Functionalized carbon black for elastomer composites with low hysteresis

The prime application of elastomeric composites is tire compounds. The tuning of dynamic rigidity and hysteresis is key to achieve the desired tire performances. Car tires require hysteresis to be high at low temperatures, to promote wet traction, and low at medium-high temperatures, for low energy dissipations. To achieve these properties amorphous precipitated silica is commonly selected as reinforcing filler due to its nano dimensions and the possibility of establishing chemical bonds with the elastomers’ chains. Carbon black (CB), another common filler for tire compounds, does not have functional groups able to promote chemical bonds with the rubber matrix yet it would be highly desirable. A CB with a cradle to gate LCA comparable if not even better than silica’s LCA could be used in replacement of silica in tire compounds. In this work, a pyrrole compound (PyC) containing a thiol group was used to functionalize CB by the so-called “pyrrole methodology” . The thiol group was expected to react with the sulphur-based crosslinking system, thus forming chemical bonds with the rubber chains. The synthesis of the PyC and the functionalization reaction were characterized by high atom efficiency. A poly(styrene-co-butadiene) copolymer from anionic solution polymerization was used as the main rubber for the compound preparation. The crosslinked composite material filled with functionalized CB revealed substantial improvements with respect to the composite with pristine CB, in particular: high rigidity and low hysteresis at high temperature. These findings seem to confirm the formation of the expected rubber-filler chemical bond and are even comparable to those of silica- based rubber composites. The results here reported pave the way to CB-based rubber composites with a low environmental impact

Functionalized carbon black for elastomeric composites with low dissipation of energy

The most important application of elastomeric composites, tire compounds, relies on the following dynamic-mechanical properties: dynamic rigidity and hysteresis. For car tires, hysteresis is tuned as a function of temperature: high at low temperature and low at medium-high temperature, to promote traction on wet roads and low energy dissipation (rolling resistance), respectively. To obtain these properties, amorphous precipitated silica is used as reinforcing filler. The strengths of silica are: nano dimensions and the possibility of incorporating and establishing chemical bonds with the elastomers’ chains. Carbon black (CB), which is also largely used in tire compounds, does not have functional groups able to promote chemical bonds with the rubber matrix. It would be highly desirable to functionalize the surface of carbon black with such functional groups: a CB with a cradle to gate LCA comparable if not even better than silica’s LCA could be used in replacement of silica in tire compounds. In this work, a pyrrole compound (PyC) was used for functionalizing CB by applying the so-called “pyrrole methodology”. The selected PyC contained a thiol group which was expected to react with the sulphur-based crosslinking system, thus forming chemical bonds with the rubber chains. The synthesis of the PyC and the functionalization reaction were characterized by high atom efficiency. A poly(styrene-co-butadiene) copolymer from anionic solution polymerization was used as the main rubber for the compound preparation. The crosslinked composite material filled with functionalized CB revealed substantial improvements with respect to the composite with pristine CB, in particular: high rigidity and low hysteresis at high temperature. These findings seem to confirm the formation of the expected rubber-filler chemical bond and are even comparable to those of silicabased rubber composites. The results here reported pave the way to CB-based rubber composites with a low environmental impact

Two steps one pot process for the conversion of dimethylfuran to pyrrole compounds with almost null E factor

The replacement of the oil-based chemicals with those derived from biomasses is one of the most exciting challenges of the last decades. For example, 1,4-dicarbonyl compounds have a great importance in chemical synthesis, thanks to their high chemoselectivity and there is an increasing interest for preparing them from biomasses. In particular, 2,5-hexanedione could be synthesized starting from lignocellulosic sources, through the acid-ring opening reaction of 2,5-dimethylfuran as the bio-based feedstock.[1] The reaction of 2,5-hexanedione and a generic primary amine leads to pyrrole compounds. Many examples have been reported by some of the authors.[2] In this work a sustainable process for the preparation of pyrrole compounds starting from a bio-based reagent has been developed. The selected starting material was 2,5-dimethyl furan. In this work, the ring opening reaction of 2,5-dimethylfuran was optimized by tuning parameters such as the amount of water, type and amount of acid, time and temperature. 2,5-hexanedione was obtained with a high yield (95%) without the need of purification. Then, different primary amines, in particular biosourced, have been used to prepare a variety of pyrrole compounds, with high yield (at least 90%) and with high carbon efficiency, without producing waste. The pyrrole compounds have then been used for the functionalization of a nanosized graphite, promoting the exfoliation to few layers graphene

