polymers

Editorial
Silicon-Containing Polymeric Materials
Ignazio Blanco

Department of Civil Engineering and Architecture and INSTM UdR, University of Catania, Viale Andrea Doria 6,
95125 Catania, Italy; iblanco@unict.it

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. Particularly 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 ensure that it will continue to play, in the years to come, a vital role in everyday life.
In addition to silicones or polysiloxanes [1–4], which have been known and manufactured
for many years, silica-reinforced polymers, silsesquioxanes, and POSS-based polymers
also offer a multitude of very useful consumer products [5]. The combination of silicon
and oxygen atoms with organic groups has led 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. This is why the editorial Board
of Polymers decided to institute, belong to the section of Polymer Chemistry, the Topical
Collection “Silicon-Containing Polymeric Materials”, offering the possibility of publishing
novel researches exploring silicon-containing polymeric materials and their applications.
The Topical collection hosted three special issues: POSS-Based Polymers; Siloxane-
Based Polymers; Silsesquioxane (POSS) Polymers, Copolymers and Nanoparticles; and it
collected 112 papers and many views, downloads and citations, demonstrating the vitality





 of this area of the polymeric world. The highly cited works are summarized in this editorial.
Catauro and co-workers used pure silica and silica-based hybrids materials, containing
Citation: Blanco, I.
polyethylene glycol (PEG), to synthesize, using the sol-gel technique, novel phenol-based
Silicon-Containing Polymeric
materials with phenolic antioxidant chlorogenic acid (CGA) at various percentages, aim-
Materials. Polymers 2021, 13, 188.
https://doi.org/10.3390/polym
ing to reduce the matrix’s degradation and thus the loss of its properties. Thermal and
13020188
soaking analyses demonstrated the improvement of matrix performance by maintaining
its bioactivity, despite the presence of PEG and CGA [6].
Academic Editor: Shin-ichi Yusa Liang et al. used surface modified and unmodified fumed nano-silica for reinforcing
Received: 31 December 2020 silicone rubber composites for high voltage insulating materials in power transmission
Accepted: 4 January 2021 and substation systems. During the evaluation of silicone composites they observed
Published: 7 January 2021 modifications in the dielectric response with both of the two type of silica used: a paralleled
combination of Maxwell-Wagner-Sillars interface polarization and DC conduction by using
Publisher’s Note: MDPI stays neu- the modified silica; a quasi-DC transport process by using the unmodified nano-silica. They
tral with regard to jurisdictional clai- also observed an improvement in the mechanical strength with increasing silica content [7].
ms in published maps and institutio- Elías-Zúñiga and colleagues studied magnetorheological elastomers (MREs) based
nal affiliations. on a silicone–rubber matrix and carbonyl iron microparticles. After the preparation of the
samples, with and without the application of an external magnetic field, the researchers
evaluated the rheological behavior of isotropic and anisotropic composites, finally plotting
Copyright: © 2021 by the author. Li-
the Cole-Cole diagrams to quantify the interfacial adhesion between particles and silicone.
censee MDPI, Basel, Switzerland.
They recorded a different performance for the anisotropic and isotropic composites, with
This article is an open access article
the latter showing a reduction in the loss and storage modulus compared with the bare
distributed under the terms and con- material. Conversely, in the anisotropic composites, the good particles’ dispersion led to
ditions of the Creative Commons At- an increase of the modulus and damping properties and an increase of the loss and the
tribution (CC BY) license (https:// storage modulus compared to those of the bare material [8].
creativecommons.org/licenses/by/ Marine antifouling coatings based on silicone elastomers, unlike biocide-based ones,
4.0/). do not release biocides into the marine environment, but the antifouling efficacy during

Polymers 2021, 13, 188. https://doi.org/10.3390/polym13020188 https://www.mdpi.com/journal/polymers

