IE833016L - Method of preparing compounds of silicon and hydrogen¹especially silane - Google Patents

Method of preparing compounds of silicon and hydrogen¹especially silane

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Publication number
IE833016L
IE833016L IE833016A IE301683A IE833016L IE 833016 L IE833016 L IE 833016L IE 833016 A IE833016 A IE 833016A IE 301683 A IE301683 A IE 301683A IE 833016 L IE833016 L IE 833016L
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IE
Ireland
Prior art keywords
magnesium
hydride
silane
reaction
optionally
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IE833016A
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IE56457B1 (en
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Studiengesellschaft Kohle Mbh
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Publication date
Application filed by Studiengesellschaft Kohle Mbh filed Critical Studiengesellschaft Kohle Mbh
Publication of IE833016L publication Critical patent/IE833016L/en
Publication of IE56457B1 publication Critical patent/IE56457B1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/04Hydrides of silicon
    • C01B33/043Monosilane
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/0896Compounds with a Si-H linkage

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Silicon Polymers (AREA)
  • Catalysts (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

1. Process for the preparation of silicon hydride compounds, in particular of silane (SiH4 ) from halogen silanes, characterized in that halogen silanes, in particular tetrachlorosilane, are reacted with magnesium hydride in a solvent in the absence of additional catalysts and/or activators, which magnesium hydride is obtained by reacting magnesium with hydrogen in the presence of a catalyst consisting of a halide of a metal of sub-Groups IV to VIII of the periodic System and of an organic magnesium compound or of a magnesium hydride and optionally in the presence of a polycyclic aromatic compound or af a tertiary amine and optionally in the presence of a magnesium halide MgX2 where X = Cl, Br, l.

