Search Results (66)

Divinylisoprene rubber, a copolymer of butadiene and isoprene, is used as raw material for rubber technical products, combining isoprene rubber’s elasticity and butadiene rubber’s wear resistance. These properties depend quantitatively on the copolymer composition, which depends on the kinetics of its synthesis. This work aims to theoretically describe how the monomer mixture composition in the butadiene–isoprene copolymerization affects the activity of the TiCl₄-Al(i-C₄H₉)₃ catalytic system (expressed by active sites concentration) via kinetic modeling. This enables development of a reliable kinetic model for divinylisoprene rubber synthesis, predicting reaction rate, molecular weight, and composition, applicable to reactor design and process intensification. Active sites concentrations were calculated from experimental copolymerization rates and known chain propagation constants for various monomer compositions. Kinetic equations for active sites formation were based on mass-action law and Langmuir monomolecular adsorption theory. An analytical equation relating active sites concentration to monomer composition was derived, analyzed, and optimized with experimental data. The results show that monomer composition’s influence on active sites concentration is well described by a two-step kinetic model (physical adsorption followed by Ti–C bond formation), accounting for competitive adsorption: isoprene adsorbs more readily, while butadiene forms more stable active sites. Full article

Ultra-high-molecular-weight polyethylene (UHMWPE) is a pivotal material in engineering and biomedical applications due to its exceptional mechanical strength, wear resistance, and impact performance. However, its extreme melt viscosity, caused by extensive chain entanglements, severely limits processability via conventional melt-processing techniques. Recent advances in catalytic synthesis have enabled the production of disentangled UHMWPE (dis-UHMWPE), which exhibits enhanced processability while retaining superior mechanical properties. Notably, heterogeneous catalytic systems, utilizing supported fluorinated bis (phenoxy-imine) titanium (FI) catalysts, polyhedral oligomeric silsesquioxanes (POSS)-modified Z-N catalysts, and other novel catalysts, have emerged as promising solutions, combining structural control with industrial feasibility. Moreover, optimizing polymerization conditions further enhances chain disentanglement while maintaining ultra-high molecular weights. These systems utilize nanoscale supports and ligand engineering to spatially isolate active sites, tailor the chain propagation/crystallization kinetics, and suppress interchain entanglement during polymerization. Furthermore, characterization techniques such as melt rheology and differential scanning calorimetry (DSC) provide critical insights into chain entanglement, revealing distinct reorganization kinetics and bimodal melting behavior in dis-UHMWPE. This development of hybrid catalytic systems opens up new avenues for solid-state processing and industrial-scale production. This review highlights recent advances concerning interaction between catalyst design, polymerization control, and material performance, ultimately unlocking the full potential of UHMWPE for next-generation applications. Full article

In this study, density functional theory (DFT) was used to analyze the processes that govern the interactions among triethylaluminum (TEAL), the Ziegler–Natta (ZN) catalyst, and the inhibitory compounds dimethylamine (DMA) and diethylamine (DEA) during olefin polymerization. The structural and charge characteristics of these inhibitors were examined through steric maps and DFT calculations. Combined DFT calculations (D3-B3LYP/6-311++G(d,p)) and IR spectroscopic analysis show that the most efficient way to deactivate the ZN catalyst is via the initial formation of the TEAL·DMA complex. This step has a kinetic barrier of only 27 kcal mol⁻¹ and a negative ΔG, in stark contrast to the >120 kcal mol⁻¹ required to form TEAL·DEA. Once generated, TEAL·DMA adsorbs onto the TiCl₄/MgCl₂ cluster with adsorption energies of −22.9 kcal mol⁻¹ in the gas phase and −25.4 kcal mol⁻¹ in n-hexane (SMD model), values 5–10 kcal mol⁻¹ more favorable than those for TEAL·DEA. This explains why, although dimethylamine is present at only 140 ppm, its impact on productivity (−19.6%) is practically identical to that produced by 170 ppm of diethylamine (−20%). The persistence of the ν(Al–N) band at ~615 cm⁻¹, along with a >30% decrease in the Al–C/Ti–C bands between 500 and 900 cm⁻¹, the downward shift of the N–H stretch from ~3300 to 3200 cm⁻¹, and the +15 cm⁻¹ increase in ν(C–N) confirm Al←N coordination and blockage of alkyl transfer, establishing the TEAL·DMA → ZN pathway as the dominant catalytic poisoning mechanism. Full article

