Disilane Cleavage with Selected Alkali and Alkaline Earth Metal Salts
The industry‐scale production of methylchloromonosilanes in the Müller–Rochow Direct Process is accompanied by the formation of a residue, the direct process residue (DPR), comprised of disilanes MenSi2Cl6‐n (n=1–6). Great research efforts have been devoted to the recycling of these disilanes into m...
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| Published in | Chemistry : a European journal Vol. 25; no. 57; pp. 13202 - 13207 |
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| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
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Germany
Wiley Subscription Services, Inc
11.10.2019
John Wiley and Sons Inc |
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| Abstract | The industry‐scale production of methylchloromonosilanes in the Müller–Rochow Direct Process is accompanied by the formation of a residue, the direct process residue (DPR), comprised of disilanes MenSi2Cl6‐n (n=1–6). Great research efforts have been devoted to the recycling of these disilanes into monosilanes to allow reintroduction into the siloxane production chain. In this work, disilane cleavage by using alkali and alkaline earth metal salts is reported. The reaction with metal hydrides, in particular lithium hydride (LiH), leads to efficient reduction of chlorine containing disilanes but also induces disproportionation into mono‐ and oligosilanes. Alkali and alkaline earth chlorides, formed in the course of the reduction, specifically induce disproportionation of highly chlorinated disilanes, whereas highly methylated disilanes (n>3) remain unreacted. Nearly quantitative DPR conversion into monosilanes was achieved by using concentrated HCl/ether solutions in the presence of lithium chloride.
Too valuable for disposal or incineration: Simple recycling of the Müller–Rochow Direct Process residue with LiH yields monosilanes suitable for the reintroduction into the silicone production chain. |
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| AbstractList | The industry-scale production of methylchloromonosilanes in the Müller-Rochow Direct Process is accompanied by the formation of a residue, the direct process residue (DPR), comprised of disilanes Me
Si
Cl
(n=1-6). Great research efforts have been devoted to the recycling of these disilanes into monosilanes to allow reintroduction into the siloxane production chain. In this work, disilane cleavage by using alkali and alkaline earth metal salts is reported. The reaction with metal hydrides, in particular lithium hydride (LiH), leads to efficient reduction of chlorine containing disilanes but also induces disproportionation into mono- and oligosilanes. Alkali and alkaline earth chlorides, formed in the course of the reduction, specifically induce disproportionation of highly chlorinated disilanes, whereas highly methylated disilanes (n>3) remain unreacted. Nearly quantitative DPR conversion into monosilanes was achieved by using concentrated HCl/ether solutions in the presence of lithium chloride. The industry‐scale production of methylchloromonosilanes in the Müller–Rochow Direct Process is accompanied by the formation of a residue, the direct process residue (DPR), comprised of disilanes MenSi2Cl6‐n (n=1–6). Great research efforts have been devoted to the recycling of these disilanes into monosilanes to allow reintroduction into the siloxane production chain. In this work, disilane cleavage by using alkali and alkaline earth metal salts is reported. The reaction with metal hydrides, in particular lithium hydride (LiH), leads to efficient reduction of chlorine containing disilanes but also induces disproportionation into mono‐ and oligosilanes. Alkali and alkaline earth chlorides, formed in the course of the reduction, specifically induce disproportionation of highly chlorinated disilanes, whereas highly methylated disilanes (n>3) remain unreacted. Nearly quantitative DPR conversion into monosilanes was achieved by using concentrated HCl/ether solutions in the presence of lithium chloride. Too valuable for disposal or incineration: Simple recycling of the Müller–Rochow Direct Process residue with LiH yields monosilanes suitable for the reintroduction into the silicone production chain. Abstract The industry‐scale production of methylchloromonosilanes in the Müller–Rochow Direct Process is accompanied by the formation of a residue, the direct process residue (DPR), comprised of disilanes Me n Si 2 Cl 6‐ n ( n =1–6). Great research efforts have been devoted to the recycling of these disilanes into monosilanes to allow reintroduction into the siloxane production chain. In this work, disilane cleavage by using alkali and alkaline earth metal salts is reported. The reaction with metal hydrides, in particular lithium hydride (LiH), leads to efficient reduction of chlorine containing disilanes but also induces disproportionation into mono‐ and oligosilanes. Alkali and alkaline earth chlorides, formed in the course of the reduction, specifically induce disproportionation of highly chlorinated disilanes, whereas highly methylated disilanes ( n >3) remain unreacted. Nearly quantitative DPR conversion into monosilanes was achieved by using concentrated HCl/ether solutions in the presence of lithium chloride. The industry‐scale production of methylchloromonosilanes in the Müller–Rochow Direct Process is accompanied by the formation of a residue, the direct process