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

Deadline for manuscript submissions: closed (15 March 2018) | Viewed by 87575

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Prof. Dr. Ignazio Blanco

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Department of Civil Engineering and Architecture, University of Catania, Viale A. Doria 6, 95125 Catania, Italy
Interests: materials; polymers; thermal properties; nanocomposites; composites
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Dear Colleagues,

Since the birth of chemistry, inorganic and organic compounds have been considered two separate worlds owing to their completely different properties and structure. Due to the progress of the science in this field, it is possible today to obtain hybrid inorganic–organic materials, thus having the properties of both of them, different than those achievable by a simple blend at macroscopic level. In this frame, the synthesis of Siloxane-Based Polymers represents at the same time a challenge and a fascinating field of research, and offers the opportunity of obtaining compounds with new unique properties. We invite authors to submit original research and review articles that report the synthesis and characterization of these hybrid materials and that attest an enhancement of their chemical, physical and mechanical properties in respect to the polymer matrix. We are interested in traditional and new chemical processes will contribute to the preparation of such materials and in new processing technologies articles. The aim is also to cover the exploration of the interaction between inorganic filler and organic matrix.

We cordially invite experts in the field of siloxane-based polymers to submit papers to this Special Issue.

Prof. Dr. Ignazio Blanco
Guest Editor

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Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

Siloxane
Copolymer
Hybrid materials
POSS
Coatings
Membrane
Nanomedicine
Thermal properties
Mechanical properties
Pendent groups
Optical properties

Related Special Issue

Silicon-Containing Polymeric Materials in Polymers (130 articles)

Published Papers (14 papers)

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Research

Jump to: Review

14 pages, 4877 KiB

Open AccessArticle

A Novel Synthetic UV-Curable Fluorinated Siloxane Resin for Low Surface Energy Coating

by Chunfang Zhu, Haitao Yang, Hongbo Liang, Zhengyue Wang, Jun Dong, Lei Xiong, Jianping Zhou, Junjun Ke, Xi Xu and Weixian Xi

Polymers 2018, 10(9), 979; https://doi.org/10.3390/polym10090979 - 03 Sep 2018

Cited by 14 | Viewed by 6660

Abstract

Low surface energy materials have attracted much attention due to their properties and various applications. In this work, we synthesized and characterized a series of ultraviolet (UV)-curable fluorinated siloxane polymers with various fluorinated acrylates—hexafluorobutyl acrylate, dodecafluoroheptyl acrylate, and trifluorooctyl methacrylate—grafted onto a hydrogen-containing poly(dimethylsiloxane) backbone. The structures of the fluorinated siloxane polymers were measured and confirmed by proton nuclear magnetic resonance and Fourier transform infrared spectroscopy. Then the polymers were used as surface modifiers of UV-curable commercial polyurethane (DR-U356) at different concentrations (1, 2, 3, 4, 5, and 10 wt %). Among three formulations of these fluorinated siloxane polymers modified with DR-U356, hydrophobic states (91°, 92°, and 98°) were obtained at low concentrations (1 wt %). The DR-U356 resin is only in the hydrophilic state at 59.41°. The fluorine and siloxane element contents were investigated by X-ray photoelectron spectroscopy and the results indicated that the fluorinated and siloxane elements were liable to migrate to the surface of resins. The results of the friction recovering assays showed that the recorded contact angles of the series of fluorinated siloxane resins were higher than the original values after the friction-annealing progressing. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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12 pages, 2476 KiB

Open AccessArticle

Sol-Gel Synthesis, Spectroscopic and Thermal Behavior Study of SiO₂/PEG Composites Containing Different Amount of Chlorogenic Acid

by Michelina Catauro, Elisabetta Tranquillo, Roberta Risoluti and Stefano Vecchio Ciprioti

Polymers 2018, 10(6), 682; https://doi.org/10.3390/polym10060682 - 19 Jun 2018

Cited by 51 | Viewed by 5140

Abstract

In this work, new phenol-based materials have been synthesized by the sol-gel method, in which different amounts of the phenolic antioxidant chlorogenic acid (CGA) (from 5 wt % to 20 wt %) were embedded in two different silica matrices: pure silica and silica-based hybrids materials, containing 50 wt % of polyethylene glycol (PEG). The incorporation of CGA in different sol-gel matrices might protect them from degradation, which could cause the loss of their properties. The two series of materials were chemically characterized by Fourier transform infrared (FTIR) spectroscopy. In addition, the thermal behavior of both series of materials containing CGA was studied by thermogravimetry under both air and inert N₂ flowing gas atmosphere. The bioactivity was evaluated by soaking the synthesized hybrids in a simulated body fluid, showing that the bioactivity of the silica matrix is not modified by the presence of PEG and CGA. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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13 pages, 2045 KiB