Description

•i 7 This invention relates to a process for the preparation of silicon hydride compounds, in particular silane (Sill^) which is used industrially for the production of highly pure silicon.
S Of the 'wo conventional methods for the synthesis of silane, namely the protolytic decomposition of magnesium silicide (MgjSi) and the reaction of tetrachlorosilane with metal hydrides (Gmelin's Handbuch d. Anorg.Chem., Si, Supplement Volume 1, page 59 (1982)), the latter 10 has the advantage, inter alia, that the silane can be obtained free from unwanted impurities, in particular of higher silanes.
Since the discovery of lithium aluminium hydride and its use for the synthesis of metal hydrides and hydrides 15 of other elements (Finholt, Bond, Wilzbach and Schlesinger, J.Ainer.Chem.Soc. 6^, 2962 (1947)), the reaction of SiCl^ wi t.h LiAlH4 is regarded as the best and simplest laboratory method for the preparation of silane (Norman, Webster, Jolly, Inorg.Syn. JJ_, 170 (1968)). Silane prepared by 20 this method is suitable for the production of silicon for the semi-conductor and solar cell industry since it is free from boron hydride compounds and higher silanes (Gmelin's Handbuch, loc.cit page 63). For industrial application of this reaction on a large scale, however, 25 the relatively high cost of lithium aluminium hydride is found to be a disadvantage. There has therefore been no lack of attempts in the last 20 to 25 years to replace LiAlH^, which is suitable for this purpose but expensive, by less expensive metal hydrides, if necessary in complex 30 form. According to Zakharkin et al (Bull. Acad. Sci.(USSR), Chem. Sci. Div. (1962, 1784) and Antipin et al (J.Appl. Chem.(USSR) 42, 416 (1969)), SiCl4 , HSiClj and alkoxysilanes react, with N.iAlll^ of KA111 ^ in TIIF or diglyme even at low "I l..cin|"M .11 ii i I .(> lor in silane in high yields. Nothing is known about the industrial application of this method to the synthesis of silane.
It is significant in relation to the present invention that the simple, binary hydrides of alkali metals and alkaline earth metals such as NaH, MgH2 and CaH^ have not hitherto been used as such for the preparation of silane but only after their conversion into complex hydrides of aluminium (by a reaction with AlCl^: GB-A 832 333 C.A. 16765 (1960), Vit et al, Czech. 126672 (1962/6U), C.A. 7t), 39392 (1969)) or in the presence of activators or catalysts. The reason for this is presumably the low solubility and/or reactivity of the binary metal hydrides which are produced from the elements at high temperatures and pressures. Zinc haiides, zinc hydrides and zinc alkyls and zinc oxide (GB-A 909 950, C.A. 58 (1963) 2185) and metallic zinc and zinc alloys (US-A 3 050 366, C.A. SjJ (1963) 280) have been recommended as catalysts for the reaction of NaH, CaH2 or MgH2 with SiCl^, but the ZnCl2 required as "catalyst" for the reaction of SiCl4 with, for example, NaH in THF is used in a molar ratio of SnCl2 : SiCl^ =1:2, i.e. in virtually stoichiometric quantity. Boron alkyls and aluminium alkyls (DE-C 1 034 1 59, C.A. 5_6, 16764 ; Jenkner, Chemiker Ztg. 85, 264/72 (1961)) and boron and aluminium hydrides (DE-C 1 085 505, C.A. 21505 (1961) and DE-C 1 096 341, C.A. 26388 (1961)) have also been recommended as catalysts or activators for the -production of SiH^ from NaH and SiCl4, but when' these catalystrs or activators are employed there is a risk of the silane containing the unwanted alkyl silanes (when AlR^ is used as activator) or boron compounds (when boron activators are used) as impurities. According to SU-A 126 672, C.A. 84 166812 (1976), on the other hand, these disadvantages do not arise when NaAlH4 is used as activator.
The experiments described in GB-A 909 950 for the preparation of silane SiH^ using magnesium hydride should be j;.ul irul.uly noted. Thi- said doi.-uinent: i.'Xpl ic i 1.1 y states th.it m.'ujnesi.urn hydrides art; unsuiitable for the preparation of high purity silane by a reaction with haloqen silanes.
It is clear from what has been said above that no simple and economical technical solution is as yet available for the production of silane from binary metal hydrides by their reaction with halogen silanes.
According to EP-A 0 003 564, however, metallic magnesium may be hydrogenated under mild reaction conditions with the aid of homogeneous transition metal catalysts to produce a magnesium hydride which in contrast to magnesium hydride prepared by the conventional method (high temperature hydrogenation) is highly reactive.
The process described there is one in which magnesium is reacted with hydrogen in the presence of a catalyst consisting of a halide of a metal of sub-Groups IV to VIII of the Periodic System and of an organic magnesium compound or of a magnesium hydride and optionally in the presence of a polycyclic aromatic compound or of a tertiary amine or optionally in the presence of a magnesium halide MgX2 where X = Cl, Br or I.
It has now surprisingly been found that magnesium hydride which is readily available by this method is eminently suitable for the production of silanes from tetrachlorosilane or other chlorosilanes without the use of any further catalysts or activators.
When carried out in a cyclic or linear ether or a polyether such as THF or glyme as solvent, the reaction will take place even at room temperature or at slightly elevated temperature (50 to 70°C) and gives rise to the corresponding silanes in high yields.
In combination with.the above mentioned synthesis of magnesium hydride, therefore, silane is obtained by a two-stage synthesis from the inexpensive raw materials, Mg . Hj and, for example, SiCl^, as follows: Catalyst Mg + H2 Activator * My2 2 MgH2 + SiCl4 SiH4 + 2 MgCl2. 1 5 20 25 # ' 30 Another advantage of this method is that the hydrogen-ation of magnesium and subsequent reaction of MgH2 with SiCl2 can be carried out in one and the same reaction vessel using, for example, THF as reaction medium.
Alternatively, the MgH2 prepared according to EP-A 0 003 564 may be isolated in solid form and then used in another suitable solvent for the reaction with chloro-silanes, e.g. SiCl4.
The invention is described in more detail below with the aid of the following Examples without, however, being limited to these.
Example 1 0.68 g of the magnesium hydride prepared according to EP-A 0 003 564 using Ti catalyst was introduced under argon into an apparatus consisting of a 100 ml three-necked flask equipped with a dropping funnel, internal thermometer, magnetic stirrer and cooling finger (-78°C) and an attached gas burette filled with mercury, and the magnesium hydride was covered with a layer of 20 ml of absolute THF. A solution of 1.40 g (0.7 ml, 6.1 mmol) of SiCl4 in 20 ml of THF was added dropwise to the MgH2 suspension at room temperature with stirring. The reaction mixture was slowly heated and evolution of gas set in at about 40°C. The gas evolved was measured by means of the gas burette. The heat of the reaction temporarily raised the temperature of the reaction mixture to 65°C.
After completion of the reaction, the amount of gas evolved was 134 ml (20°C, 1 bar). MS Analysis of the gas showed it to contain 20.9 mol-% of SiH4 (remainder argon). Taking into account the total volume of the apparatus, the SiH4 -5- yield w.if. c.\] c:u 1 a ted from ll.is i.o be BO'..
KXdmpl2 The experiment was carried out as i.n Example 1 , using an in situ produced suspension of Mgll^ in THF (Ti cata- 5 lyst). The reaction of MgH^ with SiCl^ to form SiH^ in this case already took place at 25 to 28"C. The yield of SiH. was 76'f.. 4 Example 3 18.56 g of the magnesium hydride prepared according 10 to EP-A 0 003 564 (Ti catalyst) was introduced under argon into an apparatus consisting of a 1-litre three-necked flask equipped with dropping funnel , internal thermometer, magnetic guide and reflux condenser (methanol 10°C) and attached to a cooling trap (-78°C), and the 15 reactant was covered with a layer of 250 ml of absolute glyme. A solution of 107.20 g (126 ml, 0.99 mol) of (CH^)SiCl in 100 ml of glyme was added dropwise to the MgH^ suspension over a period of 3 hours with stirring, the temperature of the mixture rising to 25 to 27°C. 20 After all the (CH^JSiCl had been added, the reaction was briefly heated to boiling in the stream of argon. The yield of trimethylsilane condensed in the cooling trap (b.p. 6.7°C) was 80%. -6- ♦

