Self-Initiated Butyl Acrylate Polymerizations in Bulk and in Solution Monitored By In-Line Techniques

High-temperature acrylate polymerizations are technically relevant, but yet not fully understood. In particular the mechanism and the kinetics of the thermal self-initiation is a topic of current research. To obtain more detailed information the conversion dependence of the polymerization rate, rbr, is determined via in-line DSC and FT-NIR spectroscopy for reactions in bulk and in solution at temperatures ranging from 80 to 160 °C. Solution polymerizations revealed that dioxane is associated with the highest rbr, while aromatic solvents result in the lowest values of rbr. Interestingly, rbr for polymerizations in solution with dioxane depends on the actual monomer concentration at a given time in the system, but is not depending on the initial monomer concentration. The overall rate of polymerization in bulk and in solution is well represented by an equation with three or four parameters, respectively, being estimated by multiple linear regression and the temperature as additional parameter.

Investigations on the Ethylene Polymerization with Bisarylimine Pyridine Iron (BIP) Catalysts

The kinetics and terminations of ethylene polymerization, mediated by five bisarylimine pyridine (BIP) iron dichloride precatalysts, and activated by large amounts of methyl aluminoxane (MAO) was studied. Narrow distributed paraffins from initially formed aluminum polymeryls and broader distributed 1-polyolefins and (bimodal) mixtures, thereof, were obtained after acidic workup. The main pathway of olefin formation is beta-hydrogen transfer to ethylene. The rate of polymerization in the initial phase is inversely proportional to the co-catalyst concentration for all pre-catalysts; a first-order dependence was found on ethylene and catalyst concentrations. The inhibition by aluminum alkyls is released to some extent in a second phase, which arises after the original methyl groups are transformed into n-alkyl entities and the aluminum polymeryls partly precipitate in the toluene medium. The catalysis is interpretable in a mechanism, wherein, the relative rate of chain shuttling, beta-hydrogen transfer and insertion of ethylene are determining the outcome. Beta-hydrogen transfer enables catalyst mobility, which leads to a (degenerate) chain growth of already precipitated aluminum alkyls. Stronger Lewis acidic centers of the single site catalysts, and those with smaller ligands, are more prone to yield 1-olefins and to undergo a faster reversible alkyl exchange between aluminum and iron.

3-Carboxylic Acid and Formyl-Derived Coumarins as Photoinitiators in Photo-Oxidation or Photo-Reduction Processes for Photopolymerization upon Visible Light: Photocomposite Synthesis and 3D Printing Applications

In this paper, nine organic compounds based on the coumarin scaffold and different substituents were synthesized and used as high-performance photoinitiators for free radical photopolymerization (FRP) of meth(acrylate) functions under visible light irradiation using LED at 405 nm. In fact, these compounds showed a very high initiation capacity and very good polymerization profiles (both high rate of polymerization (Rp) and final conversion (FC)) using two and three-component photoinitiating systems based on coum/iodonium salt (0.1%/1% w/w) and coum/iodonium salt/amine (0.1%/1%/1% w/w/w), respectively. To demonstrate the efficiency of the initiation of photopolymerization, several techniques were used to study the photophysical and photochemical properties of coumarins, such as: UV-visible absorption spectroscopy, steady-state photolysis, real-time FTIR, and cyclic voltammetry. On the other hand, these compounds were also tested in direct laser write experiments (3D printing). The synthesis of photocomposites based on glass fiber or carbon fiber using an LED conveyor at 385 nm (0.7 W/cm2) was also examined.

Ethylene Polymerization via Zirconocene Catalysts and Organoboron Activators: An Experimental and Kinetic Modeling Study

Forty years after the discovery of metallocene catalysts, there are still several aspects that remain unresolved, especially when the “conventional” alkylaluminum activators are not used. Herein, we systematically investigated the synthesis of polyethylene (PE) via three different zirconocene catalysts, with different alkyl substituents, activated via different organoboron compounds. The polymerization behavior, as well as the properties of the materials, were evaluated. The results demonstrate that the highest catalytic activity is shown by bis(cyclopentadienyl)dimethylzirconium activated by trityl tetra(pentafluorophenyl)borate. Additionally, it was found that toluene is the optimum solvent for these systems and at these reaction conditions. Moreover, to validate our experimental results, a comprehensive mathematical model was developed on the basis of thermodynamic and kinetic principles. The concentration of ethylene transferred to the solvent phase (toluene) in a liquid–vapor equilibrium (LVE) system was estimated based on Duhem’s theorem. Arrhenius expressions for the kinetic rate constants of a proposed kinetic mechanism were estimated by a kinetic model, in which the rate of polymerization was fitted by a least-square optimization procedure and the molecular weight averages by the method of moments. The simulations of the coordination polymerization suggest the presence of two types of active sites, principally at low temperatures, and the reactivation of the deactivated sites via a boron-based activator. However, the effect of the temperature on the reactivation step was not clear; a deeper understanding via designed experiments is required.

SPECIFIC PROPERTIES OF TUBULIN IN THE PREFRONTAL CORTEX IN CONTROL, SCHIZOPHRENIA AND VASCULAR DEMENTIA

The aim of the study was to evaluate the rate of polymerization of tubulin into microtubules and determine the level of colchicine binding (colchicine-binding activity of tubulin) in the prefrontal cortex in schizophrenia, vascular dementia (VD) and control. Colchicine-binding activity of tubulin was determined by Sherlinе in tubulin-enriched extracts of proteins from the samples. Measurement of light scattering during the polymerization of the tubulin was carried out using the nephelometric method at a wavelength of 450-550 nm. There was a significant decrease in colchicine-binding activity and the rate of tubulin polymerization in the prefrontal cortex in both diseases, and in VD to a greater extent than in schizophrenia. The obtained results suggest that not only in Alzheimer's disease, but also in other mental diseases such as schizophrenia and VD, there is a decrease in the level of tubulin in the prefrontal cortex of the brain, although to a lesser extent than in Alzheimer's disease, and consequently the amount of microtubules.