Polybutadiene (PB) and polyisoprene (PI) rubbers are indispensable synthetic elastomeric materials widely used in tires, footwear, hose, belts, sealants, electricity, construction, and other applications. Nowadays, PB and PI elastomers are produced from butadiene (BD) and isoprene (IP) monomers via transition-metal-mediated coordination polymerization. Transition metal catalytic systems consist of a precise characteristic structural unit at the molecular level: well known as “single-site catalysts” (SSCs). These have experienced a revolutionary advance in the recently developed conjugated dienes synthetic rubber method. Among the SSCs, a class of rare-earth, metal-centered half-sandwich molecule has been identified as a high-performance catalytic system for conjugated dienes polymerization. These novel half-sandwich rare-earth (HSRE) catalytic systems exhibit several irreplaceable advantages compared with the conventional Ziegler–Natta-type catalytic systems. These HSRE catalytic systems can create novel conjugated diene rubbers (CDRs) with high catalytic reactivity, high stereoselectivity, an adjustable polymer chain microstructure, and high molecular weights and are considered to be the next generation of ecofriendly and economic catalytic systems for industrial applications. This paper delivers a concise review of some important synthetic methods for representative HSRE complexes with characteristic structures and of the utilization of some HSRE catalytic systems for the preparation of high-performance CDRs, especially highly stereoregular PI and PB materials. Full article

Organic electron donors are essential components of Ziegler-Natta (ZN) catalysts to produce isotactic polypropylene. In particular, aromatic or aliphatic diesters are widely used as ‘Internal Donors’ (ID) in MgCl₂/ID/TiCl₄ precatalyst formulations. Diesters are reactive with AlEt₃ (by far the most common ZN precatalyst activator) and are partly removed from the solid phase in the early stages of the polymerization process; this is detrimental for catalyst functioning, and a surrogate donor (‘External Donor’ (ED), usually an alkoxysilane) is added to the system to restore performance. Recent studies, however, demonstrated that even in cases where most of the diester is extracted by AlEt₃, the active sites retain a ‘memory’ of it in several aspects of the catalytic behavior (such as, e.g., the average productivity and the polydispersity index of the polymer produced). Considering that the residual diester is always in molar excess with respect to the active Ti, one may speculate that long-lasting interactions between the latter and diester molecules can occur. In turn, this should imply that the reactivity of AlEt₃ is different with binary MgCl₂/ID or ternary MgCl₂/ID/TiCl₄ mixtures. In this work, the latter hypothesis was explored for a library of diester IDs with large structural diversity. In line with the anticipation, the fractional amount of ID extracted by AlEt₃ was generally lower for ternary mixtures, although to an extent exquisitely dependent on diester structure. Full article

Chromophore quench-labeling (CQL) is an elegant and effective method to count the fraction of active metal (x*) in olefin polymerizations mediated by molecular transition metal catalysts. In this study, the method was successfully applied for the first time to a heterogeneous Ti-based Ziegler–Natta catalyst of industrial relevance. CQL experiments using 1-hexene as the monomer ended up with a value of x* = 0.49 ± 0.09%, close to that measured for the same catalyst in the polymerization of propene under otherwise identical conditions using an alternative quenched flow (QF) approach. We ascribe such a low x* value to the fact that the catalytically active species are transient metastable surface Ti adducts, as proposed in the recent literature. Full article

External donor (De) modification is an effective way to enhance the stereoselectivity of propylene polymerization with supported Ziegler–Natta catalysts. Aminosilane as a novel type of external donor has been found to have the excellent ability of enhancing the isoselectivity of propylene polymerization. In this work, dipiperidyldimethoxysilane (Donor-Py) was compared with cyclohexyl(methyl)dimethoxysilane (Donor-C) and dicyclopentyldimethoxysilane (Donor-D) for propylene polymerization in the presence or absence of hydrogen. By analyzing the effects of external donors on catalytic activity, polymer chain structures and their distributions, and the number and reactivity of three groups of active centers with different stereoselectivities, the performance of each De in enhancing stereoselectivity was compared. Propylene polymerization in the presence of RSi(OR’)₃-type De (R = n-propyl or i-butyl, R’ = methyl or ethyl) and hydrogen was also studied. Donor-Py produced PP with higher molecular weight and was more sensitive to hydrogen than Donor-D. According to the fractionation results, Donor-Py produced PP with the lowest content of medium-isotactic PP and the highest content of highly isotactic PP, especially at high hydrogen concentrations. By raising hydrogen concentrations, the number of active centers was enhanced in systems with Donor-C and Donor-D while it was reduced when Donor-Py was added. When Donor-Py was used as De, the effects of H₂ concentration on active center distributions and the reactivity of different active centers were evidently different from those of Donor-C and Donor-D. Donor-Py showed the best performance among the De used in this work in producing PP with both high isotacticity and good processability. The mechanism of De effects and hydrogen effects is discussed based on the results of polymerization kinetics and PP chain structures. Full article