Open AccessArticle

Structural and Thermoanalytical Characterization of 3D Porous PDMS Foam Materials: The Effect of Impurities Derived from a Sugar Templating Process

by José González-Rivera, Rossella Iglio, Giuseppe Barillaro, Celia Duce and Maria Rosaria Tinè

Polymers 2018, 10(6), 616; https://doi.org/10.3390/polym10060616 - 05 Jun 2018

Cited by 73 | Viewed by 11739

Abstract

Polydimethylsiloxane (PDMS) polymers are extensively used in a wide range of research and industrial fields, due to their highly versatile chemical, physical, and biological properties. Besides the different two-dimensional PDMS formulations available, three-dimensional PDMS foams have attracted increased attention. However, as-prepared PDMS foams contain residual unreacted low molecular weight species that need to be removed in order to obtain a standard and chemically stable material for use as a scaffold for different decorating agents. We propose a cleaning procedure for PDMS foams obtained using a sugar templating process, based on the use of two different solvents (hexane and ethanol) as cleaning agents. Thermogravimetry coupled with Fourier Transform Infrared Spectroscopy (TG-FTIR) for the analysis of the evolved gasses was used to characterize the thermal stability and decomposition pathway of the PDMS foams, before and after the cleaning procedure. The results were compared with those obtained on non-porous PDMS bulk as a reference. Micro-CT microtomography and scanning electron microscopy (SEM) analyses were employed to study the morphology of the PDMS foam. The thermogravimetric analysis (TGA) revealed a different thermal behaviour and crosslinking pathway between bulk PDMS and porous PDMS foam, which was also influenced by the washing process. This information was not apparent from spectroscopic or morphological studies and it would be very useful for planning the use of such complex and very reactive systems. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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14 pages, 11213 KiB

Open AccessArticle

Hyperbranched Polysiloxanes Based on Polyhedral Oligomeric Silsesquioxane Cages with Ultra-High Molecular Weight and Structural Tuneability

by Ning Liu, Jianyi Yu, Yaoyong Meng and Yuzhou Liu

Polymers 2018, 10(5), 496; https://doi.org/10.3390/polym10050496 - 04 May 2018

Cited by 8 | Viewed by 4822

Abstract

Hyperbranched siloxane-based polymers with ultra-high molecular weight were synthesized by the Piers–Rubinsztajn reaction between octakis(dimethylsiloxy) octasilsesquioxane with different dialkoxysilanes, using tris(pentafluorophenyl) borane as the catalyst. The origin of the high molecular weight is explained by the high reactivity of the catalyst and strain energy of isolated small molecule in which all eight silane groups close into rings on the sides of a single cubic cage. The structural tuneability was further demonstrated by use of methyl(3-chloropropyl)diethoxysilane, which generates a polymer with similar ultra-high molecular weight. Introduction of phosphonate groups through the chloropropyl sites later leads to functionalized polymers which can encapsulate various transition metal nanoparticles. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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18 pages, 2308 KiB

Open AccessArticle

Synthesis, Characterization and Microstructure of New Liquid Poly(methylhydrosiloxanes) Containing Branching Units SiO_4/2

by Jerzy J. Chruściel, Marzena Fejdyś and Witold Fortuniak

Polymers 2018, 10(5), 484; https://doi.org/10.3390/polym10050484 - 28 Apr 2018

Cited by 12 | Viewed by 6293

Abstract

Six liquid branched poly(methylhydrosiloxanes) of new random structures (PMHS-Q), containing quadruple branching units SiO_4/2 (Q), both MeHSiO (D^H) and Me₂SiO (D) chain building units (or only mers MeHSiO), and terminal groups Me₃SiO_0.5 (M) were prepared by a hydrolytic polycondensation method of appropriate organic chlorosilanes and tetraethyl ortosilicate (TEOS), in diethyl ether medium at temperature below 0 °C. Volatile low molecular weight siloxanes were removed by a vacuum distillation at 150–155 °C. Yields of PMHS-Q reached from 55–69 wt%. Their dynamic viscosities were measured in the Brookfield HBDV+IIcP cone-plate viscometer and ranged from 10.7–13.1 cP. Molecular weights (MW) of PMHS-Q (M_n = 2440–6310 g/mol, M_w = 5750–10,350 g/mol) and polydispersities of MW (M_w/M_n = 2.0–2.8) were determined by a size exclusion chromatography (SEC). All polymers were characterized by FTIR, ¹H- and ²⁹Si-NMR, and an elemental analysis. A microstructure of siloxane chains was proposed on a basis of ²⁹Si-NMR results and compared with literature data. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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12 pages, 5824 KiB

