Hexagonal Boron Nitride as Filler for Silica-Based Elastomer Nanocomposites

Two-dimensional hexagonal boron nitride (hBN) has attracted tremendous attention over the last few years, thanks to its stable structure and its outstanding properties, such as mechanical strength, thermal conductivity, electrical insulation, and lubricant behavior. This work demonstrates that hBN can also improve the rheological and mechanical properties of elastomer composites when used to partially replace silica. In this work, commercially available pristine hBN (hBN-p) was exfoliated and ball-mill treated in air for different durations (2.5, 5, and 10 h milling). Functionalization occurred with the -NH and -OH groups (hBN-OH). The functional groups were detected using Fourier-Transform Infrared pectroscopy (FT-IR) and were estimated to be up to about 7% through thermogravimetric analysis. The presence of an increased amount of oxygen in hBN-OH was confirmed using Scanning Electron Microscopy coupled with Energy-Dispersive X-ray Spectroscopy. (SEM-EDS). The number of stacked layers, estimated using WAXD analysis, decreased to 8–9 in hBN-OH (10 h milling) from about 130 in hBN-p. High-resolution transmission electron microscopy (HR-TEM) and SEM-EDS revealed the increase in disorder in hBN-OH. hBN-p and hBN-OH were used to partially replace silica by 15% and 30%, respectively, by volume, in elastomer composites based on poly(styrene-co-butadiene) from solution anionic polymerization (S-SBR) and poly(1,4-cisisoprene) from Hevea Brasiliensis (natural rubber, NR) as the elastomers (volume (mm3) of composites released by the instrument). The use of both hBNs in substitution of 30% of silica led to a lower Payne effect, a higher dynamic rigidity, and an increase in E0 of up to about 15% at 70 C, with similar/lower hysteresis. Indeed, the composites with hBN-OH revealed a better balance of tan delta (higher at low temperatures and lower at high temperatures) and better ultimate properties. The functional groups reasonably promote the interaction of hBN with silica and with the silica’s coupling agent, sulfur-based silane, and thus promoted the interaction with the elastomer chains. The volume of the composite, measured using a high-pressure capillary viscometer, increased by about 500% and 400% after one week of storage in the presence of hBN-p and hBN-OH. Hence, both hBNs improved the processability and the shelf life of the composites. Composites obtained using hBN-OH had even filler dispersion without the detachments of the filler from the elastomer matrix, as shown through TEM micrographs. These results pave the way for substantial improvements in the important properties of silica-based composites for tire compounds, used to reduce rolling resistance and thus the improve environmental impacts

Bio-Based Pyrrole Compounds Containing Sulfur Atoms as Coupling Agents of Carbon Black with Unsaturated Elastomers

In this work, the hysteresis of elastomer composites suitable for tire compounds was reduced by using CB functionalized with pyrrole compounds containing sulfur-based functional groups reactive with the elastomer chains. CB was functionalized with bio-based pyrrole compounds: 2-(2,5-dimethyl-1H-pyrrol-1-yl)ethane-1-thiol (SHP) and 1,2-bis(2-(2,5-dimethyl-1H-pyr-rol-1-yl)ethyl)disulfide (SSP), bearing an -SH and an -SS- functional group, respectively. SHP and SSP were synthesized via a one-pot two-step synthesis, with yields higher than 70%, starting from biosourced chemicals as follows: 2,5-hexanedione from 2,5-dimethylfuran, cysteine and cysteamine. The functionalization of CB was carried out by mixing the CB with PyC and heating, with quantitative yields ranging from 92 to 97%. Thus, the whole functionalization process was characterized by a high carbon efficiency. The formation of the covalent bond between SHP, SSP and CB, in line with the prior art of such a functionalization technology, was proven by means of extraction and TGA analyses. The reactivity of the sulfur-based functional groups with unsaturated polymer chains was demonstrated by using squalene as the model compound. Poly(styrene-co-butadiene) from solution anionic polymerization and poly(1,4-cis-isoprene) from Hevea Brasiliensis were the elastomers employed for the preparation of the composites, which were crosslinked with a sulfur-based system. Pristine CB was partially replaced with CB/SHP (33%) and CB/SSP (33% and 66%). The PyC resulted in better curing efficiency, an increase in the dynamic rigidity of approximately 20% and a reduction in the hysteresis of approximately 10% at 70 degree celsius, as well as similar/better ultimate tensile properties. The best results were achieved with a 66% replacement of CB with CB/SSP. This new family of reactive carbon blacks paves the way for a new generation of 'green tires', reinforced by a CB reactive with the polymer chains, which provides high mechanical properties and low rolling resistance. Such a reactive CB eliminates the use of silica, and thus the ethanol emission resulting from the condensation of silane is used as a coupling agent. In addition, CB-based tires are characterized by a higher mileage, at a moment in which the reduction in tire wear has become a primary concern

