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The synthesis of polymeric materials starting from CO2 as a feedstock is an active task of research. In particular, the copolymerization of CO2 with epoxides via ring-opening copolymerization (ROCOP) offers a simple, efficient route to synthesize aliphatic polycarbonates (APC). In many cases, APC display poor physical and chemical properties, limiting their range of application. The terpolymerization of CO2 with epoxides and organic anhydrides or cyclic esters offers the possibility, combining the ROCOP with ring-opening polymerization (ROP), to access a wide range of materials containing polycarbonate and polyester segments along the polymer chain, showing enhanced properties with respect to the simple APC. This review will cover the last advancements in the field, evidencing the crucial role of the catalytic system in determining the microstructural features of the final polymer.
David Hermann Lamparelli; Carmine Capacchione. Terpolymerization of CO2 with Epoxides and Cyclic Organic Anhydrides or Cyclic Esters. Catalysts 2021, 11, 961 .
AMA StyleDavid Hermann Lamparelli, Carmine Capacchione. Terpolymerization of CO2 with Epoxides and Cyclic Organic Anhydrides or Cyclic Esters. Catalysts. 2021; 11 (8):961.
Chicago/Turabian StyleDavid Hermann Lamparelli; Carmine Capacchione. 2021. "Terpolymerization of CO2 with Epoxides and Cyclic Organic Anhydrides or Cyclic Esters." Catalysts 11, no. 8: 961.
Soluble heterocomplexes consisting of sodium hydride in combination with trialkylaluminum derivatives have been used as anionic initiating systems at 100 °C in toluene for convenient homo-, co- and ter-polymerization of myrcene with styrene and isoprene. In this way it has been possible to obtain elastomeric materials in a wide range of compositions with interesting thermal profiles and different polymeric architectures by simply modulating the alimentation feed and the (monomers)/(initiator systems) ratio. Especially, a complete study of the myrcene-styrene copolymers (PMS) was carried out, highlighting their tapered microstructures with high molecular weights (up to 159.8 KDa) and a single glass transition temperature. For PMS copolymer reactivity ratios, rmyr = 0.12 ± 0.003 and rsty = 3.18 ± 0.65 and rmyr = 0.10 ± 0.004 and rsty = 3.32 ± 0.68 were determined according to the Kelen–Tudos (KT) and extended Kelen–Tudos (exKT) methods, respectively. Finally, this study showed an easy accessible approach for the production of various elastomers by anionic copolymerization of renewable terpenes, such as myrcene, with commodities.
David Lamparelli; Magdalena Kleybolte; Malte Winnacker; Carmine Capacchione. Sustainable Myrcene-Based Elastomers via a Convenient Anionic Polymerization. Polymers 2021, 13, 838 .
AMA StyleDavid Lamparelli, Magdalena Kleybolte, Malte Winnacker, Carmine Capacchione. Sustainable Myrcene-Based Elastomers via a Convenient Anionic Polymerization. Polymers. 2021; 13 (5):838.
Chicago/Turabian StyleDavid Lamparelli; Magdalena Kleybolte; Malte Winnacker; Carmine Capacchione. 2021. "Sustainable Myrcene-Based Elastomers via a Convenient Anionic Polymerization." Polymers 13, no. 5: 838.
Polymeric membranes based on the semi-crystalline syndiotactic–polystyrene (sPS) become hydrophilic, and therefore conductive, following the functionalization of the amorphous phase by the solid-state sulfonation procedure. Because the crystallinity of the material, and thus the mechanical strength of the membranes, is maintained and the resistance to oxidation decomposition can be improved by doping the membranes with fullerenes, the sPS becomes attractive for proton-exchange membranes fuel cells (PEMFC) and energy storage applications. In the current work we report the micro-structural characterization by small-angle neutron scattering (SANS) method of sulfonated sPS films and sPS–fullerene composite membranes at different temperatures between 20 °C and 80 °C, under the relative humidity (RH) level from 10% to 70%. Complementary characterization of membranes was carried out by FTIR, UV-Vis spectroscopy and prompt–γ neutron activation analysis in terms of composition, following the specific preparation and functionalization procedure, and by XRD with respect to crystallinity. The hydrated ionic clusters are formed in the hydrated membrane and shrink slightly with the increasing temperature, which leads to a slight desorption of water at high temperatures. However, it seems that the conductive properties of the membranes do not deteriorate with the increasing temperature and that all membranes equilibrated in liquid water show an increased conductivity at 80 °C compared to the room temperature. The presence of fullerenes in the composite membrane induces a tremendous increase in the conductivity at high temperatures compared to fullerenes-free membranes. Apparently, the observed effects may be related to the formation of additional hydrated pathways in the composite membrane in conjunction with changes in the dynamics of water and polymer.
Maria-Maddalena Schiavone; David Hermann Lamparelli; Yue Zhao; Fengfeng Zhu; Zsolt Revay; Aurel Radulescu. The Effects of Temperature and Humidity on the Microstructure of Sulfonated Syndiotactic–polystyrene Ionic Membranes. Membranes 2020, 10, 187 .
