TEMPO‐controlled radical suspension polymerization of poly(styrene)‐block‐poly(styrene‐co‐acrylonitrile) and poly(styrene)‐block‐poly(styrene‐co‐butyl methacrylate)

Suspension polymerization expands the study of controlled radical polymerization to high conversions and is known as a method to synthesize polymers with high molecular weights. The radical block copolymerizations of styrene (S) and acrylonitrile (AN) or butyl methacrylate (BUMA) controlled by 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) was performed in an oil/water pressure reactor system at a temperature of 125°C. TEMPO‐terminated styrene homopolymer was employed as macroinitiator. The systems were examined by varying the composition of the monomer mixture at a constant reaction time, as well as by varying the reaction time for a characteristic monomer composition to get all of the possible conversion range. The solubility effects of acrylonitrile in the suspension medium were considered. Furthermore, the yield of the reaction was improved through initiator addition by taking control of the reaction. The polymerizations could proceed under control up to a conversion of 80–90%. By using the copolymerization equations, the solubility of pure acrylonitrile in the suspension medium could be calculated and was found to be 8 wt.‐%.     

Studium der lebenden radikalischen Polymerisation mit der Differential Scanning Calorimetry (DSC)

The living radical polymerization of styrene, some styrene-analogous vinyl monomers as well as methyl methacrylate (MMA) and butyl methacrylate (BuMA) was investigated with a differential scanning calorimeter. The ability to polymerize was estimated by dynamic measurements, showing that p-methylstyrene, p-chlorostyrene, 3,4-dimethoxystyrene and 4-vinylpyridine polymerize in the presence of 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) while MMA and BuMA do not. Isothermal measurements revealed an activation energy of E_A = 81 kJ mol^–1 for thermal bulk polymerization of styrene and values of E_A = 78–94 kJ mol^–1 were measured with different iniferter systems. These polymerizations have induction times which depend on the reaction temperature and the initial concentration of the iniferter systems. An influence of the kind of nitroxyl radical on the induction times was not observed.     

Aluminum Production in the Times of Climate Change: The Global Challenge to Reduce the Carbon Footprint and Prevent Carbon Leakage

JOM - This paper addresses the global challenge of greenhouse gas emissions facing the aluminum industry. The demand, production and use of aluminum are increasing and so are the emissions. From...     

High conversion study of “living” radical polymerization of styrene using DSC

The influence of temperature on nitroxide-controlled living radical polymerization of styrene was examined. It has been established that only in a temperature range of 110°C to 150°C nitroxides are able to control radical polymerization. At temperatures above 160°C the reaction was of rather a free radical character. The results were similar for all the various nitroxides used as capping agents: TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl), 4-hydroxy-TEMPO, 4-oxo-TEMPO and 4-acetamido-TEMPO. Differences were found only in the induction times of polymerization and were probably due to side reactions with the initiator (benzoyl peroxide). Living radical polymerization can be best controlled with these nitroxides at temperatures between 120°C and 140°C.     

Influence of N-oxyls on the free radical autopolymerization of styrene

Through comparative studies on the controlled thermally initiated radical polymerization of styrene in the presence of N-oxyls, the effect of the type of the N-oxyls (2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (OH-TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl (oxo-TEMPO) and 4-acetamido-2,2,6,6-tetramethylpiperidine-N-oxyl (acetamido-TEMPO)), as well as the concentration of the N-oxyls (3–20 mmol L^–1) are discussed. The radical formation proceeds exclusively through the thermal initiation of styrene, i.e. without using any initiator. It is observed, that the thermal self-initiation of styrene increases the radical yield remarkably with the N-oxyls concentration, independent of the type of the N-oxyl. The concentration-dependent side reactions of substituted N-oxyls are remarkably more pronounced than those of unsubstituted N-oxyl. This leads to the reduction of the overall rate of polymerization (v_br) as compared to TEMPO (v_br = v_br (thermal polymerization)) with respect to the concentration, but independent of the type of substituents.     

Untersuchungen zur Naßvernetzung von Lyocell-Fasern

The high wet fibrillation tendency of Lyocell fibres forms the background to this investigation. The wet abrasion behaviour can be improved by crosslinking reactions. Substances containing sulfato ethyl sulfonyl groups but different bridging groups were synthesised and optimised regarding to their application. The wet fibrillation tendency can be reduced clearly with these selected substances. If the concentration of the crosslinking agent on the fibre is the basis of comparisons the different structures have a similar effect on the fibrillation tendency. So the swollen Lyocell fibre permits a crosslinking reaction with curing agents of different size.     

The Chemistry of the Postpharyngeal Gland of Female European Beewolves

Females of the European beewolf, Philanthus triangulum, possess a large glove-shaped gland in the head, the postpharyngeal gland (PPG). They apply the content of the PPG to their prey, paralyzed honeybees, where it delays fungal infestation. Here, we describe the chemical composition of the gland by using combined GC-MS, GC-FTIR, and derivatization. The PPG of beewolves contains mainly long-chain unsaturated hydrocarbons (C23–C33), lower amounts of saturated hydrocarbons (C14–C33), and minor amounts of methyl-branched hydrocarbons (C17–C31). Additionally, the hexane-soluble gland content is comprised of small amounts of an unsaturated C25 alcohol, an unknown sesquiterpene, an octadecenylmethylester, and several long-chain saturated (C25, C27) and unsaturated (C23–C27) ketones, some of which have not yet been reported as natural products. Surprisingly, we found a dimorphism with regard to the major component of the PPG with some females having (Z)-9-pentacosene, whereas others have (Z)-9-heptacosene as their predominant component. The biological relevance of the compounds for the prevention of fungal growth on the prey and the significance of the chemical dimorphism are discussed.     

Deeper Insight into Structures of Modified AEROSIL Particles Synthesized via Conventional Heating and Microwave Heating

The contribution deals with the comparison of microwave heating and conventional oil bath heating. Silicon dioxide nanoparticles were grafted with MPTMS under acid conditions. Those particles contain a polysiloxane shell with physically adsorbed and chemically bound fractions which can be separated by Soxhlet extraction. The resulting fractions were analyzed with TGA and MALDI‐TOF MS; one to determine the amount of physically adsorbed and chemically bound fractions and the other to get deeper insight into the polysiloxane structures. Furthermore, it was our aim to clarify which fraction can be visualized using MALDI‐TOF MS. Our results show that the ratio of chemically bound MPTMS is higher when using microwave heating, but the same structures in the physically adsorbed fraction were built in both cases.

     

Polymer/Clay Nanocomposites: Influence of Ionic Strength on the Structure and Adhesion Characteristics in Multilayered Films

The aim of the present contribution is to understand how ionic strength, brought by the addition of salt to laponite/PEO nanocomposite dispersions, influences the texture and adhesion characteristics at nano‐ and microscales in multilayered nanocomposite films prepared from such dispersions. At the nano‐scale, SAXS and XRD measurements indicated that the clay platelets orient parallel to the film plane and that the polymer chains intercalate the clay platelets regardless of salt addition. A gradual transition from an agglomerated structure, containing polymer‐rich and clay‐rich domains, to a fine‐balanced structure with smaller distinct details without excess PEO was observed, via AFM, on the exposed edges of cryo‐microtomed films with increasing ionic strength.