Investigation of ring-opening polymerization of 5-[2-{2-(2-methoxyethoxy)ethoxy}-ethoxymethyl]-5-methyl-1,3-dioxa-2-one by organometallic catalysts

To develop new polymer-based materials, the design of aliphatic carbonate has received attention and become a well-known cyclic monomer. In view of carbonate ring polymer scope, poly(trimethylene carbonate) (PTMC) has been continuously developed for further applications due to its unique degradability. PTMC bearing oligo ethylene glycol units, PTMCM-MOE3OM, were typically prepared via ring-opening polymerization (ROP) using amidine-based catalysts such as 1,8-diazabicyclo[5.4.0] undec-7-ene (DBU) and benzyl alcohol (BnOH) as an initiator. To improve the polymer molecular weight or other properties, several know-how synthetic catalysts based on organometallic complexes are under consideration as potential catalysts. With the existence of diverse classes of metallic complexes, the inorganic complexes were investigated for their catalytic activity based on tris(dimethylsilyl)amido chelating, bis(phenolate) chelating, and macrocyclic tetradentate (NNNN)-type cyclen chelating with a metal-core of tin (II), scandium (III), lutetium (III), and zinc (II). In this study, we found that involving a Zn(II) dimethylcyclen/alkoxide ligand and Mg complexes could accelerate the reaction and finish the polymerization under ambient conditions within 2 hr. Molecular weight reached 11,000 g/mol (40%) and 8,100 g/mol (> 96%). Subsequently, we concluded that Zn and Mg complexes were high reactivity for initiating the ROP of TMCM-MOE3OM upon steadily degree of polymerization.     

Quantification and elucidation of the UV-light triggered initiation kinetics of TPO and BAPO in liquid acrylate monomer

The initiation kinetics of two important UV-light-triggered initiators for the radical polymerization [diphenyl-2,4,6-trimethyl benzoyl phosphine oxide (TPO) and phenyl-bis(2,4,6-trimethyl benzoyl) phosphine oxide (BAPO)] has been quantified in dependence on the initiator concentration (0.25–2 mol %), the light intensity at 365 nm (0–2000 mW cm⁻²), the thickness of the sample (50–200 μm), the temperature (25–80 °C), the monomer [2-ethyl hexyl acrylate (EHA) and 2-ethyl hexyl methacrylate (EHMA)] and the atmosphere (oxygen free and air) directly in the liquid acrylate monomer. The determination of the kinetic parameters was done by applying two independent procedures: (1) following the initiator decay with respect to the irradiation time, evaluated by radiometric measurements of the UV-light absorption at 365 nm and (2) via titration of the initiation process by using defined under-stoichiometric to stoichiometric amounts of TEMPO as inhibitor, evaluated by means of FTIR-ATR spectroscopy. The validity of the titration procedure was proven by means of ¹³C and ³¹P NMR studies of ¹³C-labeled TPO and was explained by a Lewis acid/base interaction between the carbonyl carbon of the initiator and the oxygen of TEMPO. Both methods resulted in very close kinetic parameters. Thus, reliable values for the extinction coefficients ε₃₆₅ at 365 nm, for the effective rate constants of the α cleavage (containing the quantum yield and the initiator efficiency) when dissolved in the liquid monomer could be provided for both initiators for the first time. The effect of dioxygen quenching in dependence of sample thickness and the temperature dependence on the initiation step were evaluated. EHA was compared with EHMA as liquid monomer, and a yet unmentioned inhibition in case of EHMA was discovered. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48357.     

Complexes of Ir(III)-octaethylporphyrin with peptides as probes for sensing cellular O2

Ir(III)-porphyrins are a relatively new group of phosphorescent dyes that have potential for oxygen sensing and labeling of biomolecules. The requirement of two axial ligands for the Ir(III) ion permits simple linkage of biomolecules by a one-step ligand-exchange reaction, for example, using precursor carbonyl chloride complexes and peptides containing histidine residue(s). Using this approach, we produced three complexes of Ir(III)-octaethylporphyrin with cell-penetrating (Ir1 and Ir2) and tumor-targeting (Ir3) peptides and studied their photophysical properties. All of the complexes were stable and possessed bright, long-decay (unquenched lifetimes exceeding 45 μs) phosphorescence at around 650 nm, with moderate sensitivity to oxygen. The Ir1 and Ir2 complexes showed positive staining of a number of mammalian cell types, thus demonstrating localization similar to endoplasmic reticulum and ATP- and temperature-independent intracellular accumulation (direct translocation mechanism). Their low photo- and cytotoxicity allows intracellular oxygen to be probed.     

N-Substituted Nipecotic Acids as (S)-SNAP-5114 Analogues with Modified Lipophilic Domains

Potential mGAT4 inhibitors derived from the lead substance (S)-SNAP-5114 have been synthesized and characterized for their inhibitory potency. Variations from the parent compound included the substitution of one of its aromatic 4-methoxy and 4-methoxyphenyl groups, respectively, with a more polar moiety, including a carboxylic acid, alcohol, nitrile, carboxamide, sulfonamide, aldehyde or ketone function, or amino acid partial structures. Furthermore, it was investigated how the substitution of more than one of the aromatic 4-methoxy groups affects the potency and selectivity of the resulting compounds. Among the synthesized test substances (S)-1-{2-[(4-formylphenyl)bis(4-methoxyphenyl)-methoxy]ethyl}piperidine-3-carboxylic acid, that features a carbaldehyde function in place of one of the aromatic 4-methoxy moieties of (S)-SNAP-5114, was found to have a pIC₅₀ value of 5.89±0.07, hence constituting a slightly more potent mGAT4 inhibitor than the parent substance while showing comparable subtype selectivity.     

