For the first time, the use of epoxy resins for the immobilisation of catalytically active metal species is reported. The resins were cured using metal acetylacetonates and alkoxides as polymerisation initiators and the thus obtained thermosets were tested as epoxidation catalysts. Outstanding long-term catalyst activities and selectivities were observed for molybdenum-containing resins in the epoxidation of cyclohexene with tert-butyl hydroperoxide. Mechanistic investigations indicate a superposition of heterogeneous and homogeneous catalysis and a heterogeneous contribution to the catalytic activity of at least 15% can be estimated. Metal leaching is extremely low and depends on the catalyst preparation mode. The catalysts were employed batchwise in up to 60 reactions exceeding an application period of 50 days. Based on these results catalyst lifetimes of approximately 1500 days can be expected. They were applied without any reconditioning and loss of activity thus offering promising perspectives for industrial applications in continuously operating processes.

Molybdenum-doped epoxy resin was prepared from Mo(OEt)5 and the tetraglycidyl derivatives of 4,4′-methylenedianiline (TGMDA). Excellent long-term catalyst activity and selectivity were observed for this resin in the epoxidation of cyclohexene with tert-butyl hydroperoxide (TBHP). This catalyst was readily recovered and reused 60 times without any loss of catalytic activity.

The reaction of Zn(SCN)(2) with one or two equivalents of 1-(3-aminopropyl)-imidazole (api) yields the coordination polymers [Zn(SCN)(2)(api)](n) (1) and [Zn(SCN)(2)(aPi)(2)](n) (2), respectively. Single-crystal X-ray diffraction analysis reveals one-dimensional polymeric chain structures for both compounds. The structure of 1 consists of tetrahedral Zn(SCN)(2)(aPi)(2) units linked by one molecule 1-aminopropyl imidazole in an unsymmetric mode, i.e., each metal center is coordinated by an imidazole nitrogen as well as a nitrogen of the aminopropyl group. The metal ions in 2 display an octahedral coordination geometry with each Zn(SCN)(2)(aPi)2 unit linked by two molecules of the imidazole, thus, exhibiting two imidazole and two amino groups in the coordination sphere. The polymers were further characterized by IR-, H-1 NMR- and C-13 NMR-spectroscopy. (c) 2005 Elsevier B.V. All rights reserved.

Chemie Ingenieur TechnikVolume 77, Issue 8 p. 1207-1207 Vortrag Metalldotierte Hochleistungsduromere – Neue Katalysatoren für die Epoxidierung von Alkenen U. Arnold Dr., U. Arnold Dr. ulrich.arnold@itc-cpv.fzk.de Institut für Technische Chemie (ITC-CPV), Forschungszentrum Karlsruhe GmbH, Postfach 3640, D-76021 KarlsruheSearch for more papers by this authorM. Döring Prof., M. Döring Prof. Institut für Technische Chemie (ITC-CPV), Forschungszentrum Karlsruhe GmbH, Postfach 3640, D-76021 KarlsruheSearch for more papers by this author U. Arnold Dr., U. Arnold Dr. ulrich.arnold@itc-cpv.fzk.de Institut für Technische Chemie (ITC-CPV), Forschungszentrum Karlsruhe GmbH, Postfach 3640, D-76021 KarlsruheSearch for more papers by this authorM. Döring Prof., M. Döring Prof. Institut für Technische Chemie (ITC-CPV), Forschungszentrum Karlsruhe GmbH, Postfach 3640, D-76021 KarlsruheSearch for more papers by this author First published: 10 August 2005 https://doi.org/10.1002/cite.200590195AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume77, Issue8Special Issue: GVC/DECHEMA-JahrestagungenAugust, 2005Pages 1207-1207 RelatedInformation