Hydrogenation of 2-Butyn-1,4-diol in the Presence of Functional Crosslinked Resin Supported Pd Catalyst. The Role of Polymer Properties in Activity/Selectivity Pattern

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• 作者：Anna Knapik ; Alicja Drelinkiewicz ; Anna Waksmundzka-Góra ; Agnieszka Bukowska ; Wiktor Bukowski and Jaroslaw Noworól
• 关键词：Palladium ; Functional resin ; 2 ; Butyne ; 1 ; 4 ; diol ; Hydrogenation
• 刊名：Catalysis Letters
• 出版年：2008
• 出版时间：April, 2008
• 年：2008
• 卷：122
• 期：1-2
• 页码：155-166
• 全文大小：754.7 KB
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Catalysis
  Physical Chemistry
  Industrial Chemistry and Chemical Engineering
  Pharmacy
  
• 出版者：Springer Netherlands
• ISSN：1572-879X

文摘

Functional gel type resins of various crosslinking degrees (3–20%) with C=O and carboxylic groups were used as the supports for Pd catalysts (0.5–2 wt% Pd). The role of polymer properties was studied in the hydrogenation of 2-Butyne-1,4-diol (B3-D) to alkene (B2-D) and alkane (B1-D). Hydrogenation was studied at atmospheric pressure of hydrogen using THF, H₂O and THF + H₂O mixtures as the solvents. Systematic studies were carried out to determine the role of the type of solvent, crosslinking degree of polymer, the content of Pd in catalysts, initial B3-D concentration and the procedure of catalyst reduction in activity/selectivity behaviour of catalysts. Swelling degree of polymer matrix under the catalytic run exhibits crucial role in the activity and selectivity to alkene, B2-D. In the presence of highly expanded catalyst (THF solvent, 3% crosslinking degree, 1 wt% Pd) the alkyne, B3-D, is hydrogenated to alkene, B2-D, with selectivity ca. 85% up to high B3-D conversion (90%). The suppression of alkene to alkane hydrogenation in the stage of B3-D is ascribed to high ability of Pd centres in the Pd/OFP catalysts to strong adsorption of alkyne substrate. It may also be related to steric hindrances of polymer in the vicinity of active Pd centres. At small content of added water (5% by vol.) to THF the catalysts offer very attractive performance in terms of activity and 98% selectivity to alkene. Water facilitates interactions of B3-D with functional groups of polymer that leads to better expansion of polymer matrix and more effective suppression of alkene hydrogenation in the alkyne stage.