldehyde-free decorative paper with high CO2 adsorption capacity. Here, cellulose nanocrystals (CNC) were prepared by hydrolyzing microcrystalline cellulose with sulfuric acid. The N-(2-aminoethyl) (3-amino-propyl) methyldimethoxysilane (AEAPMDS) was grafted onto the CNCs by liquid phase hydrothermal treatment, and the aqueous solution was substituted by tert-butanol to obtain aminated CNCs (AEAPMDS-CNCs). The as-prepared AEAPMDS-CNCs were applied to formaldehyde-free decorative paper by the spin-coating method. The effects of various parameters on the properties of synthetic materials were systematically studied, and the optimum reaction conditions were revealed. Moreover, the surface bond strength and abrasion resistance of modified formaldehyde-free decorative paper were investigated. The experimental results showed that AEAPMDS grafted successfully without destroying the basic morphology of the CNCs. The formaldehyde-free decorative paper coated with AEAPMDS-CNCs had high CO2 adsorption capacity and exhibited excellent performance of veneer to plywood. Therefore, laminating the prepared formaldehyde-free decorative paper onto indoor furniture can achieve the purpose of capturing indoor CO2 and have a highly potential use for the indoor decoration. Full article
Show Figures

Figure 1

Open AccessArticle
Molecular Insights into Sequence Distributions and Conformation-Dependent Properties of High-Phenyl Polysiloxanes
Polymers 2019, 11(12), 1989; https://doi.org/10.3390/polym11121989 - 02 Dec 2019
Abstract
The excellent performance and wide applications of phenyl polysiloxanes are largely due to their phenyl units and monomer sequences. However, the relationship between molecular structure and material properties has not been explicitly elucidated. In this work, the sequence distribution and microstructure of random [...] Read more.
The excellent performance and wide applications of phenyl polysiloxanes are largely due to their phenyl units and monomer sequences. However, the relationship between molecular structure and material properties has not been explicitly elucidated. In this work, the sequence distribution and microstructure of random copolymers were quantitatively investigated by means of a molecular dynamics (MD) simulation combined with experimental verification. The results of 29Si NMR showed that the large number of phenyl units not only shortened the length of the dimethyl units, but also significantly increased the proportion of consecutive phenyl units. The simulation results indicated the attraction between adjacent phenyl groups that were effectively strengthened intra- and inter- molecular interactions, which determined the equilibrium population of conformations and the dynamics of conformational transitions. Furthermore, the evolution of bond angle distribution, torsion distribution, and mean-squared displacements (MSD) shed light on the conformational characteristics that induce the unique thermodynamics properties and photophysical behavior of high-phenyl polysiloxanes. Differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA), spectrofluorimetry, and laser scanning confocal microscopy (LSCM) were performed to verify the conclusions drawn from the simulation. Overall, the complementary use of MD simulations and experiments provided a deep molecular insight into structure–property relationships, which will provide theoretical guidance for the rational design and preparation of high-performance siloxanes. Full article
Show Figures

Graphical abstract

Open AccessArticle
Surface Modification of Fumed Silica by Plasma Polymerization of Acetylene for PP/POE Blends Dielectric Nanocomposites
Polymers 2019, 11(12), 1957; https://doi.org/10.3390/polym11121957 - 28 Nov 2019
Cited by 2
Abstract
Novel nanocomposites for dielectric applications-based polypropylene/poly(ethylene-co-octene) (PP/POE) blends filled with nano silica are developed in the framework of the European ‘GRIDABLE’ project. A tailor-made low-pressure-plasma reactor was applied in this study for an organic surface modification of silica. Acetylene gas was used as [...] Read more.
Novel nanocomposites for dielectric applications-based polypropylene/poly(ethylene-co-octene) (PP/POE) blends filled with nano silica are developed in the framework of the European ‘GRIDABLE’ project. A tailor-made low-pressure-plasma reactor was applied in this study for an organic surface modification of silica. Acetylene gas was used as the monomer for plasma polymerization in order to deposit a hydrocarbon layer onto the silica surface. The aim of this modification is to increase the compatibility between silica and the PP/POE blends matrix in order to improve the dispersion of the filler in the polymer matrix and to suppress the space charge accumulation by altering the charge trapping properties of these silica/PP/POE blends composites. The conditions for the deposition of the acetylene plasma-polymer onto the silica surface were optimized by analyzing the modification in terms of weight loss by thermogravimetry (TGA). X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray fluorescence spectroscopy (EDX) measurements confirmed the presence of hydrocarbon compounds on the silica surface after plasma modification. The acetylene plasma modified silica with the highest deposition level was selected to be incorporated into the PP/POE blends matrix. X-ray diffraction (XRD) showed that there is no new crystal phase formation in the PP/POE blends nanocomposites after addition of the acetylene plasma modified silica. Differential scanning calorimetry results (DSC) show two melting peaks and two crystallization peaks of the PP/POE blends nanocomposites corresponding to the PP and POE domains. The improved dispersion of the silica after acetylene plasma modification in the PP/POE blends matrix was shown by means of SEM–EDX mapping. Thermally stimulated depolarization current (TSDC) measurements confirm that addition of the acetylene plasma modified silica affects the charge trapping density and decreases the amount of injected charges into PP/POE blends nanocomposites. This work shows that acetylene plasma modification of the silica surface is a promising route to tune charge trapping properties of PP/POE blend-based nanocomposites. Full article
Show Figures

Graphical abstract

Open AccessArticle
Facile Fabrication of Superhydrophobic Surface from Fluorinated POSS Acrylate Copolymer via One-Step Breath Figure Method and Its Anti-Corrosion Property
Polymers 2019, 11(12), 1953; https://doi.org/10.3390/polym11121953 - 28 Nov 2019
Cited by 2
Abstract
Novel fluorinated polyhedral oligomeric silsesquioxane (POSS) acrylic copolymers were synthesized by the radical solution polymerization. The superhydrophobic coating was prepared using a one-step breath figure method. Chemical constitution, morphology, hydrophobicity, and anticorrosion ability of as-prepared coatings were investigated by the corresponding equipment. The [...] Read more.
Novel fluorinated polyhedral oligomeric silsesquioxane (POSS) acrylic copolymers were synthesized by the radical solution polymerization. The superhydrophobic coating was prepared using a one-step breath figure method. Chemical constitution, morphology, hydrophobicity, and anticorrosion ability of as-prepared coatings were investigated by the corresponding equipment. The addition of proper fluorinated POSS can synchronously promote the formation of the micro-nano convex structure and the enrichment of fluorinated groups on the surface. Compared to commercial acrylic coating, the fluorinated POSS coating presented enhanced anticorrosion performance. The impedance was the highest and the corrosion current density was the lowest for superhydrophobic coating with 25 wt % fluorinated POSS. Full article
Show Figures

Graphical abstract

Open AccessArticle
Improvement of Rice Husk/HDPE Bio-Composites Interfacial Properties by Silane Coupling Agent and Compatibilizer Complementary Modification
Polymers 2019, 11(12), 1928; https://doi.org/10.3390/polym11121928 - 22 Nov 2019
Cited by 1
Abstract
Composites using agricultural and forestry residues as raw materials with potentially high-performance, multifunctional and biodegradable ecological advantages, are viewed as very promising for new-generation lightweight and low-cost bio-based sustainable building materials. At present, the research on wood-plastic composite materials is relatively mature. However, [...] Read more.
Composites using agricultural and forestry residues as raw materials with potentially high-performance, multifunctional and biodegradable ecological advantages, are viewed as very promising for new-generation lightweight and low-cost bio-based sustainable building materials. At present, the research on wood-plastic composite materials is relatively mature. However, it is still a challenge to effectively use other biomass and improve the interface of the high-polymer compound system. Herein, we proposed a simple and effective method to enhance the interfacial adhesion properties of rice husk fibre and High Density Polyethylene (HDPE) composites by the silane coupling agent KH-550 and compatibilizer Maleic anhydride grafted polyethylene (MAPE) with complementary modification. It was found that the coupling agent KH-550 cross-linked with the hydroxyl group on the husk fibre surface and solidified with the high polymer by –NH–, –C=O– functional group generation. Compatibilizer MAPE strengthened the two phases by covalently bonding with an ester linkage and lowered the roughness of the cross-section of the composites. Meanwhile the modification enhanced the dispersibility, and mechanical properties of the husk-high polymer compound system, the bending and flexural strength were improved by 11.5% and 28.9% with KH-550, and MAPE added, respectively. The flexural strength of the composites increased by 40.7% after complementary modification. Furthermore, the complementary modification treatment reduced the hydrophilic hydroxyl groups and increased the molecular chain to improve the water-resistance, elastic modulus and toughness of the composite. This study prepared a bio-composite, which is expected to expand the use of agricultural and forestry residues as an extension of wood-plastic composites. Full article
Show Figures

Figure 1

Open AccessArticle
Dispersed-Monolayer Graphene-Doped Polymer/Silica Hybrid Mach-Zehnder interferometer (MZI) Thermal Optical Switch with Low-Power Consumption and Fast Response
Polymers 2019, 11(11), 1898; https://doi.org/10.3390/polym11111898 - 18 Nov 2019
Cited by 2
Abstract
This article demonstrates a dispersed-monolayer graphene-doped polymer/silica hybrid Mach–Zehnder interferometer (MZI) thermal optical switch with low-power consumption and fast response. The polymer/silica hybrid MZI structure reduces the power consumption of the device as a result of the large thermal optical coefficient of the [...] Read more.
This article demonstrates a dispersed-monolayer graphene-doped polymer/silica hybrid Mach–Zehnder interferometer (MZI) thermal optical switch with low-power consumption and fast response. The polymer/silica hybrid MZI structure reduces the power consumption of the device as a result of the large thermal optical coefficient of the polymer material. To further decrease the response time of the thermal optical switch device, a polymethyl methacrylate, doped with monolayer graphene as a cladding material, has been synthesized. Our study theoretically analyzed the thermal conductivity of composites using the Lewis–Nielsen model. The predicted thermal conductivity of the composites increased by 133.16% at a graphene volume fraction of 0.263 vol %, due to the large thermal conductivity of graphene. Measurements taken of the fabricated thermal optical switch exhibited a power consumption of 7.68 mW, a rise time of 40 μs, and a fall time of 80 μs at a wavelength of 1550 nm. Full article
Show Figures