Polymers 2021, 13, 188 2 of 6

idle periods is strongly reduced. With the aim to enhance this specific performance,
Gevaux et al. reinforced a silicone matrix with various amounts of hydrolysable polymers,
such as poly(ε-caprolactone) (PCL), poly(bis(trimethylsilyloxy)methylsilyl methacrylate).
The France researchers evaluated the attachment of macrofoulers on these coatings by field
tests in the Mediterranean Sea, demonstrating the short or long-term antifouling effect of
these hydrolyzable polymers embedded in the silicone matrix [9].
Lopez-Manchado and co-workers applied themselves in the tailoring of the mechan-
ical and transport properties of silicone rubber nanocomposites with thermally reduced
Graphene Oxide (TRGO), aiming to improve their thermal conductivity for application
in power electronics and electric motors. The researchers from Spain, by regulating the
morphological and structural characteristics of TRGO, as well as its concentration in the
composite, demonstrated that TRGOs with high specific surface area and a partial aro-
matic restoration are suitable to improve both the mechanical properties and the electrical
conductivity of silicone rubber composites [10].
Yang et al. employed their studies on the balance of the properties requirement of
silicone-based hydrogel contact lenses, such as water content, oxygen permeability, optical
transparency, contact angle, protein adsorption and cell toxicity. They observed that the
presence of 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane enhances the oxygen
permeability while the presence of N,N-dimethylacrylamide and 1-vinyl-2-pyrrolidinone
influenced the hydrophilicity of the hydrogels. Since their hydrogel showed good oxygen
permeability, stiffness and optical transparency, as well as anti-protein adsorption, they
concluded that this silicone-hydrogel can be commercialized for contact lens [11].
Instead of the random and more commercialized cage-structured silsesquioxanes,
Bae et al. designed and synthesized, in a very short time by sol–gel method and free-radical
polymerization, a structurally ordered siloxane backbone with a ladder-like structure. This
structure turned out an essential factor for high performance, they tested by optical, ther-
mal and mechanical characterization, suggesting the ladder-like structured methacrylate
siloxane hybrid as a powerful alternative for the methacrylate polysilsesquioxane [12].
Niemczyk et al., by the means of Thermogravimetry-Fourier Transform Infrared
Spectroscopy (TG-FTIR) and cone calorimeter analysis, evaluated the effects of a novel
group of silsesquioxanes, namely siloxane-silsesquioxane resins (S4SQ), as possible flame
retardants for polypropylene (PP). By using a small amount of S4SQ, they observed a
beneficial effect due to the formation of a continuous ceramic layer on the material surface
during its combustion, which improved both thermal stability and flame retardancy of the
PP. Based on the TG-FTIR results the polish researchers proposed a possible mechanism
for the degradation of S4SQ resins to explain their role during the combustion of the
PP/S4SQ composites [13].
Tong and his colleagues focused their studies on the effects of the variation in electron-
deficient units on the properties of photovoltaic polymers. Namely, they designed and
synthesized three alternated D- p-A type 5,10-bis(triisopropylsilylethynyl)dithieno[2,3-
d:20 ,30 -d’]-benzo[1,2-b:4,5-b’]dithiophene (DTBDT-TIPS)-based semiconducting conjugated
copolymers (CPs), PDTBDT-TIPS-DTBT-OD, PDTBDT-TIPS-DTFBT-OD, and PDTBDT-
TIPS-DTNT-OD, bearing different A units, including benzothiadiazole (BT), 5,6-difluorinated-
BT (FBT) and naphtho[1,2-c:5,6-c’]-bis[1,2,5]thiadiazole (NT). Their investigation, and
the obtained results, certified the replacement of BT with NT in a D- p-A type polymer
backbone as a good strategy for tuning the molecular structure aiming at producing highly
efficient polymer solar cells (PSCs). In particular, the optimized photovoltaic device based
on the PDTBDT-TIPS-DTNT-OD showed a drastic enhancement of the power conversion
efficiency, and deteriorated after incorporating fluorine into the BT, due to the oversized
aggregation and large phase separation morphology in the blend films [14].
Łagód and co-workers studied the effects of polysiloxanes hydrophobised’s incorpora-
tion in basalt fibres–reinforced cement mortars. Specifically, they evaluated the roughness,
the adhesion properties and the surface free energy (SFE), finding a decrease in the surface
roughness and an increase in the frost resistance. Unfortunately, the polymer admixture
Polymers 2021, 13, 188 3 of 6