Open AccessArticle

Non-Leachable Hydrophilic Additives for Amphiphilic Coatings

by Guillaume Gillet, Fabrice Azemar, Fabienne Faÿ, Karine Réhel and Isabelle Linossier

Polymers 2018, 10(4), 445; https://doi.org/10.3390/polym10040445 - 16 Apr 2018

Cited by 6 | Viewed by 5536

Abstract

Amphiphilic surfaces are particularly effective at inhibiting the adhesion of microorganisms (bacteria, cells, microalgae, etc.) in liquid media. The aim of this study is to determine the best hydrophilic linker to promote bonding between poly(ethylene glycol) (PEG) as a hydrophilic additive and poly(dimethyl siloxane) (PDMS) as the hydrophobic matrix. Various parameters have been studied (molecular weight, linker type, and polymer end-group), as well as the efficiency of the linking, the capacity of PEG to access to the surface of the film, and overall film homogeneity. According to the results, a PDMS linker paired with a PEG moiety allows for compatibilization of the compounds during cross-linking. This compatibilization seems to provide a good bonding with the matrix and a good surface access to the hydrophilic moiety. Therefore, this structure comprising a linking function attached to the PDMS–PEG copolymer has high potential as a non-releasable additive for amphiphilic coating applications. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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20 pages, 52323 KiB

Open AccessArticle

Effect of Polysiloxanes on Roughness and Durability of Basalt Fibres–Reinforced Cement Mortar

by Danuta Barnat-Hunek, Grzegorz Łagód, Stanisław Fic and Monika Jarosz-Hadam

Polymers 2018, 10(4), 420; https://doi.org/10.3390/polym10040420 - 09 Apr 2018

Cited by 24 | Viewed by 4100

Abstract

The influence of roughness and the way it affects the adhesion properties and surface free energy (SFE) of polysiloxanes hydrophobised basalt fibres–reinforced cement mortars were determined in this article. The physical properties of mortars were investigated in the experimental part, which also explored the impact of hydrophobisation and basalt fibres (BF) addition on SFE, frost resistance, contact angle (CA), and roughness. A device capable of calculating all parameters was used to indicate the surface roughness and 3D topography. Prior to and after conducting surface and weight hydrophobisation, the contact angle of mortars was specified. Subsequently, it was used for carrying out SFE calculation by means of Neumann’s method, enabling us to characterize the adhesion properties and wettability of mortars. The research indicated that the surface roughness was substantially decreased, in turn raising the frost resistance. The corrosion resistance drops when the surface roughness, water absorption, and number of fibres in the mortar increase. The SEM images presenting the structure of polysiloxane coating and mortars were provided. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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12 pages, 24838 KiB

Open AccessArticle

Improving the Mechanical and Electrical Properties of Ceramizable Silicone Rubber/Halloysite Composites and Their Ceramic Residues by Incorporation of Different Borates

by Jianhua Guo, Xuming Chen and Yong Zhang

Polymers 2018, 10(4), 388; https://doi.org/10.3390/polym10040388 - 01 Apr 2018

Cited by 29 | Viewed by 5311

Abstract

Ceramizable silicone rubber (MVQ)/halloysite (HNT) composites were fabricated by incorporation of three different borates, including sodium tetraborate decahydrate, ammonium pentaborate, and zinc borate into MVQ matrix, respectively. The composites without any borates were also prepared as control. The effect of the borates on the mechanical and electrical properties of MVQ/HNT composites was investigated. The ceramic residues were obtained from the decomposition of the composites after sintering at 1000 °C. The effect of the borates on the linear shrinkage, weight loss, and flexural and impact strength of the residues was also studied. The fracture surfaces of the composites and their corresponding residues were observed by SEM. The proposed ceramizable mechanism of the composites by incorporation of different borates was revealed by XRD analysis. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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11 pages, 13667 KiB