Graphical abstract

Open AccessCommunication
Facile Functionalization of Poly(Dimethylsiloxane) Elastomer by Varying Content of Hydridosilyl Groups in a Crosslinker
Polymers 2019, 11(11), 1842; https://doi.org/10.3390/polym11111842 - 08 Nov 2019
Abstract
Crosslinked poly(dimethylsiloxane) (PDMS) has been widely used as a dielectric elastomer for electrically driven actuators because it exhibits high elasticity, low initial modulus, and excellent moldability in spite of low dielectric constant. However, further improvement in the characteristics of the PDMS elastomer is [...] Read more.
Crosslinked poly(dimethylsiloxane) (PDMS) has been widely used as a dielectric elastomer for electrically driven actuators because it exhibits high elasticity, low initial modulus, and excellent moldability in spite of low dielectric constant. However, further improvement in the characteristics of the PDMS elastomer is not easy due to its chemical non-reactivity. Here, we report a simple method for functionalizing the elastomer by varying content of hydridosilyl groups in PDMS acted as a crosslinker. We synthesized poly(dimethylsiloxane-co-methylvinylsiloxane) (VPDMS) and poly(dimethylsiloxane-co-methylsiloxane) (HPDMS). Tri(ethylene glycol) divinyl ether (TEGDE) as a polar molecule was added to the mixture of VPDMS and HPDMS. TEGDE was reacted to the hydridosilyl group in HPDMS during crosslinking between VPDMS and HPDMS in the presence of platinum as a catalyst. Permittivity of the crosslinked film increased from ca. 25 to 36 pF/m at 10 kHz without a decline in other physical properties such as transparency and elasticity (T > 85%, E ~150 kPa, ɛ ~270%). It depends on the hydridosilyl group content of HPDMS. The chemical introduction of a new molecule into the hydridosilyl group in HPDMS during crosslinking would provide a facile, effective method of modifying the PDMS elastomers. Full article
Show Figures

Graphical abstract

Open AccessArticle
Preparation and Characterization of Soy Protein Isolate-Based Nanocomposite Films with Cellulose Nanofibers and Nano-Silica via Silane Grafting
Polymers 2019, 11(11), 1835; https://doi.org/10.3390/polym11111835 - 07 Nov 2019
Abstract
Soy protein isolate (SPI) has attracted considerable attention in the field of packaging technology due to its easy processability, biodegradability, and good film-forming characteristics. However, SPI-based films often suffer from inferior mechanical properties and high moisture sensitivity, thus restricting their practical application. In [...] Read more.
Soy protein isolate (SPI) has attracted considerable attention in the field of packaging technology due to its easy processability, biodegradability, and good film-forming characteristics. However, SPI-based films often suffer from inferior mechanical properties and high moisture sensitivity, thus restricting their practical application. In the present study, herein, a biobased nanocomposite film was developed by cross-linking SPI matrix from the synergistic reinforcement of cellulose nanofibers (CNF) and nano-silica (NS) particles. First, we functionalized the CNF with NS using a silane agent (KH560) as an efficient platform to enhance the interfacial interaction between SPI and CNF/NS, resulting from the epoxy-dominated cross-linking reaction. The chemical structure, thermal stability, and morphology of the resultant nanocomposite films were comprehensively investigated via Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). These results supported successful surface modification and indicated that the surface-tailored CNF/NS nanohybrid possesses excellent adhesion with SPI matrix through covalent and hydrogen-bonding interactions. The integration of CNF/NS into SPI resulted in nanocomposite films with an improved tensile strength (6.65 MPa), representing a 90.54% increase compared with the pristine SPI film. Moreover, the resulting composites had a significantly decreased water vapor permeation and a higher water contact angle (91.75°) than that of the unmodified film. The proposed strategy of synergistic reinforcements in the biobased composites may be a promising and green approach to address the critical limitations of plant protein-based materials in practical applications. Full article
Show Figures

Graphical abstract

Open AccessArticle
Core-Shell Structure Design of Hollow Mesoporous Silica Nanospheres Based on Thermo-Sensitive PNIPAM and pH-Responsive Catechol-Fe3+ Complex
Polymers 2019, 11(11), 1832; https://doi.org/10.3390/polym11111832 - 07 Nov 2019
Cited by 1
Abstract
A kind of core-shell hybrid nanoparticle comprised of a hollow mesoporous silica nanoparticles (HMS) core and a copolymer shell bearing N-(3,4-dihydroxyphenethyl) methacrylamide (DMA) and N-isopropylacrylamide (NIPAM) as responsive moieties was prepared. Moreover, the factors that could impact the surface morphology and hierarchical porous [...] Read more.
A kind of core-shell hybrid nanoparticle comprised of a hollow mesoporous silica nanoparticles (HMS) core and a copolymer shell bearing N-(3,4-dihydroxyphenethyl) methacrylamide (DMA) and N-isopropylacrylamide (NIPAM) as responsive moieties was prepared. Moreover, the factors that could impact the surface morphology and hierarchical porous structure were discussed. In the presence of Fe3+, catechol-Fe3+ complexes were formed to achieve pH-responsive polymer shell, combining with thermal-sensitiveness of poly(N-isopropylacrylamide). Doxorubicin (DOX) was applied as a model drug and the behaviors of its loading/release behaviors were investigated to prove the idea. The results exhibited a significant drug loading capacity of 8.6% and embed efficiency of 94.6% under 1 mg ml–1 DOX/PBS solution. In fact, the loading capacity of drug can be easily improved to as high as 28.0% by increasing the DOX concentration. The vitro cytotoxicity assay also indicated that the as-prepared nanoparticles have no significant cytotoxicity on RAW 264.7 cells. The in vitro experiment showed that the cumulative release of DOX was obviously dependent on the temperature and pH values. This pH/temperature-sensitive hollow mesoporous silica nanosphere is expected to have potential applications in controlled drug release. Full article
Show Figures

Graphical abstract

Open AccessArticle
Preparation and Performance of Silica/ESBR Nanocomposites Modified by Bio-Based Dibutyl Itaconate
Polymers 2019, 11(11), 1820; https://doi.org/10.3390/polym11111820 - 06 Nov 2019
Abstract
Ester-functionalized styrene-butadiene rubber (dibutyl itaconate-styrene-butadiene rubber) (D-ESBR) was synthesized by low-temperature emulsion polymerization using dibutyl itaconate (DBI) as a modified monomer containing ester groups. Nonpetroleum-based silica with hydroxy groups was used as a filler to enhance the D-ESBR, which can provide excellent mechanical [...] Read more.
Ester-functionalized styrene-butadiene rubber (dibutyl itaconate-styrene-butadiene rubber) (D-ESBR) was synthesized by low-temperature emulsion polymerization using dibutyl itaconate (DBI) as a modified monomer containing ester groups. Nonpetroleum-based silica with hydroxy groups was used as a filler to enhance the D-ESBR, which can provide excellent mechanical properties, low rolling resistance, and high wet skid resistance. During the preparation of the silica/D-ESBR nanocomposites, a hydrogen-bonding interface was formed between the hydroxy groups on the surface of silica and the ester groups in the D-ESBR macromolecules. As the content of ester groups in the D-ESBR increases, the dispersion of silica in the nanocomposites is gradually improved, which was verified by rubber process analyzer (RPA) and scanning electron microscopy (SEM). Overall mechanical properties of the silica/D-ESBR modified with 5 wt % DBI were improved and became superior to that of the non-modified nanocomposite. Compared with the non-modified silica/D-ESBR, the DBI modified silica/D-ESBR exhibited a lower tan δ value at 60 °C and comparable tan δ value at 0 °C, indicating that the DBI modified silica/D-ESBR had lower rolling resistance without sacrificing wet skid resistance. Full article
Show Figures

Graphical abstract

Open AccessArticle
Silicone Resin Polymer Used in Preventive Maintenance of Asphalt Mixture Based on Fog Seal
Polymers 2019, 11(11), 1814; https://doi.org/10.3390/polym11111814 - 05 Nov 2019
Cited by 2
Abstract
The commonly used materials in fog seal are emulsified asphalt and modified emulsified asphalt. Nevertheless, there are some intractable problems including aging under ultraviolet, poor permeability, and moisture susceptibility. Therefore, silicone resin polymer was used as a kind of innovative fog seal material [...] Read more.
The commonly used materials in fog seal are emulsified asphalt and modified emulsified asphalt. Nevertheless, there are some intractable problems including aging under ultraviolet, poor permeability, and moisture susceptibility. Therefore, silicone resin polymer was used as a kind of innovative fog seal material in this study. Physicochemical properties of solidified silicone resin were characterized. X-ray computed tomography and 3D reconstruction technology were used to evaluate permeability and distribution of silicone resin polymer in an asphalt mixture. Moisture sensitivity and high-temperature performance of the asphalt mixture maintained by silicone resin polymer were also detected. The results show that surface characteristic of silicone resin can effectively isolate moisture, thereby improving moisture resistance of the asphalt mixture. Silicone resin was found to be evenly distributed throughout the pores of a sample when the dosage was 400 or 600 mL/m2. The pore filling rate increased by 16.3% when the dosage was changed from 200 to 400 mL/m2, whereas it only increased by 3.7% when dosage increased from 400 to 600 mL/m2. Moisture damage resistance of asphalt mixtures generally increased as the dosage of silicone was increased. However, as the dosage increased from 400 to 600 mL/m2, the growth rate in residual Marshall stability (RMS) and tensile strength ratio (TSR) slowed significantly since the pore filling effect of silicone has reached the upper limit. Dosage of silicone resin has little effect on the results of the rutting test while it has significant influence on Hamburg wheel tracking test (HWT). Furthermore, it was found that 400 mL/m2 is the optimum silicone dosage for open-graded friction course (OGFC)-13 mixture in consideration of permeability, distribution, performance of mixture, and economic cost. Full article
Show Figures