Ethylene Polymerization via Zirconocene Catalysts and Organoboron Activators: an Experimental and Kinetic Modeling Study

After 40 years of the discovery of metallocene catalysts, there are still several aspects that remain unresolved, especially when the “conventional” alkylaluminum activators are not used. Herein, we systematically investigate the synthesis of PE via three different zirconocene catalysts, with different alkyl substituents, activated via different organoboron compounds. The polymerization behavior, as well as the properties of the materials, are evaluated. The results demonstrate that the highest catalytic activity is shown by Bis(cyclopentadienyl)dimethylzirconium activated by trityl tetra(pentafluorophenyl)borate. Also finding that toluene is the optimum solvent for these systems and at these reaction conditions. Moreover, to validate our experimental results, a comprehensive mathematical model is developed on the basis of thermodynamic and kinetic principles. The concentration of ethylene transferred to the solvent phase (toluene) in a liquid-vapor equilibrium (LVE) system is estimated based on the Duhem’s theorem. Arrhenius expressions for the kinetic rate constants of a proposed kinetic mechanism are estimated by a kinetic model, in which the rate of polymerization is fitted by a least-square optimization procedure and the molecular weight averages by the method of moments. The simulations of the coordination polymerization suggest the presence of two types of active sites, principally at low temperatures, and the reactivation of the deactivated sites via a boron-based activator. However, the effect of the temperature on the reactivation step is no clear; a deeper understanding via designed experiments is required.

Expandable polystyrene without any embedded blowing agent

In this research, in-situ suspension polymerization of styrene in the presence of graphene, without any blowing agent, was investigated. Steam used in the expansion process of graphene-filled expandable polystyrene (GEPS). The dispersed graphene nano-sheets in the polystyrene matrix may absorb water in high temperatures, which evaporates by lowering the pressure and expansion precedes. The effects of graphene type and loading and steam temperature on the expansion ratio evaluated. Scanning electron microscopy (SEM) used to reveal the cross-section morphologies before and after expansion. The effect of graphene on the polymerization kinetics evaluated by differential scanning calorimetry (DSC). The results showed that by increasing the graphene loading, the rate of polymerization decreased, and the expansion ratio increased. The highest expansion ratio of about 4.8 was for particles containing 0.4% of graphene. Therefore, it was shown that by using graphene as a dispersed phase, polystyrene particles expanded without any organic blowing agents. Here, the idea of expandable polymers without any embedded blowing agent is introduced, which eliminates the release of volatile organic compounds and makes the process environmentally friendly.

Effects of Post-Translational Modifications of Fibrinogen on Clot Formation, Clot Structure, and Fibrinolysis

Objective: Post-translational modifications of fibrinogen influence the occurrence and progression of thrombotic diseases. In this systematic review, we assessed the current literature on post-translational modifications of fibrinogen and their effects on fibrin formation and clot characteristics. Approach and Results: A systematic search of Medline, Embase, Cochrane Library, and Web of Science was performed to find studies reporting post-translational modifications of fibrinogen and the effects on clot formation and structure. Both in vitro studies and ex vivo studies using patient material were included. One hundred five articles were included, describing 11 different modifications of fibrinogen. For the best known and studied modifications, conclusions could be drawn about their effect on clot formation and structure. Oxidation, high levels of nitration, and glycosylation inhibit the rate of polymerization, resulting in dense clots with thinner fibers, while low levels of nitration increase the rate of polymerization. Glycation showed different results for polymerization, but fibrinolysis was found to be decreased, as a consequence of increased density and decreased permeability of clots. Acetylation also decreases the rate of polymerization but results in increased fiber diameters and susceptibility to fibrinolysis. Other modifications were studied less or contrasting results were found. Therefore, substantial gaps in the knowledge about the effect of post-translational modifications remain. Conclusions: Overall, post-translational modifications do affect clot formation and characteristics. More studies need to be performed to reveal the effects of all post-translational modifications and the effects on thrombotic diseases. Expanding the knowledge about modifications of fibrinogen can ultimately contribute to optimizing treatments for thrombotic diseases.

Gelatin Type A from Porcine Skin Used as Co-Initiator in a Radical Photo-Initiating System

In the present study, a different approach for the preparation of poly(ethylene glycol) diacrylate-gelatin (PEGDA-gelatin) hydrogels was investigated. Gelatin type A from porcine skin was used as the co-initiator of a radical photo-initiating system instead of the traditional aliphatic or aromatic amines. This became possible because, upon visible-light irradiation, the amine sequences within gelatin generate initiating free-radicals through the intermolecular proton transfer in a Norrish type II reaction with camphorquinone (CQ). PEGDA-gelatin hydrogels were prepared by visible-light-induced photopolymerization. The gelatin content in the precursor formulations was varied. The influence of gelatin on the kinetics of the photocuring reaction was investigated, and it was found that gelatin fastened the rate of polymerization at all concentrations. The covalent attachment of gelatin segments within the cross-linked hydrogels was evaluated by means of attenuated total reflectance-infrared spectroscopy (ATR-FTIR) spectroscopy after solvent extraction. The thermo-mechanical properties, as well as the swelling behavior and gel content, were also investigated.