CA1218828A - Method of preparing compounds of silicon and hydrogen, especially silane - Google Patents
Method of preparing compounds of silicon and hydrogen, especially silaneInfo
- Publication number
- CA1218828A CA1218828A CA000443887A CA443887A CA1218828A CA 1218828 A CA1218828 A CA 1218828A CA 000443887 A CA000443887 A CA 000443887A CA 443887 A CA443887 A CA 443887A CA 1218828 A CA1218828 A CA 1218828A
- Authority
- CA
- Canada
- Prior art keywords
- magnesium
- reaction
- process according
- hydrogen
- halogensilane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000001257 hydrogen Substances 0.000 title claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 title claims abstract 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract 3
- 239000010703 silicon Substances 0.000 title abstract description 6
- 229910052710 silicon Inorganic materials 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 title abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title 1
- 229910012375 magnesium hydride Inorganic materials 0.000 claims abstract description 23
- -1 polycyclic aromatic Chemical class 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 150000004820 halides Chemical class 0.000 claims abstract description 4
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000000737 periodic effect Effects 0.000 claims abstract description 3
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims 1
- 239000012190 activator Substances 0.000 abstract description 8
- 235000001055 magnesium Nutrition 0.000 abstract 3
- 229940091250 magnesium supplement Drugs 0.000 abstract 3
- 235000009434 Actinidia chinensis Nutrition 0.000 description 9
- 235000009436 Actinidia deliciosa Nutrition 0.000 description 9
- 244000298697 Actinidia deliciosa Species 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 239000005046 Chlorosilane Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 150000004681 metal hydrides Chemical class 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 244000298715 Actinidia chinensis Species 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/04—Hydrides of silicon
- C01B33/043—Monosilane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0896—Compounds with a Si-H linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Silicon Polymers (AREA)
- Catalysts (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Method of preparing compounds of silicon and hydro-gen, especially silane (SiH4), from halogensilanes character-ized by reacting the halogensilane, especially tetrachloro-silane, in a solvent in the absence of additional catalysts or activators with magnesium hydride obtained by converting magnesium with hydrogen in the presence of a catalyst con-sisting of a halide of a metal of Subgroups IV-VIII of the periodic table and of a magnesium-organic compound or magnes-ium hydride, in the presence of a polycyclic aromatic or ter-tiary amine if necessary, and in the presence of a magnesium halide, MgX2, in which X = Cl, Br, or I. The halogensilane can be reacted with the magnesium hydride in the same vessel that the magnesium was hydrogenated.
Method of preparing compounds of silicon and hydro-gen, especially silane (SiH4), from halogensilanes character-ized by reacting the halogensilane, especially tetrachloro-silane, in a solvent in the absence of additional catalysts or activators with magnesium hydride obtained by converting magnesium with hydrogen in the presence of a catalyst con-sisting of a halide of a metal of Subgroups IV-VIII of the periodic table and of a magnesium-organic compound or magnes-ium hydride, in the presence of a polycyclic aromatic or ter-tiary amine if necessary, and in the presence of a magnesium halide, MgX2, in which X = Cl, Br, or I. The halogensilane can be reacted with the magnesium hydride in the same vessel that the magnesium was hydrogenated.
Description
METHOD OF PREPARING COMPOUNDS OF SILICON AND HYDROGEN, ESPECIALLY SOLON
The present invention concerns a method of pro-paring compounds of silicon and hydrogen, especially Solon (Sue), which is employed commercially for the manufacture of high-purity silicon.
There are two conventional methods of synthesizing Solon: the protolytic decomposition of magnesium solaced (Mg2Si) and the reaction of tetrachlorosilane with metal Hyde rides (Gmelin, _and_uch d. an_rg. them., Six Supply .1, 59 [1982]). The advantage of the latter method is that the sit-aye is free of undesirable contaminants, especially higher sullenness.
Since the discovery of lithium aluminum hydrides (Lyle) and its application to the synthesis of metal Hyde rides and other elementary hydrides (Funneled, Bond, Wilzbach Schlesinger, _ Amer. Chum. Sock 69, 2962 [1947]), the no-action of Seiko with Lyle has been considered the simplest and best laboratory method of preparing Solon (Norman, Webster, & Jolly, Inorg. Sync 11, 170 [1968]). Solon pro-pared by this method can be employed to manufacture silicon for the semiconductor and solar-cell industry because it is free of boron-hydrogen compounds and higher sullenness (Gmelin, Handbuch, foe. cit., 63). This reaction, however, is too ox-___ ___ pensive on an industrial scale because of the high price of Lyle. Many attempts have been made during the last 20 to 25 ~2~8828 years to substitute less expensive metal hydrides, complex if necessary, for the appropriate but costly Lyle. Zakharkin et at. (Bull Aged. Sat. USSR, Chum. Sat. Div. 1962, 1784) and Anti pin it allege. Apply Chum. USSR 42, 416 [1969]) report_ _ __ _ _ _ _ _ _ that Seiko, HSiC13, and alkoxysilane react with Noel or Cole in THY or diglyme even at low temperatures to form sit-aye in a good yield. Nothing is known about the industrial application of this method to the synthesis of Solon.