Graphical abstract

Open AccessEditorial
POSS-Based Polymers
Polymers 2019, 11(10), 1727; https://doi.org/10.3390/polym11101727 - 22 Oct 2019
Cited by 1
Abstract
The combination of functional polymers with inorganic nanostructured compounds has become a major area of research and technological development owing to the remarkable properties and multifunctionalities deriving from their nano and hybrid structures [...] Full article
Open AccessArticle
Hybrid Silica-Phytic Acid Coatings: Effect on the Thermal Stability and Flame Retardancy of Cotton
Polymers 2019, 11(10), 1664; https://doi.org/10.3390/polym11101664 - 12 Oct 2019
Cited by 2
Abstract
New hybrid sol–gel coatings based on tetraethoxysilane (TEOS) and phytic acid (PA) were designed and applied to cotton; the flame-retardant properties of the treated fabrics were thoroughly investigated by means of flame-spread and forced-combustion tests. The first goal was to identify the TEOS:PA [...] Read more.
New hybrid sol–gel coatings based on tetraethoxysilane (TEOS) and phytic acid (PA) were designed and applied to cotton; the flame-retardant properties of the treated fabrics were thoroughly investigated by means of flame-spread and forced-combustion tests. The first goal was to identify the TEOS:PA weight ratio that allowed the achievement of the best flame-retardant properties, with the lowest final dry add-on on the fabrics. Therefore, different TEOS:PA sols were prepared and applied to cotton, and the resulting coated fabrics were thoroughly investigated. In particular, solid-state NMR spectroscopy was exploited for assessing the condensation degree during the sol–gel process, even for evaluating the occurrence of possible reactions between phytic acid and the cellulosic substrate or the alkoxy precursor. It was found that a total dry add-on of 16 wt % together with 70:30 TEOS:PA weight ratio provided cotton with self-extinction, as clearly indicated by flame-spread tests. This formulation was further investigated in forced-combustion tests: a significant reduction of heat release rate (HRR), of the peak of HRR, and of total heat release (THR) was found, together with a remarkable increase of the residues after the test. Unfortunately, the treated fabrics were not resistant to washing cycles, as they significantly lost their flame-retardant properties, consequently to the partial removal of the deposited hybrid coatings. Full article
Show Figures

Graphical abstract

Open AccessArticle
Facile Strategy of Improving Interfacial Strength of Silicone Resin Composites Through Self-Polymerized Polydopamine Followed via the Sol-Gel Growing of Silica Nanoparticles onto Carbon Fiber
Polymers 2019, 11(10), 1639; https://doi.org/10.3390/polym11101639 - 10 Oct 2019
Cited by 3
Abstract
In the present research, to enhance interfacial wettability and adhesion between carbon fibers (CFs) and matrix resin, hydrophilic silica nanoparticles (SiO2) were utilized to graft the surface of CFs. Polydopamine (PDA) as a “bio-glue” was architecturally built between SiO2 and [...] Read more.
In the present research, to enhance interfacial wettability and adhesion between carbon fibers (CFs) and matrix resin, hydrophilic silica nanoparticles (SiO2) were utilized to graft the surface of CFs. Polydopamine (PDA) as a “bio-glue” was architecturally built between SiO2 and CFs to obtain a strong adhesion strength and homogenous SiO2 distribution onto the surface of CFs. The facile modification strategy was designed by self-polymerization of dopamine followed by the hydrolysis of tetraethoxysilane (TEOS) onto carbon fibers. Surface microstructures and interfacial properties of CFs, before and after modification, were systematically investigated. The tight and homogeneous coverage of SiO2 layers onto the CF surface, with the assistance of a PDA layer by self-polymerization of dopamine, significantly enhanced fiber surface roughness and wettability, resulting in an obvious improvement of mechanical interlocking and interfacial interactions between CFs and matrix resin. The interlaminar shear strength (ILSS) and the interfacial shear strength (IFSS) of CF/PDA/SiO2 reinforced composites exhibited 57.28% and 41.84% enhancements compared with those of untreated composites. In addition, impact strength and the hydrothermal aging resistance of the resulting composites showed great improvements after modification. The possible reinforcing mechanisms during the modification process have been discussed. This novel strategy of developed SiO2-modified CFs has interesting potential for interfacial improvements for advanced polymer composites. Full article
Show Figures

Graphical abstract

Open AccessArticle
In situ Fabrication of Multi-Walled Carbon Nanotubes/Silica Hybrid Colloidosomes by Pickering Emulsion Templating Using Trialkoxysilanes of Opposite Polarity
Polymers 2019, 11(9), 1480; https://doi.org/10.3390/polym11091480 - 10 Sep 2019
Cited by 1
Abstract
A simple and effective way to prepare multi-walled carbon nanotubes (MWNT)//silica hybrid microcapsules (colloidosomes) is presented. These microcapsules have been generated by emulsion templating in a biphasic oil-in-water (o/w) system. Two trialkoxysilanes of complementary polarity, (3-aminopropyl)triethoxysilane (APTES) and dodecyltriethoxysilane (DTES), were used to [...] Read more.
A simple and effective way to prepare multi-walled carbon nanotubes (MWNT)//silica hybrid microcapsules (colloidosomes) is presented. These microcapsules have been generated by emulsion templating in a biphasic oil-in-water (o/w) system. Two trialkoxysilanes of complementary polarity, (3-aminopropyl)triethoxysilane (APTES) and dodecyltriethoxysilane (DTES), were used to chemically immobilize the silica nanoparticles at the o/w interface and stabilize the as-generated Pickering emulsions. The effects of varying the o/w ratio and the concentration of the added solids on the type of emulsion formed, the oil droplet size, as well as the emulsion stability have been investigated. The emulsion phase fraction was dependent on the silica content while the droplet size increased with increasing oil volume percentage. A solid shell emerged around the oil droplets from copolymerization between silane monomers. The thickness of the resulting shells was several hundreds of nm. Although MWNTs and silica nanoparticles both were co-assembled at the o/w interface, silica has shown to be the sole stabilizer, with APTES being crucial for the formation of the shell structure. Drop-casting of the emulsion and air-drying led to hierarchical open porous MWNT-silica nanocomposites. These new structures are promising as electrically conductive thin films for variety of applications, such as electro-optics, encapsulation, or chemical sensing. Full article
Show Figures

Figure 1

Open AccessArticle
A Simple Preparation Route for Bio-Phenol MQ Silicone Resin via the Hydrosilylation Method and its Autonomic Antibacterial Property
Polymers 2019, 11(9), 1389; https://doi.org/10.3390/polym11091389 - 23 Aug 2019
Cited by 2
Abstract
MQ silicone resins represent a broad range of hydrolytic condensation products of monofunctional silane (M units) and tetrafunctional silane (Q units). In this work, a Bio-Phenol MQ silicone resin (BPMQ) was designed and synthesized by the hydrosilylation of hydrogen containing MQ silicone resin [...] Read more.
MQ silicone resins represent a broad range of hydrolytic condensation products of monofunctional silane (M units) and tetrafunctional silane (Q units). In this work, a Bio-Phenol MQ silicone resin (BPMQ) was designed and synthesized by the hydrosilylation of hydrogen containing MQ silicone resin and eugenol in the presence of chloroplatinic acid. The structure, thermal property, and antibacterial property against Escherichia coli of the modified MQ silicone resin were investigated. The results showed that BPMQ has been prepared successfully, and the thermal stability of this modified polymer improved significantly because of the introduction of phenyl in eugenol. The temperature at the maximum degradation rate increased from 250 °C to 422.5 °C, and the residual yields mass left at 600 °C were increased from 2.0% to 28.3%. In addition, its antibacterial property against Escherichia coli was also enhanced markedly without adding any other antimicrobial agents. This improved performance is ascribed to special functional groups in the structure of eugenol. The BPMQ polymer is expected to be applied to pressure-sensitive adhesives and silicone rubber products for the biomedical field due to its reinforcing effect and antioxidant quality. Full article
Show Figures

Graphical abstract

Open AccessArticle
Raspberry-Like Polysilsesquioxane Particles with Hollow-Spheres-on-Sphere Structure: Rational Design, Controllable Synthesis, and Catalytic Application
Polymers 2019, 11(8), 1350; https://doi.org/10.3390/polym11081350 - 14 Aug 2019
Cited by 5
Abstract
Raspberry-like hollow-spheres-on-sphere (HSOS) particles with reactive surfaces, uniform sizes and monodisperse properties were rational designed and fabricated to immobilize gold nanoparticles for the catalytic reduction of 4-nitrophenol. HSOS polysilsesquioxane (PSQ) particles were constructed by an organic alkali catalyzed sol-gel process from trialkoxysilane precursors [...] Read more.
Raspberry-like hollow-spheres-on-sphere (HSOS) particles with reactive surfaces, uniform sizes and monodisperse properties were rational designed and fabricated to immobilize gold nanoparticles for the catalytic reduction of 4-nitrophenol. HSOS polysilsesquioxane (PSQ) particles were constructed by an organic alkali catalyzed sol-gel process from trialkoxysilane precursors with stabilized polystyrene (PS) nanoparticles as both a sacrifice template and a Pickering emulsifier. The PSQ particles were fabricated in an ice bath with methyltrimethoxysilane and mercaptopropyltrimethoxysiane as a co-precursor, tetramethylammonium hydroxide (TMAH) as a catalyst, polyvinylpyrrolidone (PVP) and sodium lignosulfonat as co-stabilizers and PS latex as a hard template. The formation mechanism of the hierarchical particles was investigated in detail by the time study through imaging the particles at regular time intervals during the reaction process. Various effect factors on the morphology were studied systematically which showed that the precursor composition, the content of PS, TMAH and PVP are the most important factors. The hierarchical structure combined with the mercaptopropyl groups on both the surface and the skeleton to make it possible to adsorb guest molecules. Au nanoparticles were immobilized on the particles for the catalytic reduction of 4-nitrophenol to 4-aminophenol. The unique PSQ colloids with hollow-spheres-on-sphere extended the family of the hierarchical structures and has shown the potential applications in separations, drug delivery and heterogeneous catalysts. Full article
Show Figures

Figure 1

Open AccessArticle
Replicated Pattern Formation and Recognition Properties of 2,4-Dichlorophenoxyacetic Acid-Imprinted Polymers Using Colloidal Silica Array Molds
Polymers 2019, 11(8), 1332; https://doi.org/10.3390/polym11081332 - 11 Aug 2019
Cited by 1
Abstract
Surface imprinting is an effective and simple method to fabricate and retain imprinted templates and recognizable nanocavities after template extraction. The imprinted effects can be controlled depending on the surface morphological changes. In general, a planar film has a limited area compared to [...] Read more.
Surface imprinting is an effective and simple method to fabricate and retain imprinted templates and recognizable nanocavities after template extraction. The imprinted effects can be controlled depending on the surface morphological changes. In general, a planar film has a limited area compared to a structured film with relatively higher surface-to-volume (S/V) ratio (A/A0), leading to the conventional sensing response upon the functionality of monomers in a fixed chemical composition. To increase the limited sensing properties and develop simple fabrication of porous arrays on a large area, we herein demonstrate the 2,4-dichlorophenoxyacetic acid (2,4-D, herbicide)-imprinted porous thin film lithographically patterned using photopolymerization and silica colloidal array as a master mold, derived by a unidirectional rubbing method. The resonant frequency changes with respect to the adsorption of 2,4-D molecules on a template-extracted porous poly(MAA-co-EGDMA) (MIP) film in a 10−1 mM aqueous solution of 2,4-D for 1 h, and when compared to the planar MIP film, the higher sensing response (Δf = −283 ± 7 Hz ≈ 1543 ± 38 ng/cm2) appears on the porous MIP film due to the specific recognition toward the more accessible templated cavities of the structured porous array, indicating an imprinting effect (If) value of 3.5. In addition, a higher selectivity for 2,4-D was also displayed on the porous MIP film compared to other herbicides. From these results, it was revealed that these improved sensing properties can be determined from the effects of various parameters (template functionality, film structuring, hydroxyl groups of silica colloids, etc.). Full article
Show Figures