Open AccessArticle

POSS Dental Nanocomposite Resin: Synthesis, Shrinkage, Double Bond Conversion, Hardness, and Resistance Properties

by Yizhi Liu, Xiaorong Wu, Yi Sun and Weili Xie

Polymers 2018, 10(4), 369; https://doi.org/10.3390/polym10040369 - 26 Mar 2018

Cited by 29 | Viewed by 4962

Abstract

Nanocomposite dental resins with 0, 2, 5, and 10 wt % methacryl polyhedral oligomeric silsesquioxane (POSS) as filler in the resin matrix were prepared by a light curing method.The atomic force microscopy (AFM), fourier transform infrared spectroscopy (FTIR), nanoindentation, and nanoscratch tests were carried out to study the effect of POSS contents on the compatibility, double bond conversion, volumetric shrinkage, hardness, modulus, and resistance of the dental resins. POSS was very uniformly dispersed and showed a good compatibility with the matrix. The double bond conversion increased and the volume reduced with the addition of POSS. As the POSS addition increased, the mechanical properties increased initially. Small addition of POSS remarkably enhanced the hardness and scratch resistance of the resin matrix. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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12 pages, 5498 KiB

Open AccessArticle

PNIPAM-MAPOSS Hybrid Hydrogels with Excellent Swelling Behavior and Enhanced Mechanical Performance: Preparation and Drug Release of 5-Fluorouracil

by Peihong Li, Xiaoman Hou, Lijie Qu, Xueyan Dai and Chunling Zhang

Polymers 2018, 10(2), 137; https://doi.org/10.3390/polym10020137 - 31 Jan 2018

Cited by 33 | Viewed by 5975

Abstract

Poly(N-isopropylacrylamide) (PNIPAM) is a widely-studied polymers due to its excellent temperature sensitivity. PNIPAM-MAPOSS hybrid hydrogel, based on the introduction of acrylolsobutyl polyhedral oligomeric silsesquioxane (MAPOSS) into the PNIPAM matrix in the presence of polyethylene glycol, was prepared via radical polymerization. The modified hydrogels exhibited a thick, heterogeneous porous structure. PEG was used as a pore-forming agent to adjust the pore size. MAPOSS reduced the swelling ratios of gels, and decreased the LCST, causing the hydrogels to shrink at lower temperatures. However, its hydrophobicity helped to improve the temperature response rate. The incorporation of rigid MAPOSS into the polymer network greatly increased the compressive modulus of the hydrogel. It is worth noting that, by adjusting the amount of MAPOSS and PEG, the hydrogel could have both ideal mechanical properties and swelling behavior. In addition, hydrogel containing 8.33 wt % MAPOSS could achieve stable and sustained drug release. Thus, the prepared PNIPAM-MAPOSS hybrid hydrogel can serve as drug carrier for 5-fluorouracil and may have potential application in other biomedical fields. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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13 pages, 3373 KiB

Open AccessArticle

A New Route for Preparation of Hydrophobic Silica Nanoparticles Using a Mixture of Poly(dimethylsiloxane) and Diethyl Carbonate

by Iryna Protsak, Evgeniy Pakhlov, Valentyn Tertykh, Zi-Chun Le and Wen Dong

Polymers 2018, 10(2), 116; https://doi.org/10.3390/polym10020116 - 26 Jan 2018

Cited by 28 | Viewed by 8393

Abstract

Organosilicon layers chemically anchored on silica surfaces show high carbon content, good thermal and chemical stability and find numerous applications as fillers in polymer systems, thickeners in dispersing media, and as the stationary phases and carriers in chromatography. Methyl-terminated poly(dimethylsiloxanes) (PDMSs) are typically considered to be inert and not suitable for surface modification because of the absence of readily hydrolyzable groups. Therefore, in this paper, we report a new approach for surface modification of silica (SiO₂) nanoparticles with poly(dimethylsiloxanes) with different lengths of polymer chains (PDMS-20, PDMS-50, PDMS-100) in the presence of diethyl carbonate (DEC) as initiator of siloxane bond splitting. Infrared spectroscopy (IR), elemental analysis (CHN), transmission electron microscopy (TEM), atomic force microscopy (AFM), rotational viscosity and contact angle of wetting were employed for the characterization of the raw fumed silica and modified silica nanoparticles. Elemental analysis data revealed that the carbon content in the grafted layer is higher than 8 wt % for all modified silicas, but it decreases significantly after sample treatment in polar media for silicas which were modified using neat PDMS. The IR spectroscopy data indicated full involvement of free silanol groups in the chemisorption process at a relatively low temperature (220 °C) for all resulting samples. The contact angle studies confirmed hydrophobic surface properties of the obtained materials. The rheology results illustrated that fumed silica modified with mixtures of PDMS-x/DEC exhibited thixotropic behavior in industrial oil (I-40A), and exhibited a fully reversible nanostructure and shorter structure recovery time than nanosilicas modified with neat PDMS. The obtained results from AFM and TEM analysis revealed that the modification of fumed silica with mixtures of PDMS-20/DEC allows obtaining narrow particle size distribution with uniform dispersity and an average particle size of 15–17 nm. The fumed silica nanoparticles chemically modified with mixtures of PDMS-x/DEC have potential applications such as nanofillers of various polymeric systems, thickeners in dispersing media, and additives in coatings. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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10 pages, 2201 KiB