Claims (6)

Claims
1. . Process Cor the preparation of silicon hydride compounds, in particular of silane (SiH^) from halogen silanes. wherein halogen silanes, in parti- 5 cular tetrachlorosilane, are reacted with magnesium hydride in a solvent in the absence of additional catalysts and/or activators, which magnesium hydride is obtained by reacting magnesium with hydrogen in the presence of a catalyst consisting of a halide of a metal of sub-Groups 10 IV to VIII of the Periodic System and of an organic magnesium compound or of a magnesium hydride and optionally in the presence of a polycyclic aromatic compound or of a tertiary amine and optionally in the presence of a magnesium halide MgX£ where X = CI, Br, I. 15
2. Process according to claim 1 , wherein open chained and cyclic mono- and polyethers, preferably THF or glycol dimethylether,are used as solvents.
3. Process according to claims 1 and 2, wherein the reaction is carried out in the temperature 20 range of from 0 to 150°C, preferably from 20 to 70°C.
4. Process according to claims 1 to 3, wherein the hydrogenation of magnesium and the subsequent reaction of magnesium hydride with chlorosilanes, preferably tetrachlorosilane, are carried out as a one pot 25 process.
5. Process for the preparation of silicon hydride compounds substantially as hereinbefore described with reference to the Examples.
6. Silicon hydride compounds whenever prepared by a process as claimed in any of the preceding claims. Dated this 21st day of December 1983.; BY: TOMKINS & CO., Applicants' Agents, (Signed) 5 Dartmouth Road, Dublin 6. -7-
IE3016/83A 1982-12-22 1983-12-21 Method for preparing compounds of silicon and hydrogen,especially silane IE56457B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19823247362 DE3247362A1 (en) 1982-12-22 1982-12-22 METHOD FOR PRODUCING SILICON HYDROGEN COMPOUNDS, ESPECIALLY THE SILANE

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IE833016L true IE833016L (en) 1984-06-22
IE56457B1 IE56457B1 (en) 1991-08-14