Graphical abstract

Open AccessReview
A Review on Porous Polymeric Membrane Preparation. Part II: Production Techniques with Polyethylene, Polydimethylsiloxane, Polypropylene, Polyimide, and Polytetrafluoroethylene
Polymers 2019, 11(8), 1310; https://doi.org/10.3390/polym11081310 - 05 Aug 2019
Cited by 9
Abstract
The development of porous polymeric membranes is an important area of application in separation technology. This article summarizes the development of porous polymers from the perspectives of materials and methods for membrane production. Polymers such as polyethylene, polydimethylsiloxane, polypropylene, polyimide, and polytetrafluoroethylene are [...] Read more.
The development of porous polymeric membranes is an important area of application in separation technology. This article summarizes the development of porous polymers from the perspectives of materials and methods for membrane production. Polymers such as polyethylene, polydimethylsiloxane, polypropylene, polyimide, and polytetrafluoroethylene are reviewed due to their outstanding thermal stability, chemical resistance, mechanical strength, and low cost. Six different methods for membrane fabrication are critically reviewed, including thermally induced phase separation, melt-spinning and cold-stretching, phase separation micromolding, imprinting/soft molding, manual punching, and three-dimensional printing. Each method is described in details related to the strategy used to produce the porous polymeric membranes with a specific morphology and separation performances. The key factors associated with each method are presented, including solvent/non-solvent system type and composition, polymer solution composition and concentration, processing parameters, and ambient conditions. Current challenges are also described, leading to future development and innovation to improve these membranes in terms of materials, fabrication equipment, and possible modifications. Full article
Show Figures

Figure 1

Open AccessArticle
Improving Oxygen Permeability and Thermostability of Polycarbonate via Copolymerization Modification with Bio-Phenol Polysiloxane
Polymers 2019, 11(8), 1302; https://doi.org/10.3390/polym11081302 - 03 Aug 2019
Cited by 2
Abstract
As a new kind of functionalized polysiloxane with chemical reactivity, bio-phenol polysiloxane was synthesized through facile heterogeneous catalytic route. Bio-phenol polysiloxane/polycarbonate (Si/PC) block copolymer was synthesized via a three-step approach, and the effect of the amount of bio-phenol polysiloxane on the properties of [...] Read more.
As a new kind of functionalized polysiloxane with chemical reactivity, bio-phenol polysiloxane was synthesized through facile heterogeneous catalytic route. Bio-phenol polysiloxane/polycarbonate (Si/PC) block copolymer was synthesized via a three-step approach, and the effect of the amount of bio-phenol polysiloxane on the properties of Si/PC copolymer was then studied. The structure and morphology of Si/PC copolymer were characterized, showing that, when the amount of bio-phenol polysiloxane reached 20%, the pyrolysis temperature of Si/PC copolymer at 5% weight loss was 450.8 °C which was 76.1 °C higher than pure PC. The oxygen permeability of 20%Si/PC copolymer membrane was 502.65 cm3/m2·24h·0.1MPa, which was increased by 128.4% compared with pure PC membrane. The mechanical property and hydrophobicity of Si/PC copolymer had been improved. Full article
Show Figures

Figure 1

Open AccessArticle
Surface-Induced ARGET ATRP for Silicon Nanoparticles with Fluorescent Polymer Brushes
Polymers 2019, 11(7), 1228; https://doi.org/10.3390/polym11071228 - 23 Jul 2019
Cited by 2
Abstract
Well-defined polymer brushes attached to nanoparticles offer an elegant opportunity for surface modification because of their excellent mechanical stability, functional versatility, high graft density as well as controllability of surface properties. This study aimed to prepare hybrid materials with good dispersion in different [...] Read more.
Well-defined polymer brushes attached to nanoparticles offer an elegant opportunity for surface modification because of their excellent mechanical stability, functional versatility, high graft density as well as controllability of surface properties. This study aimed to prepare hybrid materials with good dispersion in different solvents, and to endow this material with certain fluorescence characteristics. Well-defined diblock copolymers poly (styrene)-b-poly (hydroxyethyl methyl acrylate)–co-poly (hydroxyethyl methyl acrylate- rhodamine B) grafted silica nanoparticles (SNPs-g-PS-b-PHEMA-co-PHEMA-RhB) hybrid materials were synthesized via surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP). The SNPs surfaces were modified by 3-aminopropyltriethoxysilane (KH-550) firstly, then the initiators 2-Bromoisobutyryl bromide (BIBB) was attached to SNPs surfaces through the esterification of acyl bromide groups and amidogen groups. The synthetic initiators (SNPs-Br) were further used for the SI-ARGET ATRP of styrene (St), hydroxyethyl methyl acrylate (HEMA) and hydroxyethyl methyl acrylate-rhodamine B (HEMA-RhB). The results indicated that the SI-ARGET ATRP initiator had been immobilized onto SNPs surfaces, the Br atom have located at the end of the main polymer chains, and the polymerization process possessed the characteristic of controlled/“living” polymerization. The SNPs-g-PS-b-PHEMA-co-PHEMA-RhB hybrid materials show good fluorescence performance and good dispersion in water and EtOH but aggregated in THF. This study demonstrates that the SI-ARGET ATRP provided a unique way to tune the polymer brushes structure on silica nanoparticles surface and further broaden the application of SI-ARGET ATRP. Full article
Show Figures

Graphical abstract

Open AccessArticle
Design and Application of Highly Efficient Flame Retardants for Polycarbonate Combining the Advantages of Cyclotriphosphazene and Silicone Oil
Polymers 2019, 11(7), 1155; https://doi.org/10.3390/polym11071155 - 05 Jul 2019
Cited by 2
Abstract
A novel flame retardant (HSPCTP) was successfully designed and incorporated into a polycarbonate (PC) matrix. Combining the advantages of cyclotriphosphazene and silicone oil, PC/HSPCTP composites passed UL-94 V-0 rating testing with only 3 wt% HSPCTP, and their LOI value increased from 25.0% to [...] Read more.
A novel flame retardant (HSPCTP) was successfully designed and incorporated into a polycarbonate (PC) matrix. Combining the advantages of cyclotriphosphazene and silicone oil, PC/HSPCTP composites passed UL-94 V-0 rating testing with only 3 wt% HSPCTP, and their LOI value increased from 25.0% to 28.4%. The findings showed that HSPCTP exhibits both gas-phase and solid-phase flame-retardant effects. Furthermore, the incorporation of HSPCTP into PC could suppress the release of smoke. Finally, the flame-retardant mechanism is discussed in depth. Full article
Show Figures

Figure 1

Open AccessArticle
Synthesis and Characterization of Room Temperature Vulcanized Silicone Rubber Using Methoxyl-Capped MQ Silicone Resin as Self-Reinforced Cross-Linker
Polymers 2019, 11(7), 1142; https://doi.org/10.3390/polym11071142 - 03 Jul 2019
Cited by 5
Abstract
Methoxyl-capped MQ silicone resin (MMQ) was first synthesized by the hydrosilylation of vinyl-containing MQ silicone resin and trimethoxysilane and then used in condensed room-temperature vulcanized (RTV) silicone rubber as a self-reinforced cross-linker. Results show that modified silicone rubber exhibits good light transmission. Compared [...] Read more.
Methoxyl-capped MQ silicone resin (MMQ) was first synthesized by the hydrosilylation of vinyl-containing MQ silicone resin and trimethoxysilane and then used in condensed room-temperature vulcanized (RTV) silicone rubber as a self-reinforced cross-linker. Results show that modified silicone rubber exhibits good light transmission. Compared with unmodified silicone rubber, the hardness, tensile strength and elongation of MMQ at the break are increased by 26.4 A, 2.68 MPa and 65.1%, respectively. In addition, the characteristic temperature of 10% mass loss is delayed from 353.5 °C to 477.1 °C, the temperature at maximum degradation rate is also delayed from 408.9 °C to 528.4 °C and the residual mass left at 800 °C is increased from 1.2% to 27.7%. These improved properties are assigned to the synergistic effect of the rigid structure of MMQ, the formation of a dense cross-linking structure in polymers and the uniform distribution of MMQ cross-linking agent in RTV silicone rubber. Full article
Show Figures

Figure 1

Open AccessArticle
Influence of Surface Modified Nanodiamonds on Dielectric and Mechanical Properties of Silicone Composites
Polymers 2019, 11(7), 1104; https://doi.org/10.3390/polym11071104 - 29 Jun 2019
Cited by 2
Abstract
Detonation nanodiamonds, also known as ultradispersed diamonds, possess versatile chemically active surfaces, which can be adjusted to improve their interaction with elastomers. Such improvements can result in decreased dielectric and viscous losses of the composites without compromising other in-rubber properties, thus making the [...] Read more.
Detonation nanodiamonds, also known as ultradispersed diamonds, possess versatile chemically active surfaces, which can be adjusted to improve their interaction with elastomers. Such improvements can result in decreased dielectric and viscous losses of the composites without compromising other in-rubber properties, thus making the composites suitable for new demanding applications, such as energy harvesting. However, in most cases, surface modification of nanodiamonds requires the use of strong chemicals and high temperatures. The present study offers a less time-consuming functionalization method at 40 °C via reaction between the epoxy-rings of the modifier and carboxylic groups at the nanodiamond surface. This allows decorating the nanodiamond surface with chemical groups that are able to participate in the crosslinking reaction, thus creating strong interaction between filler and elastomer. Addition of 0.1 phr (parts per hundred rubber) of modified nanodiamonds into the silicone matrix results in about fivefold decreased electric losses at 1 Hz due to a reduced conductivity. Moreover, the mechanical hysteresis loss is reduced more than 50% and dynamic loss tangent at ambient temperature is lowered. Therefore, such materials are recommended for the dielectric energy harvesting application, and they are expected to increase its efficiency. Full article
Show Figures