AMA StyleMaria-Maddalena Schiavone, David Hermann Lamparelli, Yue Zhao, Fengfeng Zhu, Zsolt Revay, Aurel Radulescu. The Effects of Temperature and Humidity on the Microstructure of Sulfonated Syndiotactic–polystyrene Ionic Membranes. Membranes. 2020; 10 (8):187.
Chicago/Turabian StyleMaria-Maddalena Schiavone; David Hermann Lamparelli; Yue Zhao; Fengfeng Zhu; Zsolt Revay; Aurel Radulescu. 2020. "The Effects of Temperature and Humidity on the Microstructure of Sulfonated Syndiotactic–polystyrene Ionic Membranes." Membranes 10, no. 8: 187.
Coupling of CO2 with epoxides is a green emerging alternative for the synthesis of cyclic organic carbonates (COC) and aliphatic polycarbonates (APC). The scope of this work is to provide a comprehensive overview of metal complexes having sulfur-containing ligands as homogeneous catalytic systems able to efficiently promote this transformation with a concise discussion of the most significant results. The crucial role of sulfur as the hemilabile ligand and its influence on the catalytic activity are highlighted as well.
Veronica Paradiso; Vito Capaccio; David Hermann Lamparelli; Carmine Capacchione. Metal Complexes Bearing Sulfur-Containing Ligands as Catalysts in the Reaction of CO2 with Epoxides. Catalysts 2020, 10, 825 .
AMA StyleVeronica Paradiso, Vito Capaccio, David Hermann Lamparelli, Carmine Capacchione. Metal Complexes Bearing Sulfur-Containing Ligands as Catalysts in the Reaction of CO2 with Epoxides. Catalysts. 2020; 10 (8):825.
Chicago/Turabian StyleVeronica Paradiso; Vito Capaccio; David Hermann Lamparelli; Carmine Capacchione. 2020. "Metal Complexes Bearing Sulfur-Containing Ligands as Catalysts in the Reaction of CO2 with Epoxides." Catalysts 10, no. 8: 825.
Sustainable lactams, which are derived from terpenes, are used for the synthesis of different novel copolymers via ring‐opening polymerization. Different conditions are tested and the incorporation of the different monomers into the polymers is elucidated. This gives access to a variety of new polymer structures and their application range is thus remarkably extended.
Malte Winnacker; David Hermann Lamparelli; Carmine Capacchione; Hicran H. Güngör; Lucas Stieglitz; Katia S. Rodewald; Matthias Schmidt; Thomas F. Gronauer. Sustainable Polyesteramides and Copolyamides: Insights into the Copolymerization Behavior of Terpene‐Based Lactams. Macromolecular Chemistry and Physics 2020, 221, 1 .
AMA StyleMalte Winnacker, David Hermann Lamparelli, Carmine Capacchione, Hicran H. Güngör, Lucas Stieglitz, Katia S. Rodewald, Matthias Schmidt, Thomas F. Gronauer. Sustainable Polyesteramides and Copolyamides: Insights into the Copolymerization Behavior of Terpene‐Based Lactams. Macromolecular Chemistry and Physics. 2020; 221 (12):1.
Chicago/Turabian StyleMalte Winnacker; David Hermann Lamparelli; Carmine Capacchione; Hicran H. Güngör; Lucas Stieglitz; Katia S. Rodewald; Matthias Schmidt; Thomas F. Gronauer. 2020. "Sustainable Polyesteramides and Copolyamides: Insights into the Copolymerization Behavior of Terpene‐Based Lactams." Macromolecular Chemistry and Physics 221, no. 12: 1.
The copolymerization of renewable monomers such as ocimene (O), myrcene (M), and farnesene (F) with butadiene (B), promoted by dichloro{1,4-dithiabutanediyl-2,2′-bis[4,6-bis(2-phenyl-2-propyl)phenoxy]}titanium (1) activated by modified methylalumoxane (m-MAO) under mild reaction conditions, was investigated. Copolymers in a wide range of compositions were obtained through a judicious control of the alimentation feed (up to 85% of terpene incorporated in the case of poly(ocimene–butadiene) (POB)). Analysis of POB, poly(myrcene–butadiene) (PMB), and poly(farnesene–butadiene) (PFB) microstructures revealed the good stereoselectivity of 1, both in the butadiene (up to 95%) and in the terpene (up to 92%, 71%, and 86% for O, M, and F, respectively) insertion. For all these new materials, a complete 13C NMR assignment was performed, revealing a multiblock structure. A sample of POB was also evaluated as a component in a model tread compound leading to improved mechanical properties with respect to the corresponding plain butadiene rubbers.
David Hermann Lamparelli; Veronica Paradiso; Francesco Della Monica; Antonio Proto; Silvia Guerra; Luca Giannini; Carmine Capacchione. Toward More Sustainable Elastomers: Stereoselective Copolymerization of Linear Terpenes with Butadiene. Macromolecules 2020, 53, 1665 -1673.
AMA StyleDavid Hermann Lamparelli, Veronica Paradiso, Francesco Della Monica, Antonio Proto, Silvia Guerra, Luca Giannini, Carmine Capacchione. Toward More Sustainable Elastomers: Stereoselective Copolymerization of Linear Terpenes with Butadiene. Macromolecules. 2020; 53 (5):1665-1673.