It is significant in relation to the present invent lion that the known methods for the production of Solon do not employ the simple binary hydrides of the alkali and alkaline-earth metals, like Nay, MgH2, and Kiwi, as such, but only after they have been converted into complex aluminum hydrides by reaction with Alec (GO Pat. 832 333, KIWI. 16765 [1960]; Vim et at., Czech 126 672 [1962, 68], KIWI. 70 39392 [1969]) or in the presence of silane-production activators or catalysts or both. This it probably because of the low Sealab-islet or reactivity or both of binary metal hydrides prepared from the chemical elements at high temperatures and pros-surest Zinc halides, zinc hydrides, and zinc alkyds or zinc oxide (GO Pat. 909 950, KIWI. 58, 2185 [1963]) and metallic zinc or zinc alloys or both (US Pat. 3 050 366, KIWI. 58, 280 [1963]) have been proposed as catalysts for the reaction of Nay, Kiwi, or MgH2 with Seiko. The ZnC12 used as a "catalyst"
in the reaction of Seiko with Nay in THY is added, however, in a mole ration of ZnC12:SiC14 = 1:2, which is almost stoichiometric. Alkyds of boron or aluminum (German Pat.
i2~8828 034 159, KIWI. 56, 16764; Junker, Chemiker Zig. 85, 264-72 [1961]) and hydrides of boron or aluminum German Pat. 1 085 505, KIWI. 21505 [1961]; German Pat. 1 096 341, KIWI. 26388 [1961]) have also been proposed catalysts of activators for the manufacture of Sue from Seiko and Nay, although this en-tails the risk of contaminating the resulting Solon with us-desired alkyd sullenness (as activators in the case of Allure) or boron compounds (in the case of boron activators). USSR
Patent 126 672, KIWI. 84, 166821 (1976) admittedly avoids these drawbacks by employing Noel as an activator.
Special note should be made of the experimental production of Solon with magnesium hydrides disclosed in GO
Patent 909 950, which expressly declares magnesium hydrides to be unsuited to the preparation of high-purity Solon by reaction with halogensilanes.
It will be obvious from the above that a simple and cost-effective industrial-scale method of employing binary metal hydrides to manufacture Solon by reaction with halo-gensilanes does not as yet exist.
European Patent 0 003 564 discloses a method em-plying homogeneous transition metal catalysts to hydrogenate metallic magnesium subject to mild reaction conditions into magnesium hydrides that, in contrast to a hydrides prepared by the conventional method of high-temperature hydrogenation, is highly reactive. In this method, the magnesium is converted with hydrogen in the presence of a catalyst consisting of a halide of a metal of Subgroups IV-VIII of the periodic table ~Z~88;Z~8 and an organomagnesium compound or a magnesium hydrides and optionally in the presence of a polycyclic aromatic compound or a tertiary amine and optionally in the presence of a mug-noisome halide, MgX2 in which X = Of, Bra or I.
It has now been discovered, surprisingly, that the magnesium hydrides this method makes so easy to obtain is out-standingly suited to the manufacture of sullenness from twitter-chlorosilane or other chlorosilanes without any additional catalysts or activators.
The reaction occurs, even at room temperature or slightly higher (50-70C), in a cyclic or linear ether or in a polyether like THY or 1,2-dimethyoxyethane as a solvent and results in a high yield of the corresponding Solon.
In combination with the above-mentioned synthesis of magnesium hydrides this results in a two-stage synthesis of Solon from the inexpensive raw materials My, Ho, and Seiko:
catalyst My + Ho ~~~~~~~~~ MgH2 activator and 2MgH2 + Sill -------I Six + 2 McCauley - or Jo - 5 -~L21~8;~8 Another advantage of this method is that the mug-noisome can be hydrogenated and the MgH2 subsequently reacted with the Seiko in a single vessel with THY as the reaction medium.
MgH2 obtained by the method disclosed in European Patent 0 003 564 can also be isolated in solid form and then reacted with a chlorosilane, Seiko for example, in another appropriate solvent.
The invention will now be specified with reference to the following examples but without being restricted to them.