Graphical abstract

Open AccessArticle
Transparent, High Glass-Transition Temperature, Shape Memory Hybrid Polyimides Based on Polyhedral Oligomeric Silsesquioxane
Polymers 2019, 11(6), 1058; https://doi.org/10.3390/polym11061058 - 18 Jun 2019
Cited by 5
Abstract
Optically transparent polyimides with excellent thermal stability and shape memory effect have potential applications in optoelectronic devices and aerospace industries. A series of optically transparent shape memory polyimide hybrid films are synthesized from 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 2,2′-bis-(trifluoromethyl)biphenyl-4,4′-diamine (TFMB) with various polyhedral oligomeric [...] Read more.
Optically transparent polyimides with excellent thermal stability and shape memory effect have potential applications in optoelectronic devices and aerospace industries. A series of optically transparent shape memory polyimide hybrid films are synthesized from 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 2,2′-bis-(trifluoromethyl)biphenyl-4,4′-diamine (TFMB) with various polyhedral oligomeric silsesquioxane (POSS) contents and then subjected to thermal imidization. The hybrid films show good optical transparency (>80% at 400 nm and >95% at 500 nm) with cutoff wavelengths ranging from 318 to 336 nm. Following the incorporation of the inorganic POSS structure, the hybrid films exhibit excellent thermal stability with glass transition temperature (Tg) ranging from 351 to 372 °C. The hybrid films possess the highest Tg compared with the previously-reported shape memory polymers. These findings show that POSS is successfully utilized to develop transparent polyimides with excellent thermal stability and shape memory effect. Full article
Show Figures

Graphical abstract

Open AccessArticle
Polydimethylsiloxane/Nanodiamond Composite Sponge for Enhanced Mechanical or Wettability Performance
Polymers 2019, 11(6), 948; https://doi.org/10.3390/polym11060948 - 01 Jun 2019
Cited by 3
Abstract
Polydimethylsiloxane (PDMS) is widely utilized in material science, chemical engineering, and environmental science due to its excellent properties. By utilizing fillers, so-called composite materials can be obtained with enhanced mechanical, wettability, or thermal conductivity performance. Here, we present a simple, cost-effective approach to [...] Read more.
Polydimethylsiloxane (PDMS) is widely utilized in material science, chemical engineering, and environmental science due to its excellent properties. By utilizing fillers, so-called composite materials can be obtained with enhanced mechanical, wettability, or thermal conductivity performance. Here, we present a simple, cost-effective approach to vary either the mechanical properties (Young’s modulus) or surface wettability of bulk PDMS and PDMS sponges simply by adding nanodiamond filler with different surface terminations, either oxidized (oND) or hydrogenated (reduced, rND) nanodiamond. Minuscule amounts of oxidized nanodiamond particles as filler showed to benefit the compressive Young’s modulus of composite sponges with up to a 52% increase in its value, while the wettability of composite sponges was unaffected. In contrast, adding reduced nanodiamond particles to PDMS yielded inclined water contact angles on the PDMS/nanodiamond composite sponges. Finally, we show that the PDMS/rND composites are readily utilized as an absorbent for oil/water separation problems. This signifies that the surface termination of the ND particle has a crucial effect on the performance of the composite. Full article
Show Figures

Graphical abstract

Open AccessArticle
Synthesis and Characterization of Silicone Contact Lenses Based on TRIS-DMA-NVP-HEMA Hydrogels
Polymers 2019, 11(6), 944; https://doi.org/10.3390/polym11060944 - 31 May 2019
Cited by 5
Abstract
In this study, silicone-based hydrogel contact lenses were prepared by the polymerization of 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane (TRIS), N,N-dimethylacrylamide (DMA), 1-vinyl-2-pyrrolidinone (NVP), and 2-hydroxyethylmethacrylate (HEMA). The properties of silicone hydrogel lenses were analyzed based on the methods such as equilibrium water content, oxygen permeability, optical transparency, [...] Read more.
In this study, silicone-based hydrogel contact lenses were prepared by the polymerization of 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane (TRIS), N,N-dimethylacrylamide (DMA), 1-vinyl-2-pyrrolidinone (NVP), and 2-hydroxyethylmethacrylate (HEMA). The properties of silicone hydrogel lenses were analyzed based on the methods such as equilibrium water content, oxygen permeability, optical transparency, contact angle, mechanical test, protein adsorption, and cell toxicity. The results showed that the TRIS content in all formulations increased the oxygen permeability and decreased the equilibrium water content, while both DMA and NVP contributed the hydrophilicity of the hydrogels. The maximum value of oxygen permeability was 74.9 barrers, corresponding to an equilibrium water content of 44.5% as well as a contact angle of 82°. Moreover, L929 fibroblasts grew on all these hydrogels, suggesting non-cytotoxicity. In general, the silicone hydrogels in this work exhibited good oxygen permeability, stiffness, and optical transparency as well as anti-protein adsorption. Hence, these silicone hydrogel polymers would be feasible for making contact lens. Full article
Show Figures

Graphical abstract

Open AccessArticle
Hydrosilylation of Reactive Quantum Dots and Siloxanes for Stable Quantum Dot Films
Polymers 2019, 11(5), 905; https://doi.org/10.3390/polym11050905 - 18 May 2019
Abstract
The reactive acrylate-terminated CdZnSeS/ZnS quantum dots (QDs) were designed and prepared by the effective synthetic route to bond with a siloxane matrix via hydrosilylation. The conventional QD with oleic acid ligands does not have any reactivity, so the QDs were functionalized to assign [...] Read more.
The reactive acrylate-terminated CdZnSeS/ZnS quantum dots (QDs) were designed and prepared by the effective synthetic route to bond with a siloxane matrix via hydrosilylation. The conventional QD with oleic acid ligands does not have any reactivity, so the QDs were functionalized to assign reactivity for the QDs by the ligand modification of two step reactions. The oleic acid of the QDs was exchanged for hydroxyl-terminated ligands as an intermediate product by one-pot reaction. The hydroxyl-terminated QDs and acrylate-containing isocyanates were combined by nucleophilic addition reaction with forming urethane bonds and terminal acrylate groups. No degradation in quantum yield was observed after ligand exchange, nor following the nucleophilic addition reaction. The modification reactions of ligands were quantitatively controlled and their molecular structures were precisely confirmed by FT-IR and 1H-NMR. The QDs with acrylate ligands were then reacted with hydride-terminated polydimethylsiloxane (H-PDMS) to form a QD-siloxane matrix by thermal curing via hydro-silylation for the first time. The covalent bonding between the QDs and the siloxane matrix led to improvements in the stability against oxygen and moisture. Stability at 85 °C and 85% relative humidity (RH) were both improved by 22% for the QD-connected siloxane QD films compared with the corresponding values for conventional QD-embedded poly(methylmethacrylate) (PMMA) films. The photo-stability of the QD film after 26 h under a blue light-emitting diode (LED) was also improved by 45% in comparison with those of conventional QD-embedded PMMA films. Full article
Show Figures

Graphical abstract

Open AccessArticle
Aluminosilicate Nanotubes Embedded Polyamide Thin Film Nanocomposite Forward Osmosis Membranes with Simultaneous Enhancement of Water Permeability and Selectivity
Polymers 2019, 11(5), 879; https://doi.org/10.3390/polym11050879 - 14 May 2019
Cited by 4
Abstract
Nanocomposite membranes are strongly desired to break a trade-off between permeability and selectivity. This work reports new thin film nanocomposite (TFN) forward osmosis (FO) membranes by embedding aluminosilicate nanotubes (ANTs) into a polyamide (PA) rejection layer. The surface morphology and structure of the [...] Read more.
Nanocomposite membranes are strongly desired to break a trade-off between permeability and selectivity. This work reports new thin film nanocomposite (TFN) forward osmosis (FO) membranes by embedding aluminosilicate nanotubes (ANTs) into a polyamide (PA) rejection layer. The surface morphology and structure of the TFN FO membranes were carefully characterized by FTIR, XPS, FESEM and AFM. The ANTs incorporated PA rejection layers exhibited many open and broad “leaf-like” folds with “ridge-and-valley” structures, high surface roughness and relatively low cross-linking degree. Compared with thin film composite (TFC) membrane without ANTs, the TFN membrane with only 0.2 w/v% ANTs loading presented significantly improved FO water permeability, selectivity and reduced structural parameters. This promising performance can be mainly contributed to the special ANTs embedded PA rejection layer, where water molecules preferentially transport through the nanochannels of ANTs. Molecular dynamic simulation further proved that water molecules have much larger flux through the nanotubes of ANTs than sodium and chloride ions, which are attributed to the intrinsic hydrophilicity of ANTs and low external force for water transport. This work shows that these TFN FO membranes with ANTs decorated PA layer are promising in desalination applications due to their simultaneously enhanced permeability and selectivity. Full article
Show Figures

Graphical abstract

Open AccessArticle
Effects of an Organic-Inorganic Hybrid Containing Allyl Benzoxazine and POSS on Thermal Properties and Flame Retardancy of Epoxy Resin
Polymers 2019, 11(5), 770; https://doi.org/10.3390/polym11050770 - 01 May 2019
Cited by 4
Abstract
A novel organic-inorganic hybrid containing allyl benzoxazine and polyhedral oligomeric silsesquioxane (POSS) was synthesized by the thiol-ene (click) reaction. The benzoxazine (BOZ)-containing POSS (SPOSS-BOZ) copolymerized with benzoxazine/epoxy resin was used to prepare composites of SPOSS-PBZ-E nanocomposites(NPs). The polymerization behavior was monitored by FTIR [...] Read more.
A novel organic-inorganic hybrid containing allyl benzoxazine and polyhedral oligomeric silsesquioxane (POSS) was synthesized by the thiol-ene (click) reaction. The benzoxazine (BOZ)-containing POSS (SPOSS-BOZ) copolymerized with benzoxazine/epoxy resin was used to prepare composites of SPOSS-PBZ-E nanocomposites(NPs). The polymerization behavior was monitored by FTIR and non-isothermal differential scanning calorimetry (DSC), which showed that the composites had completely cured with multiple polymerization mechanisms according to the oxazine ring-opening and epoxy resin (EP) polymerization. The thermal properties of the organic–inorganic polybenzoxazine (PBZ) nanocomposites were analyzed by DSC and thermogravimetric analysis (TGA). Furthermore, the X-ray diffraction analysis and the scanning electron microscopy (SEM) micrographs of the SPOSS-PBZ-E nanocomposites indicated that SPOSS was chemically incorporated into the hybrid nanocomposites in the size range of 80–200 nm. The flame retardancy of the benzoxazine epoxy resin composites was investigated by limiting oxygen index (LOI), UL 94 vertical burn test, and cone calorimeter tests. When the amount of SPOSS reached 10% or more, the vertical burning rating of the curing system arrived at V-1, and when the SPOSS-BOZ content reached 20 wt %, the thermal stability and flame retardancy of the material were both improved. Moreover, in the cone calorimeter testing, the addition of SPOSS-BOZ hindered the decomposition of the composites and led to a reduction in the peak heat release rate (pHRR), the average heat release rate (aHRR), and the total heat release (THR) values by about 20%, 25%, and 25%, respectively. The morphologies of the chars were also studied by SEM and energy dispersive X-ray spectroscopy (EDX), and the flame-retardant mechanism of POSS was mainly a condensed-phase flame retardant. The ceramic layer was formed by the enrichment of silicon on the char surface. When there are enough POSS nanoparticles, it can effectively protect the combustion of internal polymers. Full article
Show Figures

