Project description:Ethylene copolymerizations with 2-methyl-1-pentene, 1-dodecene (DD), vinylcyclohexane (VCH), [Me2Si(C5Me4)(N t Bu)]TiCl2 (1), Cp*TiMe2(O-2,6- i Pr2-4-RC6H2) [R = H (2), SiEt3 (3)]-borate, and [A(H)]+[BAr4]- [Ar = C6F5; A(H)+ = N+(H)Me(n-C18H37)2, N+(H)(CH2CF3)(n-C18H37)2, HO+(n-C14H29)2·O(n-C14H29)2, HO+(n-C16H33)2·O(n-C16H33)2; Ar = C10F7, A(H)+ = HO+(n-C14H29)2·O(n-C14H29)2 (B5), N+(H)(CH2CF3)(n-C18H37)2] catalyst systems conducted in methylcyclohexane (MCH) exhibited better comonomer incorporation than those conducted in toluene (in the presence of methylaluminoxane (MAO) or borate cocatalysts). The activity was affected by the borate cocatalyst and 1,3-B5 catalyst systems in MCH and showed the highest activity in the ethylene copolymerizations with VCH and DD.
Project description:A family of half-titanocene complexes bearing π,π-stacked aryloxide ligands and their catalytic performances towards ethylene homo-/co- polymerizations were disclosed herein. All the complexes were well characterized, and the intermolecular π,π-stacking interactions could be clearly identified from single crystal X-ray analysis, in which a stronger interaction could be reflected for aryloxides bearing bigger π-systems, e.g., pyrenoxide. Due to the formation of such interactions, these complexes were able to highly catalyze the ethylene homopolymerizations and copolymerization with 1-hexene comonomer, even without any additiveson the aryloxide group, which showed striking contrast to other half-titanocene analogues, implying the positive influence of π,π-stacking interaction in enhancing the catalytic performances of the corresponding catalysts. Moreover, it was found that addition of external pyrene molecules was capable of boosting the catalytic efficiency significantly, due to the formation of a stronger π,π-stacking interaction between the complexes and pyrene molecules.
Project description:Ultra-high molar mass polyethylene (UHMMPE) is commonly used for ballistic-resistant body armor applications due to the superior strength of the fibers fabricated from this material combined with its low density. However, polymeric materials are susceptible to thermally induced degradation during storage and use, which can reduce the high strength of these fibers, and, thus, negatively impact their ballistic resistance. The objective of this work is to advance the field of lightweight and soft UHMMPE inserts used in various types of ballistic resistant-body armor via elucidating the mechanisms of chemical degradation and evaluating this chemical degradation, as well as the corresponding physical changes, of the UHMMPE fibers upon thermal aging. This is the first comprehensive study on thermally aged UHMMPE fibers that measures their decrease in the average molar mass via high-temperature size exclusion chromatography (HT-SEC) analysis. The decrease in the molar mass was further supported by the presence of carbon-centered free radicals in the polyethylene that was detected using electron paramagnetic resonance (EPR) spectroscopy. These carbon-centered radicals result from a cascade of thermo-oxidative reactions that ultimately induce C-C ruptures along the backbone of the polymer. Changes in the crystalline morphology of the UHMMPE fibers were also observed through wide-angle X-ray diffraction (WAXS), showing an increase in the amorphous regions, which promotes oxygen diffusion into the material, specifically through these areas. This increase in the amorphous fraction of the highly oriented polyethylene fibers has a synergistic effect with the thermo-oxidative degradation processes and contributes significantly to the decrease in their molar mass.
Project description:Nanoporous materials show a promising combination of mechanical properties in terms of their relative density; while there are numerous studies based on metallic nanoporous materials, here we focus on amorphous carbon with a bicontinuous nanoporous structure as an alternative to control the mechanical properties for the function of filament composition.Using atomistic simulations, we study the mechanical response of nanoporous amorphous carbon with 50% porosity, with sp3 content ranging from 10% to 50%. Our results show an unusually high strength between 10 and 20 GPa as a function of the %sp3 content. We present an analytical analysis derived from the Gibson-Ashby model for porous solids, and from the He and Thorpe theory for covalent solids to describe Young's modulus and yield strength scaling laws extremely well, revealing also that the high strength is mainly due to the presence of sp3 bonding. Alternatively, we also find two distinct fracture modes: for low %sp3 samples, we observe a ductile-type behavior, while high %sp3 leads to brittle-type behavior due to high high shear strain clusters driving the carbon bond breaking that finally promotes the filament fracture. All in all, nanoporous amorphous carbon with bicontinuous structure is presented as a lightweight material with a tunable elasto-plastic response in terms of porosity and sp3 bonding, resulting in a material with a broad range of possible combinations of mechanical properties.
Project description:The rational design of high-temperature endurable Cu-based catalysts is a long-sought goal since they are suffering from significant sintering. Establishing a barrier on the metal surface by the classical strong metal-support interaction (SMSI) is supposed to be an efficient way for immobilizing nanoparticles. However, Cu particles were regarded as impossible to form classical SMSI before irreversible sintering. Herein, we fabricate the SMSI between sputtering reconstructed Cu and flame-made LaTiO2 support at a mild reduction temperature, exhibiting an ultra-stable performance for more than 500 h at 600 °C. The sintering of Cu nanoparticles is effectively suppressed even at as high as 800 °C. The critical factors to success are reconstructing the electronic structure of Cu atoms in parallel with enhancing the support reducibility, which makes them adjustable by sputtering power or decorated supports. This strategy will extremely broaden the applications of Cu-based catalysts at more severe conditions and shed light on establishing SMSI on other metals.