Chemical functionalization of graphene surface as filler for rubber compounds

Over the last few years, the surface modification of fillers for high-level technological applications such as polymer composites for tyre industry, conductive inks and coatings has seen a considerable increase in interest since it can increase mechanical, electrical, and thermal properties of the final material. Nano-sized carbon allotropes such as graphene and carbon nanotubes are a suitable class of compounds for these purposes: high thermal and electrical conductivity along with considerable mechanical reinforcement are the main improvements that these fillers bring to the composite and their elevated surface area allows to reduce the filler volume ratio compared to more common alternatives. An efficient and reliable method to modify the surface of these nano-fillers is the so-called pyrrole methodology, a mild procedure that involves bio-sourced reagents to introduce functional groups on the graphitic planes and that has been recently employed in the fabrication of elastomeric composites with improved mechanical properties. In order to understand the mechanism beneath the interaction between the pyrrole and the substrate and thus the behavior of the functionalized filler, a more in-depth analysis is requested. A theoretical work based on molecular dynamics simulations and a DFT study were performed in order to investigate the interaction energy, the geometry of interaction and the mobility of N-substituted pyrrole molecules adsorbed on the graphene planes. This theoretical study at atomistic level can help design a new class of high-performance fillers by better understanding the interaction mechanism given the important role of supramolecular interactions

Sepiolite with enhanced chemical reactivity as filler for rubber compounds

Reinforcing fillers are essential ingredients of rubber composites and, among them, inorganic oxides/hydroxides play a crucial role. Silica, with adequate coupling agents, is the best filler for tyre compounds with low energy dissipation and fuel consumption [1]. In recent years, interest has been increasing for biosourced fillers. Sepiolite is one of the most studied, thanks to its nanometric size and high aspect ratio [1-2]. However, sepiolite can hardly behave as a reinforcing filler, without establishing a chemical interaction with the rubber matrix. It is possible to pursue such objective by using an efficient coupling agent. In this study, sepiolite was functionalized with a pyrrole derivative, (2,5-dimethyl-1-(3-(triethoxysilyl) propyl)-1H-pyrrole) (APTESP), by simply mixing in water and heating, performing first evaporation and then the functionalization reaction. The Sepiolite/APTESP adduct was used as reinforcing filler in NR based composites, as the only filler or in a hybrid filler system with carbon black. The composites were prepared via melt blending in internal mixers. Sulfur based crosslinking was carried out and characterization was performed by means of dynamic-mechanical and tensile tests. Results The adduct Sepiolite/APTESP was successfully prepared, by using water as the reaction medium. The amount of APTESP was between 5 and 10% and the functionalization yield was higher than 70%. Sepiolite promoted the dynamic-mechanical reinforcement of the rubber composites, thanks to APTESP as coupling agent. The mechanical percolation threshold in sepiolite, as the only filler in NR, was observed at a sepiolite content of about 15 phr. When sepiolite/APTESP were used in place of CB, similar or lower values of hysteresis were obtained

Bionanocomposites based on a covalent network of chitosan and edge functionalized graphene layers

Graphene has outstanding thermal, mechanical and electronic properties. Bionanocomposites are an emerging class of materials, designed with the aim of achieving advanced structural and functional properties by using biobased polymers. As biopolymer, a great interest is for chitosan (CS), poly (N-acetyl-D-glucosamine), a copolymer of linked 2-acetamido-2-deoxy-D-glucopyranose and 2-amino-2-deoxy-D-glucopyranose. Graphene and graphene related materials are increasingly used for the preparation of bionanocomposites. In this study, a high surface area graphite was edge functionalized with hydroxyl groups (G-OH) through the reaction with KOH. G-CHO, with 4.5 mmol/g of functional group, was prepared from G-OH by means of the Reimer-Tieman reaction. Carbon papers and aerogels were prepared from chitosan and graphene layers with aldehydic edge functional groups (G-CHO) able to form chemical bonds with chitosan and thus to form a crosslinked network. Characterization of the graphitic materials was performed with elemental analysis, titration, X-ray analysis and Raman spectroscopy. CS and G-CHO were mixed with mortar and pestle and carbon papers and aerogels were obtained from a stable acidic water suspension through casting and liophilization, respectively. This work demonstrates that carbon papers and aerogels can be prepared without adopting the traditional oxidation-reduction procedure, avoiding harsh reaction conditions, dangerous and toxic reagents, solvents and catalysts and paves the way for selective modification of graphene layers, exploiting the reactivity of aromatic rings

Polyether from a biobased Janus molecule as surfactant for carbon nanotubes

A new polyether (PE) was prepared from a biobased Janus molecule, 2-(2,5-dimethyl-1H-pyrrol-1-yl)-1,3- propanediol (serinol pyrrole, SP). SP was synthesized with very high yield (about 96%) and high atom efficiency (about 80%) by reacting a biosourced molecule, such as serinol, with 2,5-hexanedione in the absence of solvent or catalyst. The reaction of SP with 1,6-dibromohexane led to PE oligomers, that were used as surfactants for multiwalled carbon nanotubes (MWCNT), in ecofriendly polar solvents such as acetone and ethyl acetate. The synergic interaction of aromatic rings and oxyalkylene sequences with the carbon allotrope led to dramatic improvement of surfactant efficiency: only 24% of SP based PE was extracted with ethyl acetate from the adduct with MWCNT, versus 98% of a typical pluronic surfactant. Suspensions of MWCNT-PE adducts in ethyl acetate were stable for months. High resolution transmission electron microscopy revealed a film of oligomers tightly adhered to MWCNT surface