Figure 1

Open AccessArticle
Effect of Silane Treatment on Mechanical Properties of Polyurethane/Mesoscopic Fly Ash Composites
Polymers 2019, 11(4), 741; https://doi.org/10.3390/polym11040741 - 24 Apr 2019
Cited by 1
Abstract
In view of the accidents such as rock mass breakage, roof fall and coal slide in coal mines, polyurethane/mesoscopic fly ash (PU/MFA) reinforcement materials were produced from polymethylene polyphenylene isocyanate (PAPI), the polyether polyol, flame retardant, and MFA using stannous octanate as a [...] Read more.
In view of the accidents such as rock mass breakage, roof fall and coal slide in coal mines, polyurethane/mesoscopic fly ash (PU/MFA) reinforcement materials were produced from polymethylene polyphenylene isocyanate (PAPI), the polyether polyol, flame retardant, and MFA using stannous octanate as a catalyst. 3-Glycidoxypropyltrimethoxysilane (GPTMS) was grafted on MFA surface, aiming to improve the mechanical properties of PU/MFA composites. The analyses of infrared spectroscopy and compression resistance reveal that the GPTMS can be successfully attached to the surface of MFA, and the optimum modification dosage of GPTMS to MFA is 2.5 wt. % (weight percent). On this basis, the effect of GPTMS on the mechanical properties of PU/MFA reinforcement materials during the curing process was systematically investigated through a compression test, a fracture toughness test, a three-point bending test, a bond property test, and a dynamic mechanics analysis. The results show that the compression property, fracture toughness, maximum flexural strength, and bond strength of PU/MFA composites increase by 21.6%, 10.1%, 8.8%, and 19.3%, respectively, compared with the values before the modification. Furthermore, the analyses of scanning electron microscope and dynamic mechanics suggest that the coupling agent GPTMS can successfully improve the mechanical properties of PU/MFA composites because it eliminates the stress concentration and exerts a positive effect on the crosslink density and hardness of PU/MFA composites. Full article
Show Figures

Figure 1

Open AccessArticle
Manifestation of Interactions of Nano-Silica in Silicone Rubber Investigated by Low-Frequency Dielectric Spectroscopy and Mechanical Tests
Polymers 2019, 11(4), 717; https://doi.org/10.3390/polym11040717 - 19 Apr 2019
Cited by 6
Abstract
Silicone rubber composites filled with nano-silica are currently widely used as high voltage insulating materials in power transmission and substation systems. We present a systematic study on the dielectric and mechanical performance of silicone rubber filled with surface modified and unmodified fumed nano-silica. [...] Read more.
Silicone rubber composites filled with nano-silica are currently widely used as high voltage insulating materials in power transmission and substation systems. We present a systematic study on the dielectric and mechanical performance of silicone rubber filled with surface modified and unmodified fumed nano-silica. The results indicate that the different interfaces between the silicone rubber and the two types of nano-silica introduce changes in their dielectric response when electrically stressed by a sinusoidal excitation in the frequency range of 10−4–1 Hz. The responses of pure silicone rubber and the composite filled with modified silica can be characterized by a paralleled combination of Maxwell-Wagner-Sillars interface polarization and DC conduction. In contrast, the silicone rubber composite with the unmodified nano-silica exhibits a quasi-DC (Q-DC) transport process. The mechanical properties of the composites (represented by their stress-strain characteristics) reveal an improvement in the mechanical strength with increasing filler content. Moreover, the strain level of the composite with a modified filler is improved. Full article
Show Figures

Graphical abstract

Open AccessArticle
Improving the Damping Properties of Nanocomposites by Monodispersed Hybrid POSS Nanoparticles: Preparation and Mechanisms
Polymers 2019, 11(4), 647; https://doi.org/10.3390/polym11040647 - 09 Apr 2019
Cited by 4
Abstract
In this work, a series of heptaphenyl siloxane trisilanol/polyhedral oligomeric silsesquioxane (T7-POSS) modified by polyols with different molecular weights were synthesized into liquid-like nanoparticle–organic hybrid materials using the grafted-from method. All grafted POSS nanoparticles changed from solid powders to liquid at [...] Read more.
In this work, a series of heptaphenyl siloxane trisilanol/polyhedral oligomeric silsesquioxane (T7-POSS) modified by polyols with different molecular weights were synthesized into liquid-like nanoparticle–organic hybrid materials using the grafted-from method. All grafted POSS nanoparticles changed from solid powders to liquid at room temperature. Polyurethane (PU) nanocomposites with POSS contents ranging from 1.75 to 9.72 wt % were prepared from these liquefied polyols-terminated POSS with polyepichlorohydrin (POSS–PECH). Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to characterize the morphology of the POSS–PECH/PU nanocomposites. The results showed that the polyol-terminated POSS particles overcame the nanoagglomeration effect and evenly disperse in the polymeric matrix. The damping factor (tan δ) of resultant nanocomposites increased from 0.90 to 1.16, while the glass transition temperature decreased from 15.8 to 9.4 °C when POSS contents increased from 0 to 9.75 wt %. The gel content, tensile strength and Fourier transform infrared (FTIR) analyses demonstrated that the molecular thermal movement ability of the polyurethane (PU) matrix increased with increasing POSS hybrid content. Therefore, the improvement of the damping properties of the composites was mainly due to the friction-related losses occurring in the interface region between the nanoparticles and the matrix. Full article
Show Figures

Graphical abstract

Open AccessArticle
Functional Nanostructured Oligochitosan–Silica/Carboxymethyl Cellulose Hybrid Materials: Synthesis and Investigation of Their Antifungal Abilities
Polymers 2019, 11(4), 628; https://doi.org/10.3390/polym11040628 - 04 Apr 2019
Cited by 3
Abstract
Functional hybrid materials were successfully synthesized from low-cost waste products, such as oligochitosan (OCS) obtained from chitosan (one of the main components in crab shells) and nanosilica (nSiO2) obtained from rice husk, in a 1:1 ratio (w/w), [...] Read more.
Functional hybrid materials were successfully synthesized from low-cost waste products, such as oligochitosan (OCS) obtained from chitosan (one of the main components in crab shells) and nanosilica (nSiO2) obtained from rice husk, in a 1:1 ratio (w/w), and their dispersion in the presence of carboxymethyl cellulose at pH 7 was stable for over one month without aggregation. The molecular weights, chemical structures, morphologies, and crystallinities of the obtained materials were characterized by GPC, FTIR, TEM, and XRD, respectively. The antifungal effects of OCS, nSiO2, and the OCS/nSiO2 hybrid materials were investigated via a disk-diffusion method. The results showed that the nanohybrid materials had better resistance to Phytophthora infestans fungus than the individual components, and a concentration of the OCS2/nSiO2 hybrid material of 800 mg L−1 was the lowest concentration where the material completely inhibited Phytophthora infestans growth, as measured via an agar dilution method. This study not only creates a novel environmentally friendly material with unique synergistic effects that can replace current toxic agrochemicals but also can be considered a new platform for further research in green agricultural applications. Full article
Show Figures

Graphical abstract

Open AccessArticle
POSS-Derived Synthesis and Full Life Structural Analysis of [email protected] as Anode Material in Lithium Ion Battery
Polymers 2019, 11(4), 576; https://doi.org/10.3390/polym11040576 - 29 Mar 2019
Cited by 4
Abstract
Polyhedral oligomeric silsesquioxane (POSS)-derived [email protected] anode material is prepared by the copolymerization of octavinyl-polyhedral oligomeric silsesquioxane (octavinyl-POSS) and styrene. Octavinyl-polyhedral oligomeric silsesquioxane has an inorganic core (-Si8O12) and an organic vinyl shell. Carbonization of the core-shell structured organic-inorganic hybrid [...] Read more.
Polyhedral oligomeric silsesquioxane (POSS)-derived [email protected] anode material is prepared by the copolymerization of octavinyl-polyhedral oligomeric silsesquioxane (octavinyl-POSS) and styrene. Octavinyl-polyhedral oligomeric silsesquioxane has an inorganic core (-Si8O12) and an organic vinyl shell. Carbonization of the core-shell structured organic-inorganic hybrid precursor results in the formation of carbon protected Si-based anode material applicable for lithium ion battery. The initial discharge capacity of the battery based on the as-obtained [email protected] material Si reaches 1500 mAh g−1. After 550 charge-discharge cycles, a high capacity of 1430 mAh g−1 was maintained. A combined XRD, XPS and TEM analysis was performed to investigate the variation of the discharge performance during the cycling experiments. The results show that the decrease in discharge capacity in the first few cycles is related to the formation of solid electrolyte interphase (SEI). The subsequent rise in the capacity can be ascribed to the gradual morphology evolution of the anode material and the loss of capacity after long-term cycles is due to the structural pulverization of silicon within the electrode. Our results not only show the high potential of the novel electrode material but also provide insight into the dynamic features of the material during battery cycling, which is useful for the future design of high-performance electrode material. Full article
Show Figures

Figure 1

Open AccessArticle
Effect of a Modified Silicone as a Thickener on Rheology of Liquid CO2 and Its Fracturing Capacity
Polymers 2019, 11(3), 540; https://doi.org/10.3390/polym11030540 - 21 Mar 2019
Abstract
The low viscosity of pure liquid CO2 hindered the development of CO2 fracturing technology. A modified silicone polymer was prepared as a CO2 thickener to investigate the effect of temperature, pressure, shear rate and thickener content (wt.%) on the apparent [...] Read more.
The low viscosity of pure liquid CO2 hindered the development of CO2 fracturing technology. A modified silicone polymer was prepared as a CO2 thickener to investigate the effect of temperature, pressure, shear rate and thickener content (wt.%) on the apparent viscosity and rheology of thickened liquid CO2. In addition, CO2 fracturing capacity was evaluated with the numerical simulation of extended finite element. The results displayed that an apparent viscosity of up to 1.3 mPa·s at 303 K and 18 MPa was attained over liquid CO2 using the thickener of 3 wt.% and Toluene of 9 wt.% as additives. Compared to the commercial linear polydimethylsiloxane, a better apparent viscosity was obtained from the mixture of this prepared thickener, Toluene and CO2. The apparent viscosity decreases with increasing temperature and shear rate. By contrast, an improving apparent viscosity was revealed with an increase in the pressure from 8 to 14 MPa and thickener content from 1 to 3 wt.%. The rheological index decreased with increasing thickener content with pressure but the rise in temperature led to an increasing rheological index. The mesh structure theory of the thickener, CO2 and Toluene molecules was in this paper gives a good explanation for the discrepancy between CO2 viscosity with the thickener content, temperature, pressure, or shear rate. Compared to pure CO2, the numerical simulation of CO2 fracturing demonstrated an excellent fracturing capacity by using the thickened CO2 fracturing fluid in shale reservoirs. This investigation could provide the basic reference for the development of CO2 fracturing technology. Full article
Show Figures