Open AccessArticle

Quartz Microcrystal-Hybridized Organosilicone Encapsulant with Enhanced Optical and Thermal Performances

by Xin Chen, Yancong Feng, Xiao Wang, En Li, Yao Wang, Lingling Shui, Hao Li, Nan Li and Guofu Zhou

Polymers 2018, 10(1), 84; https://doi.org/10.3390/polym10010084 - 16 Jan 2018

Cited by 3 | Viewed by 3914

Abstract

Encapsulant is one determining factor underpinning the device lifetimes of organic optoelectronics. However, encapsulant seriously needs improvement in optical, thermal, and mechanical properties, especially to develop organic light emitting diodes. In this study, we prepared an in situ crosslinked organosilane composite containing benzyloxy and glycidyl-modified quartz microcrystal (mQMC) as high performance encapsulant. In the present work, methylphenylsilanediol (MPSD) was introduced as a novel crosslinker to impart appropriate structural strength. Along with increasing mQMC fillers, this organosilane system shows improved properties, such as refractive index, thermal stability, and storage modulus. Specifically, these hybridized mQMCs in the organosilane framework may facilitate an approximate two-fold increase (0.238 W/(m·K)) in overall thermal conductivity at the determined concentration. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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5282 KiB

Open AccessArticle

Plateau-Shaped Flexible Polymer Microelectrode Array for Neural Recording

by Jun-Min Kim, Changkyun Im and Woo Ram Lee

Polymers 2017, 9(12), 690; https://doi.org/10.3390/polym9120690 - 08 Dec 2017

Cited by 18 | Viewed by 7250

Abstract

Conventional polymer multielectrode arrays (MEAs) have limitations resulting from a high Young’s modulus, including low conformability and gaps between the electrodes and neurons. These gaps are not a problem in soft tissues such as the brain, due to the repopulation phenomenon. However, gaps can result in signal degradation when recording from a fiber bundle, such as the spinal cord. Methods: We propose a method for fabricating flexible polydimethylsiloxane (PDMS)-based MEAs featuring plateau-shaped microelectrodes. The proposed fabrication technique enables the electrodes on the surface of MEAs to make a tight connection to the neurons, because the wire of the MEA is fabricated to be plateau-shaped, as the Young’s modulus of PDMS is similar to soft tissues and PDMS follows the curvature of the neural tissue due to its high conformability compared to the other polymers. Injury caused by the movement of the MEAs can therefore be minimized. Each electrode has a diameter of 130 μm and the 8-channel array has a center-to-center electrode spacing of 300 μm. The signal-to-noise ratio of the plateau-shaped electrodes was larger than that of recessed electrodes because there was no space between the electrode and neural cell. Reliable neural recordings were possible by adjusting the position of the electrode during the experiment without trapping air under the electrodes. Simultaneous multi-channel neural recordings were successfully achieved from the spinal cord of rodents. We describe the fabrication technique, electrode 3D profile, electrode impedance, and MEA performance in in vivo experiments in rodents. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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Review

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11 pages, 2374 KiB

Open AccessReview

Polysiloxanes in Theranostics and Drug Delivery: A Review

by Ignazio Blanco

Polymers 2018, 10(7), 755; https://doi.org/10.3390/polym10070755 - 09 Jul 2018

Cited by 42 | Viewed by 5435

Abstract

One of the historical problems of medicine is that often, diagnosis and therapy do not interface, at best. Moreover, especially in some areas, such as oncology, the stress for the organism during the two phases (diagnosis and therapy) can become excessive, and be fatal to the success of the treatment. The extraordinary progress of nanotechnology in the last 25 years has offered the opportunity to build a nanoplatform able to ferry drugs, and loads onto them both imaging and therapeutic functions, thus creating nanosystems capable of diagnosis, drug delivery, and monitoring of therapeutic response. The purpose of this unusual, and up to recent times, unimaginable, marriage between diagnosis and therapeutics is the reaching of protocols more specific to individuals. The dual use of particles/device lead to a personalized medicine. Due to their biocompatibility, versatility, physical and chemical resistance, and ability to be functionalized, silica nanoparticles and polysiloxanes are the heart and the shield of this nanoplatform, respectively. In this short review, I analyze the applications of these silicon-based materials in the field of controlled drug delivery. Full article

(This article belongs to the Special Issue Siloxane-Based Polymers)

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