Strategien zum Schließen der Stoffkreisläufe beim Recycling von Fluorpolymeren

In fluoropolymers, a large portion or even all of the hydrogen atoms in a polymer chain are replaced by fluorine, which results in a number of special properties such as high chemical and temperature resistance. As a result of this combination of properties, these high-performance polymers are not replaceable, or only with difficulty, for some applications. The recycling of polymers and the associated closing of material loops is an essential development task for the entire polymer industry. Materials such as fluoropolymers have a special position due to their chemical composition and their low market volume, as they cannot be recycled together with other bulk polymers at the end of their life cycle. This paper discusses different processes in terms of their technical maturity and suitability to allow fluoropolymers to be fully recycled.     

Microstructure of rapidly-quenched ZrO2-SiO2 glass-ceramics fabricated by container-less aerodynamic levitation technology

In this work, an aerodynamic levitation technology (ALT) was utilized to prepare ZrO₂-SiO₂ glass-ceramics with two different ZrO₂ contents, that is, 35 mol% and 50 mol%. The glass-ceramics were partially melted at ∼2000°C or fully melted at ∼3000°C by ALT, followed by rapid quenching to obtain spherical glass-ceramic beads. The phase compositions and microstructures of the glass-ceramics were characterized. Crystallization of ZrO₂ occurred during the solidification process and ZrO₂ content, processing temperature, and the addition of yttrium (3 mol%) affected the crystalline phase of ZrO₂. No ZrSiO₄ or crystalline SiO₂ were formed during the solidification process and the glass-ceramics were away from thermodynamic equilibrium due to rapid quenching. The glass-ceramics showed a microstructure of irregular-shaped ZrO₂ micro-aggregates embedded in an amorphous SiO₂ matrix, with lamellar twins and lattice defects formed within ZrO₂ crystals. For samples prepared at ∼3000°C, a liquid-liquid phase separation occurred in the melt, which eventually resulted in the formation of large and irregular-shaped ZrO₂ aggregates. In comparison, for samples prepared at ∼2000°C, pre-existed ZrO₂ crystals formed during heating acted as nucleation sites during the cooling process, followed by grain growth to form large ZrO₂ aggregates. Solidification and microstructure formation mechanisms were proposed to elucidate the solidification process during rapid cooling and the microstructure of the glass-ceramics obtained.     

Cure kinetics of the cardanyl acrylate–styrene system using isothermal differential scanning calorimetry

The curing kinetics of styrene (30 wt %) and cardanyl acrylate (70 wt %), which was synthesized from cardanol and acryloyl chloride, was investigated by differential scanning calorimetry under isothermal condition. The method allows determination of the most suitable kinetic model and corresponding parameters. All kinetic parameters including the reaction order, activation energy E_a and kinetic rate constant were evaluated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2034–2039, 2002     

Thermal Stability, Phase Evolution, and Crystallization in Si-B-C-N Ceramics Derived from a Polyborosilazane Precursor

Amorphous Si-B-C-N ceramic powder samples obtained by thermolysis of boron-modified polysilazane, {B[C₂H₄Si(H)NH]₃} _n , were isothermally annealed at different temperatures (1400–1800°C) and hold times (3, 10, 30, and 100 h). A qualitative and semiquantitative analysis of the crystallization behavior of the materials was performed using X-ray diffraction (XRD). The phase evolution was additionally followed by ¹¹B and ²⁹Si MAS NMR as well as by FT-IR spectroscopy in transmission and diffuse reflection (DRIFTS) modes. Bulk chemical analyses of selected samples were performed to determine changes in the chemistry/phase composition of the materials. It was observed that silicon carbide is the first phase to nucleate around 1400–1500°C, whereas silicon nitride nucleates at and above 1700°C. Crystallization accelerates with increasing annealing temperature and proceeds with increasing annealing time. Furthermore, the surface area of the powders strongly influences the thermal stability of silicon nitride and thus controls overall chemical and phase composition of the materials on thermal treatment.     

Synthese und charakterisierung von butadien-divinylbenzol-copolymeren

The copolymerization of butadiene with a technical divinylbenzene fraction was investigated to study the modification of cis-1,4 polybutadiene. Beside the Ziegler-Natta-catalyst nickeloctanoate/bortrifluoride/aluminiumtriethyl, another catalytic system consisting of nickeloctanoate/titaniumtetrachloride/aluminiumtriethyl was used, which allows to polymerize more divinylbenzene because of its higher activity toward vinylaromates. With the help of spectroscopical, pyrolysis-gaschromatographical and thermoanalytical methods one can obtain relations between glass-, crystallization- and melting temperature and the microstructure of the polymer. It can be shown that not only the divinylbenzene but also the trans-1,4- and the 1,2-vinyl units are statistically distributed in the polymer. By this, beside the pyrolysis-gaschromatography, particularly the differential scanning calorimetry is a useful tool to characterize the structure of partially crosslinked polymers obtained from polymerization of technical fractions.