Laboratoriumsapparate

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Crossover in dynamics of polymeric liquids: Back to Tll?

Light scattering spectra of two polymers, polyisobutylene (PIB) and polystyrene (PS), were analyzed in the broad frequency range at temperatures above the glass transition (T_g ). At high temperatures, the spectra followed the qualitative scenario suggested by mode‐coupling theory (MCT) of the glass transition. The crossover temperature (T_c ) was defined to be approximately 1.35 T_g in PIB and approximately 1.15 T_g in PS. At lower temperatures (T < T_c ), the light scattering spectra deviated strongly from the idealized MCT scenario. Different signs of the dynamic transition around T_c are discussed. The difference between the suggested interpretation and an old idea of the liquid–liquid transition in polymeric liquids is stressed: we describe the transition as purely dynamic in nature. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2785–2790, 2000     

Conditions for deuterium exchange mediated by iridium complexes formed in situ

A series of iridium-based complexes formed in situ, containing pyridine, phosphines, triphenylarsine, triphenylstibine, and triphenylamine as ligands, has been screened for ability to mediate ortho-exchange of hydrogen in a series of model substrates. Improved incorporation into a number of substrate classes has been achieved. The electronic properties and number of ligands at the metal centre are instrumental in determining which catalysts are best suited to exchange in any given substrate.     

Recent advances in the anionic synthesis of chain-end functionalized polymers

Recent results for the preparation of chain-end functionalized polymers using alkyllithium-initiated anionic polymerization are described. Termination with 4-chloro-1,1,1-trimethoxybutane has been used to prepare trimethoxy ortho ester (carboxyl)-functionalized polymers. Functionalization with the oxiranes, glycidoxypropyltrimethoxysilane, 3,4-epoxy-1-butene and 1,1,1-trifluoro-2,3-epoxypropane, has been investigated to prepare trimethoxysilyl-functionalized polymers, 1,3-diene-functionalized macro monomers and trifluoromethyl-functionalized polymers, respectively. Secondary amine-functionalized polymers have been prepared by termination with N-(benzylidene)methylamine and also using an N-benzyl tertiary amine-functionalized alkyllithium initiator followed by hydrogenolysis of the benzyl group.     

Kalk

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How well can renewable resources mimic commodity monomers and polymers?

This highlight discusses the recent progress aimed at maximizing the potential of biomass for commodity monomers and polymers. These efforts are no longer solely academic issues. In recent years, a variety of alkene, diene, aromatic, and condensation type monomers have utilized renewable resources, such as cellulose, lignin, plant oils, starches, and monoterpenes in commercial polymers. Generally, these multifaceted efforts involve pretreatment of biomass with thermal, chemical, or physical methods followed by a catalyst sequence that entails a combination of acid‐catalysis, bio‐catalysis, or metal‐based catalysis. In this regard, synthesis strategies for ethylene, propylene, α‐olefins, methylmethacrylate, 1,3‐butadiene, 1,3‐cyclohexadiene, isoprene, 1,3‐propanediol, 1,4‐butanediol, and terephthalic acid are discussed as well as opportunities for other renewable‐based monomers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012