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EP (1) EP0111924B1 (en)
JP (1) JPS59131519A (en)
AT (1) ATE40815T1 (en)
AU (1) AU577035B2 (en)
CA (1) CA1218828A (en)
DE (2) DE3247362A1 (en)
DK (1) DK161696C (en)
ES (1) ES8406982A1 (en)
IE (1) IE56457B1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3340492A1 (en) * 1983-11-09 1985-05-15 Studiengesellschaft Kohle mbH, 4330 Mülheim METHOD FOR PRODUCING FINE DISTRIBUTED, HIGHLY REACTIVE MAGNESIUM AND THE USE THEREOF
DE3409172A1 (en) * 1984-03-13 1985-09-26 D. Swarovski & Co., Wattens, Tirol METHOD FOR PRODUCING SILANE
EP0316472A1 (en) * 1987-11-17 1989-05-24 Ethyl Corporation Silane production from magnesium hydride
US4725419A (en) * 1985-05-17 1988-02-16 Ethyl Corporation Silane production from magnesium hydride
US4824657A (en) * 1985-11-27 1989-04-25 E. I. Du Pont De Nemours And Company Process for reducing silicon, germanium and tin halides
US5061470A (en) * 1990-08-03 1991-10-29 Ethyl Corporation Silane production from hydridomagnesium chloride
JPH0548070U (en) * 1991-11-28 1993-06-25 喜和 石渡 Banknote storage and payout device
DE4239246C1 (en) * 1992-11-21 1993-12-16 Goldschmidt Ag Th Process for the preparation of SiH-containing organopolysiloxanes
DE4313130C1 (en) * 1993-04-22 1994-05-26 Goldschmidt Ag Th Silanes and organosilicon hydrides prodn. - by redn. of corresp. silicon halides with non-pyrophoric storage magnesium hydride in THF etc., with continuous removal of halide deposits
DE102004062449A1 (en) * 2004-12-17 2006-07-06 Klaus Dr. Rennebeck Fuel cell system for water mineralization comprises fuel cell based on micro hollow fiber, which contains electrolytes, which carries separately from each other anode and cathode wherein electrolyte is micro hollow fiber-matrix electrolyte
NO326254B1 (en) * 2005-12-22 2008-10-27 Sinvent As Process for producing silane
DE102009056731A1 (en) 2009-12-04 2011-06-09 Rev Renewable Energy Ventures, Inc. Halogenated polysilanes and polygermanes
CN105668573A (en) * 2010-12-23 2016-06-15 爱迪生太阳能公司 Systems for producing silane
US8388914B2 (en) 2010-12-23 2013-03-05 Memc Electronic Materials, Inc. Systems for producing silane
US8821825B2 (en) 2010-12-23 2014-09-02 Sunedison, Inc. Methods for producing silane

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3050366A (en) * 1959-07-15 1962-08-21 Du Pont Production of silane by the use of a zinc catalyst
DE2804445A1 (en) * 1978-02-02 1979-08-09 Studiengesellschaft Kohle Mbh METHOD FOR MANUFACTURING MAGNESIUM HYDRIDS
DE2908928A1 (en) * 1979-03-07 1980-09-18 Studiengesellschaft Kohle Mbh METHOD FOR PRODUCING ORGANOLITHIUM COMPOUNDS IN ADDITION TO LITHIUM HYDROID
DE3536797A1 (en) * 1985-10-16 1987-04-16 Studiengesellschaft Kohle Mbh METHOD FOR PRODUCING HALOGEN MAGNESIUM ALANATE AND THE USE THEREOF

Also Published As

Publication number Publication date
AU577035B2 (en) 1988-09-15
ES528246A0 (en) 1984-08-16
DK161696C (en) 1992-01-27
IE56457B1 (en) 1991-08-14
ATE40815T1 (en) 1989-03-15
DK590083A (en) 1984-06-23
JPS59131519A (en) 1984-07-28
EP0111924A2 (en) 1984-06-27
AU2275583A (en) 1984-06-28
JPH0553727B2 (en) 1993-08-10
DK590083D0 (en) 1983-12-21
DK161696B (en) 1991-08-05
EP0111924B1 (en) 1989-02-15
EP0111924A3 (en) 1986-10-29
CA1218828A (en) 1987-03-10
DE3379199D1 (en) 1989-03-23
ES8406982A1 (en) 1984-08-16
DE3247362A1 (en) 1984-06-28

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