led to the formation of chemical bonds among the concrete components, influencing the
changes in the microstructure and the strength parameters. In particular, the hardening
process of polysiloxane gel in the aqueous environment of cement slurry and cement hy-
dration in the presence of polymer compound are disrupted, and this is the reason why the
researchers do not recommend the application of polysiloxanes in this type of mortars [15].
A completely different application area of polysiloxanes was highlighted in the review
reported in [16], where the employment of these silicon-based materials in the field of
controlled drug delivery and theranostics was analyzed. Biocompatibility, versatility,
physical and chemical resistance and the ability to be functionalized of these materials
offer the opportunity to overcome one of the historical problems of medicine, namely of
not interfacing at the best of diagnosis and therapy. In this review the research progress in
recent years is shown, which offered the opportunity to build a platform able to ferry drugs,
and load onto them both imaging and therapeutic functions, thus creating nanosystems
capable of diagnosis, drug delivery and monitoring of therapeutic response.
Despite the fact that methyl-terminated poly(dimethylsiloxanes) (PDMSs) are not
suitable for surface modification due to the absence of readily hydrolyzable groups, Le et al.
proposed a new strategy for surface modification based on the use of silica nanoparticles,
poly(dimethylsiloxanes) and diethyl carbonate (DEC) as initiator. They carried out a
spectroscopic and rheologic characterization, finding the full involvement of free silanol
groups in the chemisorption process, hydrophobic surface properties and thixotropic
behavior in industrial oil for the PDMS-x/DEC mixture [17].
In recent years, three-dimensional PDMS foams have attracted increased attention
for use as a scaffold for different decorating agents but they contain residual unreacted
low molecular weight species that need to be removed in order to obtain a standard and
chemically stable material. Duce and co-workers proposed a cleaning procedure for PDMS
foams using a sugar templating process with the employment of two solvents (hexane
and ethanol) as cleaning agents. Then they studied the PDMS’s decomposition, before
and after the cleaning procedure, comparing the obtained data with those of a PDMS
bulk used as a reference. In particular, the Italian researchers highlighted the importance
of thermogravimetric analysis (TGA) in confirming the removal by the washing of low
molecular weight oligomers and unreacted reagents, information not obtainable from
spectroscopic or morphological studies [18].
Since the development of porous polymeric membranes represents an important area
of application in separation technology, Tan and Rodrigue proposed a review work to
summarize the studies on PDMS development from the perspectives of membrane pro-
duction. They reviewed six methods for membrane fabrication, such as thermally induced
phase separation, melt-spinning and cold-stretching, phase separation micromolding,
imprinting/soft molding, manual punching and three-dimensional printing [19].
Probably the hottest topic of this collection is represented by polyhedral oligomeric
silsesquioxanes (POSSs). The wide employment of these materials in the last 25 years (it is
said of their rebirth) is attributable to the setup of a new and easy method of synthesis
by Feher [20,21] and to the intuition of Lichtenhan about the potential applications of
POSSs in the polymer’s sector for making hybrid composites [22,23]. POSSs are composed
of a silicon and oxygen cage, which is externally completed by organic groups that are
covalently bonded with the silicon atoms. The most common value of n is 8, thus generating
a very highly symmetric structure, sometimes indicated in the literature with the symbol
T8 , having a diameter usually ranging in 1.5–3 nm [24]. In comparison with the other
commonly used fillers, POSSs possess the advantage of being molecules, thus they offer
various possibilities of tuning their organic periphery as a function of the matrix which
host them, thus ensuring better compatibility.
Zhang et al. modified the organic groups obtaining acrylolsobutyl polyhedral oligomeric
silsesquioxane (MAPOSS) to be used in reinforcing, via radical polymerization. Poly(N-
isopropylacrylamide) (PNIPAM) was used as drug carrier for 5-fluorouracil. They observed
how the introduction of MAPOSS into the polymer network led to a strong enhancement of
Polymers 2021, 13, 188 4 of 6