Figure 1

Open AccessArticle
POSS Hybrid Robust Biomass IPN Hydrogels with Temperature Responsiveness
Polymers 2019, 11(3), 524; https://doi.org/10.3390/polym11030524 - 20 Mar 2019
Cited by 3
Abstract
In order to improve the performance of traditional sodium alginate (SA) hydrogels cross-linked by Ca2+ ions to meet greater application demand, a strategy was designed to structure novel SA-based gels (named OP-PN gels) to achieve both stimulus responsiveness and improved mechanical strength. [...] Read more.
In order to improve the performance of traditional sodium alginate (SA) hydrogels cross-linked by Ca2+ ions to meet greater application demand, a strategy was designed to structure novel SA-based gels (named OP-PN gels) to achieve both stimulus responsiveness and improved mechanical strength. In this strategy, the SA chains are co-cross-linked by CaCl2 and cationic octa-ammonium polyhedral oligomeric silsesquioxane (Oa-POSS) particles as the first network, and an organically cross-linked poly(N-isopropyl acrylamide) (PNIPA) network is introduced into the gels as the second network. Several main results are obtained from the synthesis and characterization of the gels. For OP-PN gels, their properties depend on the content of both uniformly dispersed Oa-POSS and PNIPA network directly. The increased Oa-POSS and PNIPA network content significantly improves both the strength and resilience of gels. Relatively, the increased Oa-POSS is greatly beneficial to the modulus of gels, and the increased PNIPA network is more favorable to advancing the tensile deformation of gels. The gels with hydrophilic PNIPA network exhibit better swelling ability and remarkable temperature responsiveness, and their volume phase transition temperature can be adjusted by altering the content of Oa-POSS. The deswelling rate of gels increases gradually with the increase of POSS content due to the hydrophobic Si–O skeleton of POSS. Moreover, the enhanced drug loading and sustained release ability of the target drug bovine serum albumin displays great potential for this hybrid gel in the biomedical field. Full article
Show Figures

Figure 1

Open AccessArticle
Anchor Effect in Polymerization Kinetics: Case of Monofunctionalized POSS
Polymers 2019, 11(3), 515; https://doi.org/10.3390/polym11030515 - 19 Mar 2019
Cited by 3
Abstract
The effect of the anchoring group on the detailed polymerization kinetics was investigated using monomethacryloxy-heptaisobutyl POSS (1M-POSS). This compound was copolymerized with lauryl methacrylate (LM) as the base monomer, at various molar ratios. The process was initiated photochemically. The polymerization kinetics were followed [...] Read more.
The effect of the anchoring group on the detailed polymerization kinetics was investigated using monomethacryloxy-heptaisobutyl POSS (1M-POSS). This compound was copolymerized with lauryl methacrylate (LM) as the base monomer, at various molar ratios. The process was initiated photochemically. The polymerization kinetics were followed by photo-DSC and photorheology while the polymers were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). For comparison, a methacrylate containing the branched siloxy-silane group (TSM) was also studied. It was found that the modifiers with a bulky substituent have a dual effect on the termination process: (i) At low concentrations, they increase the molecular mobility by increasing the free volume fraction, which leads to an acceleration of the termination and slows the polymerization; while (ii) at higher concentrations, they retard molecular motions due to the “anchor effect” that suppresses the termination, leading to acceleration of the polymerization. The anchor effect can also be considered from a different point of view: The possibility of anchoring a monomer with a long substituent (LM) around the POSS cage, which can further enhance propagation. These conclusions were derived based on kinetic results, determination of polymerization rate coefficients, and copolymer analysis. Full article
Show Figures

Graphical abstract

Open AccessReview
Synthetic Routes to Silsesquioxane-Based Systems as Photoactive Materials and Their Precursors
Polymers 2019, 11(3), 504; https://doi.org/10.3390/polym11030504 - 16 Mar 2019
Cited by 8
Abstract
Over the past two decades, organic optoelectronic materials have been considered very promising. The attractiveness of this group of compounds, regardless of their undisputable application potential, lies in the possibility of their use in the construction of organic–inorganic hybrid materials. This class of [...] Read more.
Over the past two decades, organic optoelectronic materials have been considered very promising. The attractiveness of this group of compounds, regardless of their undisputable application potential, lies in the possibility of their use in the construction of organic–inorganic hybrid materials. This class of frameworks also considers nanostructural polyhedral oligomeric silsesquioxanes (POSSs) with “organic coronae” and precisely defined organic architectures between dispersed rigid silica cores. A significant number of papers on the design and development of POSS-based organic optoelectronic as well as photoluminescent (PL) materials have been published recently. In view of the scientific literature abounding with numerous examples of their application (i.e., as OLEDs), the aim of this review is to present efficient synthetic pathways leading to the formation of nanocomposite materials based on silsesquioxane systems that contain organic chromophores of complex nature. A summary of stoichiometric and predominantly catalytic methods for these silsesquioxane-based systems to be applied in the construction of photoactive materials or their precursors is given. Full article
Show Figures

Graphical abstract

Open AccessArticle
Recycled-Oil-Based Polyurethane Modified with Organic Silicone for Controllable Release of Coated Fertilizer
Polymers 2019, 11(3), 454; https://doi.org/10.3390/polym11030454 - 10 Mar 2019
Cited by 2
Abstract
Fertilizer is very important for increasing food yield, but the extensive use of fertilizer will cause environmental pollution. To enhance the effectiveness of fertilizer, we developed the double organic silicone-modified recycled-oil-based polyurethane as a coating material to prepare degradable polymer coating urea for [...] Read more.
Fertilizer is very important for increasing food yield, but the extensive use of fertilizer will cause environmental pollution. To enhance the effectiveness of fertilizer, we developed the double organic silicone-modified recycled-oil-based polyurethane as a coating material to prepare degradable polymer coating urea for constant fertilizer release. The moisture, heat resistance, and sustained release properties of polyurethane coating materials were investigated by modification with hydroxyl-terminated polydimethyl silicone (HTPMS) and γ-Aminopropyl triethoxy silane (KH550). The content and distribution of the siloxane groups were effectively controlled by adjusting the content ratio of two kinds of organosilicon. Meanwhile, the organic–inorganic hybrid structure was further controlled to form three-dimensional networks with a uniform distribution and a small scale. The moisture and heat resistance of polyurethane were thus improved, resulting in reduced porosity and an excellent sustained release performance. Observably, the best sustained release property of modified polyurethane coated urea was obtained when the ratio of KH550 to HTPMS is 0.3:0.7. Full article
Show Figures

Graphical abstract

Open AccessArticle
Multifunctional Silicone Rubber Nanocomposites by Controlling the Structure and Morphology of Graphene Material
Polymers 2019, 11(3), 449; https://doi.org/10.3390/polym11030449 - 08 Mar 2019
Cited by 7
Abstract
Multifunctional elastomer nanocomposites have been applied in several high-tech fields. The design of materials with tailored properties capable of tuning their performance is a topical challenge. Here, we demonstrate that it is possible to modulate the mechanical and transport properties of silicone rubber [...] Read more.
Multifunctional elastomer nanocomposites have been applied in several high-tech fields. The design of materials with tailored properties capable of tuning their performance is a topical challenge. Here, we demonstrate that it is possible to modulate the mechanical and transport properties of silicone rubber nanocomposites by controlling the structure, chemical composition and morphology of the graphene material. Intrinsic graphene properties, such as remaining oxygen groups, specific surface area, and aspect ratio, among others, have a profound effect on the final properties of the nanocomposite. Thus, the thermal conductivity benefits from larger filler size and high aromatic restoration. Whereas mechanical properties and electrical conductivity require a proper balance between filler/polymer matrix interaction and a partial aromatic restoration. Full article
Show Figures

Graphical abstract

Open AccessArticle
Mechanically Robust Hybrid POSS Thermoplastic Polyurethanes with Enhanced Surface Hydrophobicity
Polymers 2019, 11(2), 373; https://doi.org/10.3390/polym11020373 - 20 Feb 2019
Cited by 3
Abstract
A series of hybrid thermoplastic polyurethanes (PUs) were synthesized from bi-functional polyhedral oligomeric silsesquioxane (B-POSS) and polycaprolactone (PCL) using 1,6-hexamethylene diisocyanate (HDI) as a coupling agent for the first time. The newly synthesized hybrid materials were fully characterized in terms of structure, morphology, [...] Read more.
A series of hybrid thermoplastic polyurethanes (PUs) were synthesized from bi-functional polyhedral oligomeric silsesquioxane (B-POSS) and polycaprolactone (PCL) using 1,6-hexamethylene diisocyanate (HDI) as a coupling agent for the first time. The newly synthesized hybrid materials were fully characterized in terms of structure, morphology, thermal and mechanical performance, as well as their toughening effect toward polyesters. Thermal gravimeter analysis (TGA) and differential scanning calorimetry (DSC) showed enhanced thermal stability by 76 °C higher in decomposition temperature (Td) of the POSS PUs, and 22 °C higher glass transition temperature (Tg) when compared with control PU without POSS. Static contact angle results showed a significant increment of 49.8° and 53.4° for the respective surface hydrophobicity and lipophilicity measurements. More importantly, both storage modulus (G’) and loss modulus (G’’) are improved in the hybrid POSS PUs and these parameters can be further adjusted by varying POSS content in the copolymer. As a biodegradable hybrid filler, the as-synthesized POSS PUs also demonstrated a remarkable effect in toughening commercial polyesters, indicating a simple yet useful strategy in developing high-performance polyester for advanced biomedical applications. Full article
Show Figures