Chicago/Turabian StyleDavid Hermann Lamparelli; Veronica Paradiso; Francesco Della Monica; Antonio Proto; Silvia Guerra; Luca Giannini; Carmine Capacchione. 2020. "Toward More Sustainable Elastomers: Stereoselective Copolymerization of Linear Terpenes with Butadiene." Macromolecules 53, no. 5: 1665-1673.
The direct synthesis of syndiotactic polystyrene-block-polyethylene copolymer (sPS-b-PE) with a diblock structure has been achieved. The synthetic strategy consists of the sequential stereocontrolled polymerization of styrene and ethylene in the presence of a single catalytic system: cyclopentadienyltitanium(IV) trichloride activated by modified methylaluminoxane (CpTiCl3/MMAO). The reaction conditions suitable for affording the partially living polymerization of these monomers were identified, and the resulting copolymer, purified from contaminant homopolymers, was fully characterized. Gel permeation chromatography coupled with two-dimensional NMR spectroscopy COSY, HSQC, and DOSY confirmed the block nature of the obtained polymer, whose thermal behaviour and thin film morphology were also investigated by differential scanning calorimetry, powder wide angle x-ray diffraction, and atomic force microscopy.
David Hermann Lamparelli; Vito Speranza; Isabella Camurati; Antonio Buonerba; Leone Oliva. Synthesis and Characterization of Syndiotactic Polystyrene-Polyethylene Block Copolymer. Polymers 2019, 11, 698 .
AMA StyleDavid Hermann Lamparelli, Vito Speranza, Isabella Camurati, Antonio Buonerba, Leone Oliva. Synthesis and Characterization of Syndiotactic Polystyrene-Polyethylene Block Copolymer. Polymers. 2019; 11 (4):698.
Chicago/Turabian StyleDavid Hermann Lamparelli; Vito Speranza; Isabella Camurati; Antonio Buonerba; Leone Oliva. 2019. "Synthesis and Characterization of Syndiotactic Polystyrene-Polyethylene Block Copolymer." Polymers 11, no. 4: 698.
1-Alkylbenzenes as a precursor of surfactants, can be produced from ethylene, styrene, and hydrogen. These intermediates, lacking tertiary carbons, are environmentally more benign than commercial ones that bear the aromatic ring linked to an internal carbon of the aliphatic chain. The one-pot synthesis of highly linear 1-alkylbenzenes (LABs) through the homogeneous catalysis of olefin poly-insertion from cheap and largely available reagents can be carried out with a high turnover and selectivity. A purposely designed reactor that allows for the fine control of the three components feed, along with temperature, plays a key role in this achievement. A turnover of 194 g of LABs per mmol of catalyst per hour can be obtained with the simultaneous removal of polyethylene as a by-product.
David Hermann Lamparelli; Antonio Ricca; Vincenzo Palma; Leone Oliva. High Conversion of Styrene, Ethylene, and Hydrogen to Linear Monoalkylbenzenes. Molecules 2018, 23, 1260 .
AMA StyleDavid Hermann Lamparelli, Antonio Ricca, Vincenzo Palma, Leone Oliva. High Conversion of Styrene, Ethylene, and Hydrogen to Linear Monoalkylbenzenes. Molecules. 2018; 23 (6):1260.
Chicago/Turabian StyleDavid Hermann Lamparelli; Antonio Ricca; Vincenzo Palma; Leone Oliva. 2018. "High Conversion of Styrene, Ethylene, and Hydrogen to Linear Monoalkylbenzenes." Molecules 23, no. 6: 1260.
Highlights•A new way for the synthesis of linear alkyl benzenes is presented.•Some poly-insertion catalysts are employed for this purpose.•Relevant issue is the regiochemistry of styrene insertion into the metal carbon bond.•The absence of regiocontrol redirects the synthesis towards α,ω-diphenylalkanes. AbstractHighly linear 1-alkylbenzenes can be obtained in mild conditions and with good selectivity, through the homogeneous catalysis of olefin polyinsertion from cheap and largely available reagents. The comparison among some ansa metallocenes shows that the coordinative framework of the catalytic metal, by regulating the regiochemistry of the styrene insertion, determines upon the selectivity of the reaction. Graphical abstract
Nunzia Galdi; David Hermann Lamparelli; Leone Oliva. One pot synthesis of linear 1-alkylbenzenes from styrene, ethylene and hydrogen. Journal of Molecular Catalysis A: Chemical 2016, 418-419, 154 -157.
AMA StyleNunzia Galdi, David Hermann Lamparelli, Leone Oliva. One pot synthesis of linear 1-alkylbenzenes from styrene, ethylene and hydrogen. Journal of Molecular Catalysis A: Chemical. 2016; 418-419 ():154-157.
Chicago/Turabian StyleNunzia Galdi; David Hermann Lamparelli; Leone Oliva. 2016. "One pot synthesis of linear 1-alkylbenzenes from styrene, ethylene and hydrogen." Journal of Molecular Catalysis A: Chemical 418-419, no. : 154-157.