the compressive modulus of the hydrogel and how by setting the MAPOSS/polyethylene
glycol (pore-forming agent) ratio it was possible to obtain a good compromise between the
mechanical properties and swelling behavior, thus achieving stable and sustained drug
release [25].
Liu and colleagues prepared resin-based composites by inserting in the POSS’s corona
methacryl groups and then adding different percentages of methacryl POSS to the matrix
by light curing method. The Chinese researchers then carried out a wide investigation
to evaluate the compatibility, double bond conversion, volumetric shrinkage, hardness,
modulus and resistance of the dental resins, which showed uniform dispersion and good
compatibility of MAPOSS with the matrix [26].
Exploiting the possibility offered by POSS to create Hybrid materials, Wei Kuo and
Gamal Mohamed discussed the various methods for inserting these nanoparticles into
polyimide (PI) matrix, a very important techno-polymer. Among the different methods of
preparation they evaluate the covalent chemical bonding and physical blending, as well as
the influence of the POSS units on the physical properties of the PIs [27].
The work of Dai and co-workers always falls in the framework of the hybrids,
which synthesized a novel copolymer by using glycidyl methacrylate (GMA), bis-9,10-
dihydro-9-oxa-10-phosphaphenanthrene-10-oxide methacrylate (bisDOPOMA), functional-
ized graphene oxide (GO) and methacryloisobutyl POSS (POSSMA) for flame retardant
purpose. They observed how the adding of 4 wt% of the hybrid reinforcement increases
the mechanical strength, thermal properties and the limiting oxygen index (LOI) of the
epoxy resin [28].
Członka et al. worked on improving the thermo-mechanical performance of rigid
polyurethane foams (RPUFs) by using different percentage (0.5–5 wt%) of closed-cage
nanostructure, such as aminopropyl isobutyl-POSS (APIB-POSS) and aminoethylaminopro-
pylisobutyl-POSS (AEAPIB-POSS). The morphology, viscoelastic, mechanical and thermal
behavior together with thermal conductivity and application properties were evaluated,
showing the best results when APIB-POSS was added to the RPUFs matrix at 0.5 wt% [29].
Other Polish researchers, Dudziec and co-workers, provided an exhaustive review
regarding the application of organic optoelectronic materials, indicating the possibility of
their use in the construction of organic–inorganic hybrid materials by using the organic
POSSs’ corona architecture linked to their rigid silica cores. They reviewed a significant
number of works dealing with the preparation of POSS-based organic optoelectronic as
well as photoluminescent (PL) materials, focusing on synthesis and catalytic methods to
prepare silsesquioxane systems for photoactive materials [30].
Remaining in the field of optoelectronic devices, Wei et al. synthesized and char-
acterized a series of optically transparent shape memory polyimide films with various
POSS contents. The use of the inorganic POSS structure gave to the hybrid films excellent
thermal stability, with a considerable increase in the glass transition temperature (Tg ) value
(+20 ◦ C), showing the successfully use of POSS in developing transparent polyimides with
excellent thermal stability and shape memory effect for space applications [31].
Dong et al. designed and fabricated raspberry-like hollow-spheres-on-sphere (HSOS)
polysilsesquioxane (PSQ) particles with reactive surfaces, uniform sizes and monodisperse
properties were rational to immobilize gold nanoparticles for the catalytic reduction of
4-nitrophenol. The synthesis process was monitored and the formation mechanism of the
hierarchical particles was investigated in detail by the time of the study through imaging
the particles at regular time intervals during the reaction. The prepared material has shown
potential applications in separations, drug delivery and heterogeneous catalysis [32].

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