As a kind of high-performance thermoplastic crystalline resin, poly(4-methyl-1-pentene) (PMP) is characterized by its low density, low dielectric constant, exceptional mechanical and chemical properties, high transparency, and gas permeability. PMP has recently received more attention since COVID-19, because it is used as a hollow-fiber membrane for extracorporeal membrane oxygenation (ECMO) based on its high permeability and excellent biocompatibility. This review summarizes the chemical structure, synthesis, properties, and application of PMP. The advancements in catalyst systems for the catalytic synthesis of PMP, including Ziegler–Natta, metallocene, post-metallocene, and late-transition metal catalysts are emphasized. Furthermore, the molecular chain structure, helical conformation, and crystallization morphology of PMP, as well as its properties and applications, are also introduced in detail. Additionally, PMP composites and functional PMP materials are also described as promising and high-performance materials. Full article

The polypropylene (PP) synthesis process is crucial in the plastics industry, requiring precise control as it directly impacts the catalytic activity and the final product’s performance. This study investigates the effects of trace amounts of four different mercaptans on the polymerization of propylene using a fourth-generation Ziegler–Natta (ZN) catalyst. Various concentrations of these mercaptans were tested, and results showed that their presence significantly reduced the melt flow index (MFI) of the final PP. The most notable MFI decrease occurred at 37.17 ppm of propyl mercaptan and 52.60 ppm of butyl mercaptan. Methyl and ethyl mercaptan also reduced the MFI at lower concentrations, indicating that mercaptans act as inhibitors by slowing down the polymerization process and reducing the fluidity of molten PP. The highest MFI increase was observed at lower concentrations of each mercaptan, suggesting that smaller molecular inhibitors require less concentration. This trend was also seen in the catalyst’s productivity, where lower concentrations of methyl mercaptan reduced PP production more effectively than higher concentrations of butyl mercaptan. Fourier transform infrared spectroscopy (FTIR) identified interactions between the mercaptans and the ZN catalyst. Computational analysis further supported these findings, providing insights into the molecular interactions and suggesting possible inhibition mechanisms that could impact the final properties of polypropylene. Full article

In this work, an attempt is made to theoretically substantiate the experimentally known facts of the influence of halogen concentration on the catalytic properties of the neodymium-based Ziegler–Natta system. Based on the structural and thermochemical data obtained using modern methods of quantum chemistry, the process of the 1,3-butadiene cis-1,4-polymerization under the model active centers of the neodymium Ziegler–Natta catalysts with different contents of chloride ions was studied. Results are presented that explain the increase in the cis-stereospecificity and activity of the polymerization system with an increase in the content of the chloride ions in the neodymium catalytic system. Reasons were established for the decrease in the concentration of active centers relative to the introduced Nd(III) with an excess of chloride ions and the occurrence of the anti-syn isomerization as a source of the formation of the trans-1,4-structures in the cis-1,4-polybutadiene. Full article

Acetylene and methylacetylene are impurities commonly found in the raw materials used for the production of polymers such as polypropylene and polyethylene. Experimental evidence indicates that both acetylene and methylacetylene can decrease the productivity of the Ziegler-Natta catalyst and alter the properties of the resulting polymer. However, there is still a lack of understanding regarding the mechanisms through which these substances affect this process. Therefore, elucidating these mechanisms is crucial to develop effective solutions to this problem. In this study, the inhibition mechanisms of the Ziegler-Natta catalyst by acetylene and methylacetylene are presented and compared with the incorporation of the first propylene monomer (chain initiation) to elucidate experimental effects. The Density Functional Theory (DFT) method was used, along with the B3LYP-D3 functional and the 6-311++G(d,p) basis set. The recorded adsorption energies were −11.10, −13.99, and −0.31 kcal mol⁻¹, while the activation energies were 1.53, 2.83, and 28.36 kcal mol⁻¹ for acetylene, methylacetylene, and propylene, respectively. The determined rate constants were 4.68 × 10¹¹, 5.29 × 10¹¹, and 2.3 × 10⁻⁸ M⁻¹ s⁻¹ for acetylene, methylacetylene, and propylene, respectively. Based on these values, it is concluded that inhibition reactions are more feasible than propylene insertion only if an ethylene molecule has not been previously adsorbed, as such an event reinforces propylene adsorption. Full article