Functionalization of graphene related materials with biosourced C-3 and C-6 building blocks. From synthesis to applications

The functionalization of sp2 carbon allotropes is one of the hot research topics in advanced research on materials. Nowadays, carbon nanotubes and graphene related materials are extensively studied due to their exceptional mechanical and electrical properties. They are capable of substantially improving the properties of polymeric materials. Their functionalization is a crucial step, for allowing an even dispersion in the matrix. In this research, the functionalization of graphene related materials was performed with biosourced C-3 and C-6 molecules. They were glycerol and galactaric acid derivatives: pyrrole compounds (PyC) and 2-pyrones. The reactions for their synthesis and for the carbon allotrope functionalization were green and characterized by high atom efficiency, with a yield up to 96%. Indeed, the reactions were carried out in the absence of solvents and catalysts and adducts were obtained by simply mixing, with the help of either thermal or mechanical energy. The developed functionalization methods were successful for: carbon black, carbon nanotubes, few layers graphene. The bulk structure of the carbon substrate was left substantially unaltered: functionalization occurred in peripheral positions, at the edges of the graphene layers. Functional groups of defined chemical structure were covalently bound to the carbon material and stable adducts, up to very high temperature, were formed. Reliable hypotheses for the functionalization mechanisms were elaborated. In Figure 1b the supposed domino reaction based on the pyrrole compound, with the Diels Alder cycloaddition as the last step is represented. Such functionalization technique was developed as a pervasive technology, which allowed to pursue a variety of applications: (i) decoration with metals to obtain catalysts for the selective deuteration of pharmaceutical molecules as well as antibacterial ingredients (ii) rubber compounds for dynamic-mechanical applications (tires) (iii) conductive inks

Silica-Based Composites with Enhanced Rheological Properties Thanks to a Nanosized Graphite Functionalized with Serinol Pyrrole

: Silica-based rubber composites have tremendous importance, as they allow the reduction in hysteresis in demanding dynamic-mechanical applications such as tire compounds and hence have a lower environmental impact. However, they also present drawbacks such as poor rheological behavior. In this work, an innovative silica-based hybrid filler system was developed, obtaining a rubber composite with an improved set of properties. A nanosized high surface area graphite (HSAG) was functionalized with 2-(2,5-dimethyl-1H-pyrrol-1-yl)propane-1,3-diol, serinol pyrrole (SP), through a simple process characterized by a high carbon efficiency. The HSAG-SP adduct, with about nine parts of SP per hundred parts of carbon filler, was used to form a hybrid filler system with silica. An elastomeric composite, with poly(styrene-co-butadiene) from anionic polymerization and poly(1,4-cis-isoprene) from Hevea brasiliensis was prepared with 50 parts of silica, which was replaced in a minor amount (15%) by either pristine HSAG or HSAG-SP. The best set of composite properties was obtained with HSAG-SP: the same dynamic rigidity and hysteresis and tensile properties of the silica-based material and appreciably better rheological properties, particularly in terms of flowability. This work paves the way for a new generation of silica-based composites, with improved properties, based on a hybrid filler system with a nanosized edge functionalized graphite

Sustainable and versatile functionalization of graphene layers

Facile, sustainable and versatile functionalization of graphene layers was performed. Functional groups were essentially at the layer edges and the structure of the graphitic substrate remained substantially unaltered. Functionalization was done with pyrrole compounds (PyC) prepared through the Paal-Knorr reaction of a primary amine with 2,5-hexanedione. A good number of primary amines were used and a large variety of functional groups were added to the graphene layers: hydroxy, silanes, aldehydes, carboxylic acid. The functionalization reactions were carried out by simply mixing the reagents and heating, e.g at 150°C for 3 hours. The reactions had good yield, up to 96%, and atom efficiency up to 80% and scale up was done to kg level. A domino process has been hypothesized as the mechanism of the functionalization reaction, made by successive Paal Knorr reaction, carbocatalyzed oxidation and cycloaddition. A good number of applications have been successfully explored: inks and varnishes, advanced lightweight nanocomposites materials, e.g.: rubbers for low dissipation of energy, flame retardant polyurethanes, biobased carbon papers and aerogels. The intellectual property of this functionalization technology is characterized by many families of Patents

