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Polymers are essential materials in our daily life. The synthesis of value-added polymers is mainly performed from fossil fuel-derived monomers. However, the adoption of the circular economy model based on the bioeconomy will reduce the dependence on fossil fuels. In this context, biorefineries have emerged to convert biomass into bioenergy and produce high value-added products, including molecules that can be further used as building blocks for the synthesis of biopolymers and bioplastics. The achievement of catalytic systems able to polymerize the natural monomer counterparts, such as terpenes or terpenoids, is still a challenge in the development of polymers with good mechanical, thermal, and chemical properties. This review describes the most common types of bioplastics and biopolymers and focuses specifically on the polymerization of terpenes and terpenoids, which represent a source of promising monomers to create bio-based polymers and copolymers.
Marta. E. G. Mosquera; Gerardo Jiménez; Vanessa Tabernero; Joan Vinueza-Vaca; Carlos García-Estrada; Katarina Kosalková; Alberto Sola-Landa; Belén Monje; Carolina Acosta; Rafael Alonso; Miguel Ángel Valera. Terpenes and Terpenoids: Building Blocks to Produce Biopolymers. Sustainable Chemistry 2021, 2, 467 -492.
AMA StyleMarta. E. G. Mosquera, Gerardo Jiménez, Vanessa Tabernero, Joan Vinueza-Vaca, Carlos García-Estrada, Katarina Kosalková, Alberto Sola-Landa, Belén Monje, Carolina Acosta, Rafael Alonso, Miguel Ángel Valera. Terpenes and Terpenoids: Building Blocks to Produce Biopolymers. Sustainable Chemistry. 2021; 2 (3):467-492.
Chicago/Turabian StyleMarta. E. G. Mosquera; Gerardo Jiménez; Vanessa Tabernero; Joan Vinueza-Vaca; Carlos García-Estrada; Katarina Kosalková; Alberto Sola-Landa; Belén Monje; Carolina Acosta; Rafael Alonso; Miguel Ángel Valera. 2021. "Terpenes and Terpenoids: Building Blocks to Produce Biopolymers." Sustainable Chemistry 2, no. 3: 467-492.
New heterometallic aluminium-alkali metal compounds have been prepared using Schiff bases with electron withdrawing substituents as ligands. The synthesis of these new species was achieved via the reaction of AlMe3 with the freshly prepared alkali-metallated ligand. The derivatives formed were characterized by NMR in solution and by single crystal X-ray diffraction in the solid state. Aluminate derivatives with lithium and sodium were prepared and a clear influence of the alkali metal in the final outcome is observed. The presence of a Na···F interaction in the solid state has a stabilization effect and the species [NaAlMe3L]2 can de isolated for the first time, which was not possible when using Schiff bases without electron withdrawing substituents as ligands.
Francisco M. García-Valle; Vanessa Tabernero; Tomás Cuenca; Jesús Cano; Marta E. G. Mosquera. Aluminates with Fluorinated Schiff Bases: Influence of the Alkali Metal–Fluorine Interactions in Structure Stabilization. Molecules 2018, 23, 3108 .
AMA StyleFrancisco M. García-Valle, Vanessa Tabernero, Tomás Cuenca, Jesús Cano, Marta E. G. Mosquera. Aluminates with Fluorinated Schiff Bases: Influence of the Alkali Metal–Fluorine Interactions in Structure Stabilization. Molecules. 2018; 23 (12):3108.
Chicago/Turabian StyleFrancisco M. García-Valle; Vanessa Tabernero; Tomás Cuenca; Jesús Cano; Marta E. G. Mosquera. 2018. "Aluminates with Fluorinated Schiff Bases: Influence of the Alkali Metal–Fluorine Interactions in Structure Stabilization." Molecules 23, no. 12: 3108.
A new type of -ate derivatives is described, where the alkali metal exerts a strong influence on the final outcome.
Francisco M. García-Valle; Vanessa Tabernero; Tomás Cuenca; Jesús Cano; Marta E. G. Mosquera. Schiff-base -ate derivatives with main group metals: generation of a tripodal aluminate metalloligand. Dalton Transactions 2018, 47, 6499 -6506.
AMA StyleFrancisco M. García-Valle, Vanessa Tabernero, Tomás Cuenca, Jesús Cano, Marta E. G. Mosquera. Schiff-base -ate derivatives with main group metals: generation of a tripodal aluminate metalloligand. Dalton Transactions. 2018; 47 (18):6499-6506.