The electron donors (ED) in Ziegler–Natta (Z-N) catalysis are classified as internal electron donors (IED) and external electron donors (EED), and both IED and EED are indispensable components for enhancing the catalytic reactivity and regulating the stereoregularity of polyolefinic materials in a typical industrial Z-N catalytic process. With the intensive research on ED, the Z-N catalyst performances have experienced successive progress in the last few decades. Polypropylenes (PP) as a commodity polyolefin material, especially the isotactic PP (iPP), are produced in multi-billion pounds per annum by utilization of the various IED- and EED-assisted Z-N catalysts systems. In the course of developing Z-N catalysts, the ED constitutes a key component of the content and represents a significant area of future research. In this review, we introduced a concise overview of the functions of IEDs in the generations of Z-N catalyst systems and the widely used IED types (A total of 11 different types of IEDs are encompassed within this study) that have been developed so far. In addition, we focused on the coordination modes of different IEDs in the MgCl₂-supported Z-N catalyst system and analyzed the effects of different types of IEDs on the PP isotacticity, regioselectivity, hydrogen sensitivity, and briefly introduced the application of environmentally friendly rosinate and salicylate IEDs. Full article

The industrial production of polypropylene–polyethylene composites (C-PP-PE) involves the generation of waste that is not usable, resulting in a significant environmental impact globally. In this research, we identified different concentrations of aluminum (8–410 ppm), chlorine (13–205 ppm), and iron (4–100 ppm) residues originating from traces of the Ziegler–Natta catalyst and the triethylaluminum (TEAL) co-catalyst. These residues accelerate the generation of plastic waste and affect the thermo-kinetic performance of C-PP-PE, as well as the formation of volatile organic compounds that reduce the commercial viability of C-PP-PE. Several families of organic compounds were quantified by gas chromatography with mass spectrometry, and it is evident that these concentrations varied directly with the ppm of Al, Cl, and Fe present in C-PP-PE. This research used kinetic models of Coats–Redfern, Horowitz–Metzger, Flynn–Wall–Ozawa, and Kissinger–Akahira–Sunose. The activation energy values (Ea) were inversely correlated with Al, Cl, and Fe concentrations. In samples PP0 and W3, with low Al, Cl, and Fe concentrations, the values (Ea) were 286 and 224 kJ mol⁻¹, respectively, using the Horowitz method. Samples W1 and W5, with a high ppm of these elements, showed Ea values of 80.83 and 102.99 kJ mol⁻¹, respectively. This knowledge of the thermodynamic behavior and the elucidation of possible chemical reactions in the industrial production of C-PP-PE allowed us to search for a suitable remediation technique to give a new commercial life to C-PP-PE waste, thus supporting the management of plastic waste and improving the process—recycling to promote sustainability and industrial efficiency. One option was using the antioxidant additive Irgafos P-168 (IG-P168), which stabilized some of these C-PP-PE residues very well until thermal properties similar to those of pure C-PP-PE were obtained. Full article

The addition of two-dimensional inorganic nanomaterials can effectively enhance the properties of polyethylene (PE). In the present study, a series of high-performance PE/oleic acid (OA)–siloxene nanocomposites were prepared by in situ polymerization using OA–siloxene-supported Ziegler–Natta catalysts. Compared with the conventional Ziegler–Natta catalyst, the polymerization activity of the OA–siloxene-supported Ziegler–Natta catalyst was enhanced to 100 kg/mol-Ti•h, an increase of 56%. The OA–siloxene fillers exhibited excellent dispersion within the PE matrix through the in situ polymerization technique. Compared to pure PE, PE/OA–siloxene nanocomposites containing 1.13 wt% content of OA–siloxene showed 68.3 °C, 126%, 37%, and 46% enhancements in T_dmax, breaking strength, modulus, and elongation at break, respectively. Full article

In this study, the impact of ethylene oxide, propylene oxide, 1,2-butene oxide, and 1,2-pentene oxide on the polymerization of propylene at an industrial level was investigated, focusing on their influence on the catalytic efficiency and the properties of polypropylene (PP) without additives. The results show that concentrations between 0 and 1.24 ppm of these epoxides negatively affect the reaction’s productivity, the PP’s mechanical properties, the polymer’s fluidity index, and the PP’s thermal properties. Fourier transform infrared spectroscopy (FTIR) revealed bands for the Ti-O bond and the Cl-Ti-O-CH₂ bonds at 430 to 475 cm⁻¹ and 957 to 1037 cm⁻¹, respectively, indicating the interaction between the epoxides and the Ziegler–Natta catalyst. The thermal degradation of PP in the presence of these epoxides showed a similar trend, varying in magnitude depending on the concentration of the inhibitor. Sample M7, with 0.021 ppm propylene oxide, exhibited significant mass loss at both 540 °C and 600 °C, suggesting that even small concentrations of this epoxide can markedly increase the thermal degradation of PP. This pattern is repeated in samples with 1,2-butene oxide and 1,2-pentene oxide. These results highlight the need to strictly control the presence of impurities in PP production to optimize both the final product’s quality and the polymerization process’s efficiency. Full article