Graphene Layers Functionalized with A Janus Pyrrole-Based Compound in Natural Rubber Nanocomposites with Improved Ultimate and Fracture Properties

The ultimate properties and resistance to fracture of nanocomposites based on poly(1,4-cis-isoprene) from Hevea Brasiliensis (natural rubber, NR) and a high surface area nanosized graphite (HSAG) were improved by using HSAG functionalized with 2-(2,5-dimethyl-1H-pyrrol-1-yl)propane-1,3-diol (serinol pyrrole) (HSAG-SP). The functionalization reaction occurred through a domino process, by simply mixing HSAG and serinol pyrrole and heating at 180 °C. The polarity of HSAG-SP allowed its dispersion in NR latex and the isolation of NR/HSAG-SP masterbatches via coagulation. Nanocomposites, based either on pristine HSAG or on HSAG-SP, were prepared through traditional melt blending and cured with a sulphur-based system. The samples containing HSAG-SP revealed ultimate dispersion of the graphitic filler with smaller aggregates and higher amounts of few layers stacks and isolated layers, as revealed by transmission electron microscopy. With HSAG-SP, better stress and elongation at break and higher fracture resistance were obtained. Indeed, in the case of HSAG-SP-based composites, fracture occurred at larger deformation and with higher values of load and, at the highest filler content (24 phr), deviation of fracture propagation was observed. These results have been obtained with a moderate functionalization of the graphene layers (about 5%) and normal lab facilities. This work reveals a simple and scalable way to prepare tougher NR-based nanocomposites and indicates that the dispersion of a graphitic material in a rubber matrix can be improved without using an extra-amount of mechanical energy, just by modifying the chemical nature of the graphitic material through a sustainable process, avoiding the traditional complex approach, which implies oxidation to graphite oxide and subsequent partial reduction

Pyrrole Compounds from the Two-Step One-Pot Conversion of 2,5-Dimethylfuran for Elastomer Composites with Low Dissipation of Energy

A one-pot, two-step process was developed for the preparation of pyrrole compounds from 2,5-dimethylfuran. The first step was the acid-catalyzed ring-opening reaction of 2,5-dimethylfuran (DF), leading to the formation of 2,5-hexanedione (HD). A stoichiometric amount of water and a sub-stoichiometric amount of sulfuric acid were used by heating at 50 °C for 24 h. Chemically pure HD was isolated, with a quantitative yield (up to 95%), as revealed by 1H-NMR, 13C-NMR, and GC-MS analyses. In the second step, HD was used as the starting material for the synthesis of pyrrole compounds via the Paal–Knorr reaction. Various primary amines were used in stoichiometric amounts. 1H-NMR, 13C-NMR, ESI-Mass, and GC-Mass analyses confirmed that pyrrole compounds were prepared with very good/excellent yields (80–95%), with water as the only co-product. A further purification step was not necessary. The process was characterized by a very high carbon efficiency, up to 80%, and an E-factor down to 0.128, whereas the typical E-factor for fine chemicals is between 5 and 50. Water, a co-product of the second step, can trigger the first step and therefore make the whole process circular. Thus, this synthetic pathway appears to be in line with the requirements of a sustainable chemical process. A pyrrole compound bearing an SH group (SHP) was used for the functionalization of a furnace carbon black (CB). The functionalized CB (CB/SHP) was utilized in place of silica, resulting in a 15% mass reduction of reinforcing filler, in an elastomeric composite based on poly(styrene-co-butadiene) from solution anionic polymerization and poly(1,4-cis-isoprene) from Hevea Brasiliensis. Compared to the silica-based composite, a reduction in the Payne effect of about 25% and an increase in the dynamic rigidity (E’ at 70 °C) of about 25% were obtained with CB/SHP