UHMWPE/SBA-15 nanocomposites synthesized by in situ polymerization

Different nanocomposites have been attained by in situ polymerization based on ultra-high molecular weight polyethylene (UHMWPE) and mesoporous SBA-15, this silica being used for immobilization of the FI catalyst bis [N-(3-tert-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinato] titanium (IV) dichloride and as filler as well. Two distinct approaches have been selected for supporting the FI catalyst on the SBA-15 prior polymerization. A study on polymerization activity of this catalyst has been performed under homogenous conditions and upon heterogenization. A study of the effect of presence of mesoporous particles and of the immobilization method is also carried out. Moreover, the thermal characterization, phase transitions and mechanical response of some pristine UHMWPEs and UHMWPE/SBA-15 materials have been carried out. Relationships with variations on molar mass, impregnation method of catalyst and final SBA-15 content have been established

MCM-41 as Nanofiller in Polyethylene Hybrid Materials

Mesoporous MCM-41 exhibits a stable framework structure, well-defined nanopores and a large surface area. When combined with metallocene polymerisation catalyst, these mesoporous materials, provide a unique route for preparing polyolefin-based nanocomposites by in situ polymerisation

Composites Based on Poly(Lactic Acid) (PLA) and SBA-15: Effect of Mesoporous Silica on Thermal Stability and on Isothermal Crystallization from Either Glass or Molten State

© 2020 by the authors.Several composites based on an L-rich poly(lactic acid) (PLA) with different contents of mesoporous Santa Barbara Amorphous (SBA-15) silica were prepared in order to evaluate the effect of the mesoporous silica on the resultant PLA materials by examining morphological aspects, changes in PLA phases and their transitions, and, primarily, the influence on some final properties. Melt extrusion was chosen for the obtainment of the composites, followed by quenching from the melt to prepare films. Completely amorphous samples were then attained, as deduced from X-ray diffraction and differential scanning calorimetry (DSC) analyses. Thermogravimetric analysis (TGA) results demonstrated that the presence of SBA-15 particles in the PLA matrix did not exert any significant influence on the thermal decomposition of these composites. An important nucleation effect of the silica was found in PLA, especially under isothermal crystallization either from the melt or from its glassy state. As expected, isothermal crystallization from the glass was considerably faster than from the molten state, and these high differences were also responsible for a more considerable nucleating role of SBA-15 when crystallizing from the melt. It is remarkable that the PLA under analysis showed very close temperatures for cold crystallization and its subsequent melting. Moreover, the type of developed polymorphs did not accomplish the common rules previously described in the literature. Thus, all the isothermal experiments led to exclusive formation of the α modification, and the observation of the α’ crystals required the annealing for long times at temperatures below 80 °C, as ascertained by both DSC and X-ray diffraction experiments. Finally, microhardness (MH) measurements indicated a competition between the PLA physical aging and the silica reinforcement effect in the as-processed amorphous films. Physical aging in the neat PLA was much more important than in the PLA matrix that constituted the composites. Accordingly, the MH trend with SBA-15 content was strongly dependent on aging times.This research was funded by AEI/FEDER, UE (grant number MAT2016-79869-C2-1-P) and ALBA Synchrotron Light Facility. TMDR is also grateful for her pre-doctoral funding (contract number BES-2017-082284).Peer reviewe

New HDPE/MCM41 nanocomposites with improved mechanical performance: synthesis and characterizatio

Ordered mesoporous silicas with a channel structure of well-defined geometries and dimensions at nanometer scale are excellent candidates to host intercalation reactions. In recent years, our research group has shown that mesoporous silicas of the M41S class combined with metallocene complexes give rise to excellent supported catalysts for ethylene polymerisation. Due to the support characteristics, the reaction is allowed to occur in the channels and in this way hybrid organic-inorganic materials can be prepared within a large range of nanofiller concentration. These HDPE/MCM-41 nanocomposites exhibit an improved mechanical performance and an easier degradability due to the additional role of MCM-41 as a promoter for PE degradation

The anticancer effect related to disturbances in redox balance on Caco-2 cells caused by an alkynyl gold(I) complex

The alkynyl gold(I) derivative Au(C=CPh)(PTA)] (PTA = 1, 3, 5-triaza-7-phosphaadamantane) induces apoptosis in colorectal carcinoma tumour cells (Caco-2) without affecting to normal enterocytes. Au(C=CPh)(PTA)] is a slight lipophilic drug, stable in PBS (Phosphate Buffered Saline) and able to bind BSA (Bovin Serum Albumin) by hydrophobic interactions. Once inside the cell, Au(C=CPh)(PTA)] targets seleno proteins such as Thioredoxin Reductase 1, increasing ROS (Reactive Oxygen Species) levels, reducing cell viability and proliferation and inducing mitochondrial apoptotic pathway, pro-apoptotic and anti-apoptotic protein imbalance, loss of mitochondrial membrane potential, cytochrome c release and activation of caspases 9 and 3. Moreover, unlike other metal-based drugs such as cisplatin, Au(C=CPh)(PTA)] does not target nucleic acid, reducing the risk of side mutation in the DNA. In consequence, our results predict a promising future for Au(C=CPh)(PTA)] as a chemotherapeutic agent for colorectal carcinoma

A novel approach for preparation of nanocomposites with an excellent rigidity/deformability balance based on reinforced HDPE with halloysite

An innovative approach, designated as supported activator (SA), allows preparation of high density polyethylene (HDPE)-based highly performant hybrid materials. This procedure makes use of a nano-sized supported methylaluminoxane (MAO)-activator, based on halloysite natural nanotubes (HNT), combined with an in situ supporting concept. The new protocol when compared with a more conventional approach gives rise to higher polymerization activities as well as ultimate materials with better morphological features, greater crystallinity, thicker crystals, and highly increased stiffness. Moreover, a remarkable synergy between rigidity and toughness is attained. The Young’s modulus of a film obtained from the nanocomposite with the highest HNT content increases more than 70 % relatively to a pristine HDPE film, while retaining the limit stretching ability of pristine HDPE (more than 800%). A beneficial impact of using a high aspect ratio support such as HNT in the mechanical properties is also observed, when compared to similar HDPE hybrid materials derived from dendrimer-like silica (DS) nanospheres. Interestingly, polymerization activity, polymer features and derived properties found in the ultimate materials are less impacted by support/filler nature than by preparation method. This fact highlights the crucial role of the synthetic methodology used and corroborates the high potential of the SA route for the preparation of high-performance polyethylene-based nanocomposites with an excellent balance between stiffness and deformability.info:eu-repo/semantics/publishedVersio