residue (DPR), comprised of disilanes Me n Si 2 Cl 6‐ n ( n =1–6). Great research efforts have been devoted to the recycling of these disilanes into monosilanes to allow reintroduction into the siloxane production chain. In this work, disilane cleavage by using alkali and alkaline earth metal salts is reported. The reaction with metal hydrides, in particular lithium hydride (LiH), leads to efficient reduction of chlorine containing disilanes but also induces disproportionation into mono‐ and oligosilanes. Alkali and alkaline earth chlorides, formed in the course of the reduction, specifically induce disproportionation of highly chlorinated disilanes, whereas highly methylated disilanes ( n >3) remain unreacted. Nearly quantitative DPR conversion into monosilanes was achieved by using concentrated HCl/ether solutions in the presence of lithium chloride. Too valuable for disposal or incineration : Simple recycling of the Müller–Rochow Direct Process residue with LiH yields monosilanes suitable for the reintroduction into the silicone production chain. The industry‐scale production of methylchloromonosilanes in the Müller–Rochow Direct Process is accompanied by the formation of a residue, the direct process residue (DPR), comprised of disilanes MenSi2Cl6‐n (n=1–6). Great research efforts have been devoted to the recycling of these disilanes into monosilanes to allow reintroduction into the siloxane production chain. In this work, disilane cleavage by using alkali and alkaline earth metal salts is reported. The reaction with metal hydrides, in particular lithium hydride (LiH), leads to efficient reduction of chlorine containing disilanes but also induces disproportionation into mono‐ and oligosilanes. Alkali and alkaline earth chlorides, formed in the course of the reduction, specifically induce disproportionation of highly chlorinated disilanes, whereas highly methylated disilanes (n>3) remain unreacted. Nearly quantitative DPR conversion into monosilanes was achieved by using concentrated HCl/ether solutions in the presence of lithium chloride. |
| Author | Auner, Norbert Santowski, Tobias Sturm, Alexander G. Holthausen, Max C. Lewis, Kenrick M. Felder, Thorsten |
| AuthorAffiliation | 1 Institut für Anorganische und Analytische Chemie Goethe-Universität Max-von-Laue-Straße 7 60438 Frankfurt/Main Germany 2 Momentive Performance Materials Inc. 769 Old Saw Mill River Rd Tarrytown NY 10591 USA 3 Momentive Performance Materials GmbH, Chempark 51368 Leverkusen Germany |
| AuthorAffiliation_xml | – name: 3 Momentive Performance Materials GmbH, Chempark 51368 Leverkusen Germany – name: 1 Institut für Anorganische und Analytische Chemie Goethe-Universität Max-von-Laue-Straße 7 60438 Frankfurt/Main Germany – name: 2 Momentive Performance Materials Inc. 769 Old Saw Mill River Rd Tarrytown NY 10591 USA |
| Author_xml | – sequence: 1 givenname: Tobias surname: Santowski fullname: Santowski, Tobias organization: Goethe-Universität – sequence: 2 givenname: Alexander G. surname: Sturm fullname: Sturm, Alexander G. organization: Goethe-Universität – sequence: 3 givenname: Kenrick M. surname: Lewis fullname: Lewis, Kenrick M. organization: Momentive Performance Materials Inc – sequence: 4 givenname: Thorsten surname: Felder fullname: Felder, Thorsten organization: Momentive Performance Materials GmbH, Chempark – sequence: 5 givenname: Max C. orcidid: 0000-0001-7283-8329 surname: Holthausen fullname: Holthausen, Max C. email: max.holthausen@chemie.uni-frankfurt.de organization: Goethe-Universität – sequence: 6 givenname: Norbert orcidid: 0000-0002-4645-5292 surname: Auner fullname: Auner, Norbert email: auner@chemie.uni-frankfurt.de organization: Goethe-Universität |
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| CitedBy_id | crossref_primary_10_1002_ange_202011738 crossref_primary_10_1002_cssc_202201953 crossref_primary_10_1021_acs_organomet_2c00141 crossref_primary_10_1002_anie_202011738 |
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| Keywords | disilane cleavage lithium chloride lithium hydride monosilanes alkali and alkaline earth metal salts |
| Language | English |
| License | 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
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| Snippet | The industry‐scale production of methylchloromonosilanes in the Müller–Rochow Direct Process is accompanied by the formation of a residue, the direct process... The industry-scale production of methylchloromonosilanes in the Müller-Rochow Direct Process is accompanied by the formation of a residue, the direct process... Abstract The industry‐scale production of methylchloromonosilanes in the Müller–Rochow Direct Process is accompanied by the formation of a residue, the direct... |
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| SubjectTerms | alkali and alkaline earth metal salts Alkali metals Alkaline earth metals Chemistry Chlorine Cleavage disilane cleavage Disproportionation Earth Lithium Lithium chloride lithium hydride Lithium hydrides Metal hydrides Metals monosilanes Reduction Reintroduction Salts Siloxanes |
| Title | Disilane Cleavage with Selected Alkali and Alkaline Earth Metal Salts |
| URI | https://onlinelibrary.wiley.com/doi/abs/10.1002%2Fchem.201902722 https://www.ncbi.nlm.nih.gov/pubmed/31355503 https://www.proquest.com/docview/2304947849/abstract/ https://search.proquest.com/docview/2266350659 https://pubmed.ncbi.nlm.nih.gov/PMC6856802 |
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