Racemic β-butyrolactone can be polymerized to crystalline polymers of reasonably high molecular weight by the use of aluminoxane catalysts. Investigations in this and other laboratories have shown that these polymers can be fairly highly isotactic, and in that form they are closely related in structure and physical properties to a reserve polyester produced by many bacteria: poly(β-hydroxybutyrate). In the present investigation, Ziegler–Natta type aluminoxane catalyst systems and a new aluminoxane derivative, tert-butylaluminoxane, were evaluated in attempts to polymerize racemic β-butyrolactone in higher yields to polymers of higher molecular weight and higher stereoregularity. The addition of group 4 metallocenes as cocatalysts for both methylaluminoxane and iso-butylaluminoxane catalysts gave higher yields of the isotactic polymer than those obtained with these catalysts alone, but surprisingly, the tert-butylaluminoxane catalysts produced predominantly syndiotactic rather than isotactic polymers.Key words: poly(β-hydroxybutyrate), β-butyrolactone, aluminoxane catalysts, isotactic poly(β-hydroxybutyrate), syndiotactic poly(β-hydroxybutyrate).
The rate of tritium /3-decay-induced isotopic exchange between tritium gas and water vapor is found to be constant within a fourfold variation in the water vapor density, but to increase as a second-order function of the tritium concentration. Inert gases, present in large excess, appeared to function purely as moderating media for the tritium /3-energy. With helium gas as the moderator and tritium concentration in the range from 0.05 to 0.7 c./l., the reaction rate in mc./l.'/day at the ambient temperature of 22 ± 2°is observed as d(HTO)/d< = 3.6 X 10-6(T2)2, where (T2) is the initial tritium concentration in mc./l. This exchange reaction is strongly inhibited by the presence of nitric oxide in the reaction mixture. The results are consistent with a reaction mechanism involving radical intermediates.
Since the second industrial revolution, the use of fossil fuels has been powering the advance of human society. However, the surge in carbon dioxide (CO2) emissions has raised unsettling concerns about global warming and its consequences. Membrane separation technologies have emerged as one of the major carbon reduction approaches because they are less energy-intensive and more environmentally friendly compared to other separation techniques. Compared to pure polymeric membranes, mixed matrix membranes (MMMs) that encompass both a polymeric matrix and molecular sieving fillers have received tremendous attention, as they have the potential to combine the advantages of both polymers and molecular sieves, while cancelling out each other’s drawbacks. In this review, we will discuss recent advances in the development of MMMs for CO2 separation. We will discuss general mechanisms of CO2 separation in an MMM, and then compare the performances of MMMs that are based on zeolite, MOF, metal oxide nanoparticles and nanocarbons, with an emphasis on the materials’ preparation methods and their chemistries. As the field is advancing fast, we will particularly focus on examples from the last 5 years, in order to provide the most up-to-date overview in this area.
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