Chicago/Turabian StyleFrancisco M. García-Valle; Vanessa Tabernero; Tomás Cuenca; Jesús Cano; Marta E. G. Mosquera. 2018. "Schiff-base -ate derivatives with main group metals: generation of a tripodal aluminate metalloligand." Dalton Transactions 47, no. 18: 6499-6506.
This paper presents a study of the effects of different treatments on the polymerization activity of mod-ified clays as cocatalysts. To achieve this goal, an intercalating cation was introduced into two smectitesand these clays were then modified with trimethyl aluminium. The results for ethylene polymeriza-tion, when a zirconocene complex was used as catalyst, and the structure analysis, allow us to obtaininteresting deductions about the generation mode of the active species. All active materials employedas support activators presented aluminium in a pentahedral environment together with acidic hydrogenatoms. These two features were detected only after TMA treatment and they seem to be crucial elementsin active cocatalyst generation. Moreover, a material without structural aluminium displayed the bestactivity pointing to the new aluminium species generated in the solid matrix as the determining factorfor the activity. We proposed a synergic effect between Lewis acid aluminium centres and acidic Brönstedprotons that generate the SiOHAl groups that activate the zirconium compound.Peer Reviewe
Claudimar Camejo Abreu; Vanessa Tabernero; María Dolores Alba; Tomás Cuenca; Pilar Terreros. Enhanced activity of clays and its crucial role for the activity in ethylene polymerization. Journal of Molecular Catalysis A: Chemical 2014, 393, 96 -104.
AMA StyleClaudimar Camejo Abreu, Vanessa Tabernero, María Dolores Alba, Tomás Cuenca, Pilar Terreros. Enhanced activity of clays and its crucial role for the activity in ethylene polymerization. Journal of Molecular Catalysis A: Chemical. 2014; 393 ():96-104.
Chicago/Turabian StyleClaudimar Camejo Abreu; Vanessa Tabernero; María Dolores Alba; Tomás Cuenca; Pilar Terreros. 2014. "Enhanced activity of clays and its crucial role for the activity in ethylene polymerization." Journal of Molecular Catalysis A: Chemical 393, no. : 96-104.
Javier Sánchez-Nieves; Vanessa Tabernero; Claudimar Camejo; Pascual Royo. Synthesis of neutral and cationic monocyclopentadienyl alkyl niobium and tantalum complexes. Journal of Organometallic Chemistry 2010, 695, 2469 -2473.
AMA StyleJavier Sánchez-Nieves, Vanessa Tabernero, Claudimar Camejo, Pascual Royo. Synthesis of neutral and cationic monocyclopentadienyl alkyl niobium and tantalum complexes. Journal of Organometallic Chemistry. 2010; 695 (22):2469-2473.
Chicago/Turabian StyleJavier Sánchez-Nieves; Vanessa Tabernero; Claudimar Camejo; Pascual Royo. 2010. "Synthesis of neutral and cationic monocyclopentadienyl alkyl niobium and tantalum complexes." Journal of Organometallic Chemistry 695, no. 22: 2469-2473.
In this work we report the polymerization behaviour of natural clays (montmorillonites, MMT) as activating supports. These materials have been modified by treatment with different aluminium compounds in order to obtain enriched aluminium clays and to modify the global Brönsted/Lewis acidity. As a consequence, the intrinsic structural properties of the starting materials have been changed. These changes were studied and these new materials used for ethylene polymerization using a zirconocene complex as catalyst. All the systems were shown to be active in ethylene polymerization. The catalyst activity and the dependence on acid strength and textural properties have been also studied. The behaviour of an artificial silica (SBA 15) modified with an aluminium compound to obtain a silicoaluminate has been studied, but no ethylene polymerization activity has been found yet.
Vanessa Tabernero; Claudimar Camejo; Pilar Terreros; Maria Dolores Alba; Tomás Cuenca. Silicoaluminates as “Support Activator” Systems in Olefin Polymerization Processes. Materials 2010, 3, 1015 -1030.
AMA StyleVanessa Tabernero, Claudimar Camejo, Pilar Terreros, Maria Dolores Alba, Tomás Cuenca. Silicoaluminates as “Support Activator” Systems in Olefin Polymerization Processes. Materials. 2010; 3 (2):1015-1030.
Chicago/Turabian StyleVanessa Tabernero; Claudimar Camejo; Pilar Terreros; Maria Dolores Alba; Tomás Cuenca. 2010. "Silicoaluminates as “Support Activator” Systems in Olefin Polymerization Processes." Materials 3, no. 2: 1015-1030.