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Many variations on protocol and analysis were explored in the pre-study. Final choices were based on a minimal condition of demonstrated reproducibility (less than 2% variance in yield at any point over three independent runs) with the objective of minimizing catalyst use and apparatus complexity. Among the factors studied were 1) comparison of batch results to protocols involving the continuous removal of the ethyl acrylate/ethanol azeotrope; 2) scale of the reaction between 8 mL and 100 mL scale; 3) the effect of the addition of molecular sieves (no effect) ; 4) the effect of added solvent (dodecane, no significant advantage); and 5) substrate to catalyst ratio (between 100 and 1000).
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Neither polymerization nor Michael addition products were observed, perhaps due to the low temperature and the presence of a radical trap (hydroquinone stabilizer).
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50
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Note
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4 is represented together with a discussion of its significance in the catalyst regeneration section (see Figure 7 and Figure 8).
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51
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70349424418
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Several different exploratory studies of lixivation were performed. These incomplete studies were all equivalent with the hypothesis that some lixivation was present during catalysis with the monopodal catalyst 1 but very little lixivation was observable for 2 and 3. For example, catalysts 1 and 2 (powders) were tested in the presence of silica beads. Zirconium microanalysis of the beads after reaction showed a similar degree of transfer of zirconium in the case of 1 (-20% transfer), but very little in the case of 2. In another study, catalyst 1 was continuously extracted (Soxhlet) with butanol for three days (the extraction bed temperature was not measured but was clearly superior to the 70°C catalytic test temperature): zirconium microanalysis of the solid showed loss of 28% of the initial zirconium.
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