Project description:The α-diimine late transition metal catalyst represents a new strategy for the synthesis of atactic polypropylene elastomer. Taking into account the properties of the material, enhancing the molecular weight of polypropylene at an elevated temperature through modifying the catalyst structure, and further increasing the activity of α-diimine catalyst for propylene polymerization, are urgent problems to be solved. In this work, two α-diimine nickel(II) catalysts with multiple hydroxymethyl phenyl substituents were synthesized and used for propylene homopolymerization. The maximum catalytic activity was 5.40 × 105 gPP/molNi·h, and the activity was still maintained above 105 gPP/molNi·h at 50 °C. The large steric hindrance of catalysts inhibited the chain-walking and chain-transfer reactions, resulting in polypropylene with high molecular weights (407~1101 kg/mol) and low 1,3-enchainment content (3.57~16.96%) in toluene. The low tensile strength (0.3~1.0 MPa), high elongation at break (218~403%) and strain recovery properties (S.R. ~50%, 10 tension cycles) of the resulting polypropylenes, as well as the visible light transmittance of approximately 90%, indicate the characteristics of the transparent elastomer.
Project description:Blends of polypropylene (PP) and ultra-high molecular weight polyethylene (UHMWPE) with elastomer-olefin block copolymers (OBC) were prepared using an ultrasonic twin-screw extruder, and the mechanical, thermal, and rheological properties of the blends were investigated. The interfacial interactions among PP, OBC, and UHMWPE showed that the PP/OBC/UHMWPE blends formed a core-shell structure with UHMWPE as the core and OBC as the shell. The crystallization temperature and the crystallinity of the blends were improved for the heterogeneous nucleation between PP- and OBC-covered UHMWPE particles. Moreover, the mechanical and thermal properties of PP/UHMWPE blends have also been greatly improved by adding OBC. Furthermore, it was evident that the OBC-covered HHMWPE particles became smaller under the application of ultrasonic irradiation, so the interfacial interactions between the particles and the PP matrix were enhanced and the impact strength of the blends was improved.
Project description:Compared to heterogenous Ziegler-Natta systems (ZNS), ansa-metallocene catalysts for the industrial production of isotactic polypropylene feature a higher cost-to-performance balance. In particular, the C2-symmetric bis(indenyl) ansa-zirconocenes disclosed in the 1990s are complex to prepare, less stereo- and/or regioselective than ZNS, and lose performance at practical application temperatures. The golden era of these complexes, though, was before High Throughput Experimentation (HTE) could contribute significantly to their evolution. Herein, we illustrate a Quantitative Structure - Activity Relationship (QSAR) model trained on a robust and highly accurate HTE database. The clear-box QSAR model utilizes, in particular, a limited number of chemically intuitive 3D geometric descriptors that screen various regions of space in and around the catalytic pocket in a modular way thus enabling to quantify individual substituent contributions. The main focus of the paper is on the methodology, which should be of rather broad applicability in molecular organometallic catalysis. Then again, it is worth emphasizing that the specific application reported here led us to identify in a comparatively short time novel zirconocene catalysts rivaling or even outperforming all previous homologues which strongly indicates that the metallocene story is not over yet.
Project description:Supercritical water liquefaction of different plastic wastes has been investigated under high-temperature and high-pressure conditions. The supercritical water liquefaction of commonly used plastic types, comprising polystyrene (PS), polypropylene (PP), and low-density polyethylene (LDPE) as well as their mixtures, is reported. The experiments were carried out at varying feedstock-to-water ratios with a residence time of 60 min under supercritical water reaction conditions. The process produced high oil yields of over 97 wt %, with the highest yields obtained at a plastic:water ratio of 1:3; at higher levels of input water, the yield of oil decreased slightly. The gas phase mainly consisted of light hydrocarbons such as methane, ethane, propane, and butane, with propane found to be the most abundant gas component. Aromatic hydrocarbons and alicyclic hydrocarbons were the major products in the product oil from the supercritical water liquefaction of polystyrene and polypropylene, whereas alkanes were predominant in the oil obtained from LDPE. Analysis of the oil obtained from binary (1:1) and ternary (1:1:1) plastic mixtures showed it exhibited aromatic hydrocarbons as the major constituent, indicating synergistic interaction. It was found that the incorporation of PP in the mixture facilitated the production of cyclic compounds and suppressed the production of alkanes. Supercritical water liquefaction offers an effective solution to plastic pollution, producing valuable products without the need for catalysts.
Project description:Isocyanides, due to the divalent carbon atom present in their structure, are among the most reactive groups of compounds in organic chemistry. Unfortunately, although according to the literature they do not have acute toxicity, they have a very unpleasant odor that makes it difficult to collaborate with them. However, despite the properties mentioned, reactions of isocyanides often lead to a variety of functional materials. In this article, we present a modified method for obtaining isocyanide-based polymers that significantly reduce the release of their hazardous vapors into the environment. For the study, a series of nickel(II) metal ion complex compounds containing organic ligands (e.g., 2,2'-bipyridyl, 1,10-phenanthroline, and diglycolate anion) were synthesized and used as catalysts in the oligomerization reaction of cyclohexyl isocyanide. The obtained oligomers were subjected to quantitative and qualitative physicochemical analyses (FT-IR, MALDI-TOF-MS, TGA/DSC, and DSC), which confirmed their structure and thermal properties. Reaction yields ranged from moderate (8-52%) to extremely high (94%) for a single catalyst. The synthesized catalytic systems are new, previously undescribed isocyanide oligomerization catalysts, which successfully led to the synthesis of poly(cyclohexyl isocyanide) and allowed us to obtain materials that can be used to produce many useful polymeric materials.