Graphical abstract

Open AccessArticle
Composites of Rigid Polyurethane Foams Reinforced with POSS
Polymers 2019, 11(2), 336; https://doi.org/10.3390/polym11020336 - 14 Feb 2019
Cited by 15
Abstract
Rigid polyurethane foams (RPUFs) were successfully modified with different weight ratios (0.5 wt%, 1.5 wt% and 5 wt%) of APIB-POSS and AEAPIB-POSS. The resulting foams were evaluated by their processing parameters, morphology (Scanning Electron Microscopy analysis, SEM), mechanical properties (compressive test, three-point bending [...] Read more.
Rigid polyurethane foams (RPUFs) were successfully modified with different weight ratios (0.5 wt%, 1.5 wt% and 5 wt%) of APIB-POSS and AEAPIB-POSS. The resulting foams were evaluated by their processing parameters, morphology (Scanning Electron Microscopy analysis, SEM), mechanical properties (compressive test, three-point bending test and impact strength), viscoelastic behavior (Dynamic Mechanical Analysis, DMA), thermal properties (Thermogravimetric Analysis, TGA, and thermal conductivity) and application properties (contact angle, water absorption and dimensional analysis). The results showed that the morphology of modified foams is significantly affected by the type of the filler and filler content, which resulted in inhomogeneous, irregular, large cell shapes and further affected the physical and mechanical properties of resulting materials. RPUFs modified with APIB-POSS represent better mechanical and thermal properties compared to the RPUFs modified with AEAPIB-POSS. The results showed that the best results were obtained for RPUFs modified with 0.5 wt% of APIB-POSS. For example, in comparison with unfilled foam, compositions modified with 0.5 wt% of APIB-POSS provide greater compression strength, better flexural strength and lower water absorption. Full article
Show Figures

Graphical abstract

Open AccessArticle
Versatile Construction of Single-Tailed Giant Surfactants with Hydrophobic Poly(ε-caprolactone) Tail and Hydrophilic POSS Head
Polymers 2019, 11(2), 311; https://doi.org/10.3390/polym11020311 - 12 Feb 2019
Cited by 4
Abstract
Giant surfactants refer to a new kind of amphiphile by incorporating functional molecular nanoparticles with polymer tails. As a size-amplified counterpart of small-molecule surfactants, they serve to bridge the gap between small-molecule surfactants and amphiphilic block copolymers. This work reports the design and [...] Read more.
Giant surfactants refer to a new kind of amphiphile by incorporating functional molecular nanoparticles with polymer tails. As a size-amplified counterpart of small-molecule surfactants, they serve to bridge the gap between small-molecule surfactants and amphiphilic block copolymers. This work reports the design and synthesis of single-tailed giant surfactants carrying a hydrophobic poly(ε-caprolactone) (PCL) as the tail and a hydrophilic cage-like polyhedral oligomeric silsesquioxane (POSS) nanoparticle as the head. The modular synthetic strategy features an efficient “growing-from” and “click-modification” approach. Starting from a monohydroxyl and heptavinyl substituted POSS (VPOSS-OH), a PCL chain with controlled molecular weight and narrow polydispersity was first grown by the ring-opening polymerization (ROP) of ε-CL under the catalysis of stannous octoate, leading to a PCL chain end-capped with heptavinyl substituted POSS (VPOSS-PCL). To endow the POSS head with adjustable polarity and functionality, three kinds of hydrophilic groups, including hydroxyl groups, carboxylic acids, and amine groups, were installed to the periphery of POSS molecule by a high-efficiency thiol-ene “click” reaction. The compounds were fully characterized by NMR, gel permeation chromatography (GPC), MALDI-TOF mass spectrometry, and TGA analysis. In addition, the preliminary self-assembly study of these giant surfactants was also investigated by TEM and dynamic laser light scattering (DLS), which indicated that they can form spherical nanoparticles with different diameters in aqueous solution. This work affords a straightforward and versatile way for synthesizing single-tailed giant surfactants with diverse head surface functionalities. Full article
Show Figures

Graphical abstract

Open AccessArticle
Hydrolyzable Additive-Based Silicone Elastomers: A New Approach for Antifouling Coatings
Polymers 2019, 11(2), 305; https://doi.org/10.3390/polym11020305 - 12 Feb 2019
Cited by 9
Abstract
Fouling Release Coatings are marine antifouling coatings based on silicone elastomers. Contrary to commonly used biocide-based antifouling coatings, they do not release biocides into the marine environment, however, they suffer from poor antifouling efficacy during idle periods. To improve their antifouling performances in [...] Read more.
Fouling Release Coatings are marine antifouling coatings based on silicone elastomers. Contrary to commonly used biocide-based antifouling coatings, they do not release biocides into the marine environment, however, they suffer from poor antifouling efficacy during idle periods. To improve their antifouling performances in static conditions, various amounts of hydrolyzable polymers were incorporated within a silicone matrix. These hydrolyzable polymers were chosen for the well-known hydrolytic degradation mechanism of their main chain, e.g. poly(ε-caprolactone) (PCL), or of their ester pending groups, e.g. poly(bis(trimethylsilyloxy)methylsilyl methacrylate) (PMATM2). The degradation kinetics of such hydrolyzable silicone coatings were assessed by mass loss measurements during immersion in deionized water. Coatings containing PMATM2 exhibited a maximum mass loss after 12 weeks, whereas PCL-based coatings showed no significant mass loss after 24 weeks. Dynamic contact angle measurements revealed the modifications of the coatings surface chemistry with an amphiphilic behavior after water exposure. The attachment of macrofoulers on these coatings were evaluated by field tests in the Mediterranean Sea, demonstrating the short or long-term antifouling effect of these hydrolyzable polymers embedded in the silicone matrix. The settlement of A. amphitrite barnacles on the different coatings indicated inhospitable behaviors towards larval barnacles for coatings with at least 15 wt % of additives. Full article
Show Figures

Graphical abstract

Open AccessArticle
A Novel POSS-Based Copolymer Functionalized Graphene: An Effective Flame Retardant for Reducing the Flammability of Epoxy Resin
Polymers 2019, 11(2), 241; https://doi.org/10.3390/polym11020241 - 01 Feb 2019
Cited by 8
Abstract
In this study, a novel copolymer, PbisDOPOMA-POSSMA-GMA (PDPG), containing methacryloisobutyl polyhedral oligomeric silsesquioxane (POSSMA), reactive glycidyl methacrylate (GMA), and bis-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide methacrylate (bisDOPOMA) and derivative functionalized graphene oxide (GO) were synthesized by a one-step grafting reaction to create a hybrid flame retardant (GO-MD-MP). GO-MD-MP [...] Read more.
In this study, a novel copolymer, PbisDOPOMA-POSSMA-GMA (PDPG), containing methacryloisobutyl polyhedral oligomeric silsesquioxane (POSSMA), reactive glycidyl methacrylate (GMA), and bis-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide methacrylate (bisDOPOMA) and derivative functionalized graphene oxide (GO) were synthesized by a one-step grafting reaction to create a hybrid flame retardant (GO-MD-MP). GO-MD-MP was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). Flame-retardant epoxy resin (EP) composites were prepared by adding various amounts of GO-MD-MP to the thermal-curing epoxy resin of diglycidyl ether of bisphenol A (DGEBA, trade name E-51). The thermal properties of the EP composites were remarkably enhanced by adding the GO-MD-MP, and the residue char of the epoxy resin also increased greatly. With the incorporation of 4 wt % GO-MD-MP, the limiting oxygen index (LOI) value was enhanced to 31.1% and the UL-94 V-0 rating was easily achieved. In addition, the mechanical strength of the epoxy resin was also improved. Full article
Show Figures

Figure 1

Open AccessArticle
New Triphenylamine-Based Oligomeric Schiff Bases Containing Tetraphenylsilane Moieties in the Backbone
Polymers 2019, 11(2), 216; https://doi.org/10.3390/polym11020216 - 27 Jan 2019
Cited by 5
Abstract
Three new triphenylamine-based oligomeric Schiff bases (polySB1, polySB2 and polySB3) containing tetraphenylsilane core (TPS-core) in the main chain were obtained from TPS-core-based diamines and bis(4-formylphenyl)phenylamine by a high-temperature polycondensation reaction. These new oligomers were structurally characterized by FT-IR, NMR and elemental analysis. All [...] Read more.
Three new triphenylamine-based oligomeric Schiff bases (polySB1, polySB2 and polySB3) containing tetraphenylsilane core (TPS-core) in the main chain were obtained from TPS-core-based diamines and bis(4-formylphenyl)phenylamine by a high-temperature polycondensation reaction. These new oligomers were structurally characterized by FT-IR, NMR and elemental analysis. All polySBs were highly soluble in common organic solvents, such as chloroform, tetrahydrofuran and chlorobenzene. Samples showed moderate molecular average molecular weight (Mw) and a high thermal stability above 410 °C. Likewise, polySBs showed absorption near 400 nm in the UV-vis range and photoluminescence. The HOMO levels and band-gap values were found in the ranges of −6.06 to −6.18 eV and 2.65–2.72 eV, respectively. The lowest band-gap value was observed for polySB2, which could be attributed to a more effective π-conjugation across the main chain. The results suggest that silicon-containing polySBs are promising wide-band-gap semiconductors materials for optoelectronic applications. Full article
Show Figures

Graphical abstract

Open AccessArticle
Blends of Cyanate Ester and Phthalonitrile–Polyhedral Oligomeric Silsesquioxane Copolymers: Cure Behavior and Properties
Polymers 2019, 11(1), 54; https://doi.org/10.3390/polym11010054 - 01 Jan 2019
Cited by 1
Abstract
Blends of cyanate ester and phthalonitrile–polyhedral oligomeric silsesquioxane copolymers were prepared, and their cure behavior and properties were compared via differential scanning calorimetry (DSC) analysis, thermogravimetric (TG) analysis, dynamic mechanical analysis, Fourier-transform far-infrared (FTIR) spectroscopy, and rheometric studies. The copolymer blends showed high [...] Read more.
Blends of cyanate ester and phthalonitrile–polyhedral oligomeric silsesquioxane copolymers were prepared, and their cure behavior and properties were compared via differential scanning calorimetry (DSC) analysis, thermogravimetric (TG) analysis, dynamic mechanical analysis, Fourier-transform far-infrared (FTIR) spectroscopy, and rheometric studies. The copolymer blends showed high chemical reactivity, low viscosity, and good thermal stability (TG temperatures were above 400 °C). The glass-transition temperature of the blends increased by at least 140 °C compared to cyanate ester resin. The blends are suitable for preparing carbon-fiber-reinforced composite materials via a winding process and a prepreg lay-up process with a molding technique. The FTIR data showed that the polymerization products contained triazine-ring structures that were responsible for the superior thermal properties. Full article
Show Figures

Figure 1