Example 1 The apparatus consisted of a three-necked 100-m~
flask equipped with a dropping funnel, internal thermometer, magnetic stirrer, and cold finger ( 78C) and connected to a mercury-filled gas burette. 0.68 g of magnesium hydrides pro-pared by the method disclosed in European Patent 0 003 564 (according to example 1, but using Tokyo instead of Crook) with the titanium catalyst were placed in an argon atmosphere in the apparatus and covered with a layer of 20 my of Abe solute THY. A solution of 1.04 g (0.7 my , 6.1 moles) of Seiko in 20 my of THY was dripped into the suspension of MgH2 while it was being stirred at room temperature. The reaction mixture was slowly heated. Gas started to form at about 40C
and its volume was determined with the burette. Reaction heat temporarily increased the temperature of the reaction mixture I; - 6 -~2~81328 to 65C. 134 my of gas (20C and 1 bar) had formed by the end of the reaction. Mass spectrometer of the gas revealed that it contained 20.9 mole Sue (the remainder being argon). In terms of the total volume of the apparatus, the yield of Sue was 80%.
Example 2 The test was conducted as in Example 1 with a sup-pension of MgH2 in THY that had been prepared in situ (lit-annum catalyst). The MgH2 started to react with the Seiko to form Sue at temperatures as low as 25-28C. The yield of Sue was 76~.
Example 3 The apparatus consisted of a three-necked I flask equipped with a dropping funnel, internal thermometer, mug-netic stirrer, and reflex condenser (methyl alcohol, 10C) and connected to a cold trap (-78C). 18.56 g of magnesium hydrides prepared by the method disclosed in European Patent 0 003 564 (according to example 1, but using Tokyo instead of Crook) with the titanium catalyst were placed in an argon at-misfire in the apparatus and covered with a layer of 250 ml of absolute 1,2-dimethoxyethane. A solution of 107.20 g (126 my , 0.99 moles) of (CH3)SiCl in 100 my of 1,2-dimethoxy-ethanes was dripped for 3 hours into the suspension of MgH2 while it was being stirred. The temperature of the mixture increased to 25-27C. When all the (CH3)SiCl had been added, I
~Z1~38Z13 the reaction mixture was briefly heated to the boiling point within the current of argon. The yield of trimethylsilane by = 6.7C) condensing in the cold trap was 80%.
It will be understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art.
The present invention concerns a method of pro-paring compounds of silicon and hydrogen, especially Solon (Sue), which is employed commercially for the manufacture of high-purity silicon.
There are two conventional methods of synthesizing Solon: the protolytic decomposition of magnesium solaced (Mg2Si) and the reaction of tetrachlorosilane with metal Hyde rides (Gmelin, _and_uch d. an_rg. them., Six Supply .1, 59 [1982]). The advantage of the latter method is that the sit-aye is free of undesirable contaminants, especially higher sullenness.
Since the discovery of lithium aluminum hydrides (Lyle) and its application to the synthesis of metal Hyde rides and other elementary hydrides (Funneled, Bond, Wilzbach Schlesinger, _ Amer. Chum. Sock 69, 2962 [1947]), the no-action of Seiko with Lyle has been considered the simplest and best laboratory method of preparing Solon (Norman, Webster, & Jolly, Inorg. Sync 11, 170 [1968]). Solon pro-pared by this method can be employed to manufacture silicon for the semiconductor and solar-cell industry because it is free of boron-hydrogen compounds and higher sullenness (Gmelin, Handbuch, foe. cit., 63). This reaction, however, is too ox-___ ___ pensive on an industrial scale because of the high price of Lyle. Many attempts have been made during the last 20 to 25 ~2~8828 years to substitute less expensive metal hydrides, complex if necessary, for the appropriate but costly Lyle. Zakharkin et at. (Bull Aged. Sat. USSR, Chum. Sat. Div. 1962, 1784) and Anti pin it allege. Apply Chum. USSR 42, 416 [1969]) report_ _ __ _ _ _ _ _ _ that Seiko, HSiC13, and alkoxysilane react with Noel or Cole in THY or diglyme even at low temperatures to form sit-aye in a good yield. Nothing is known about the industrial application of this method to the synthesis of Solon.
It is significant in relation to the present invent lion that the known methods for the production of Solon do not employ the simple binary hydrides of the alkali and alkaline-earth metals, like Nay, MgH2, and Kiwi, as such, but only after they have been converted into complex aluminum hydrides by reaction with Alec (GO Pat. 832 333, KIWI. 16765 [1960]; Vim et at., Czech 126 672 [1962, 68], KIWI. 70 39392 [1969]) or in the presence of silane-production activators or catalysts or both. This it probably because of the low Sealab-islet or reactivity or both of binary metal hydrides prepared from the chemical elements at high temperatures and pros-surest Zinc halides, zinc hydrides, and zinc alkyds or zinc oxide (GO Pat. 909 950, KIWI. 58, 2185 [1963]) and metallic zinc or zinc alloys or both (US Pat. 3 050 366, KIWI. 58, 280 [1963]) have been proposed as catalysts for the reaction of Nay, Kiwi, or MgH2 with Seiko. The ZnC12 used as a "catalyst"
in the reaction of Seiko with Nay in THY is added, however, in a mole ration of ZnC12:SiC14 = 1:2, which is almost stoichiometric. Alkyds of boron or aluminum (German Pat.
i2~8828 034 159, KIWI. 56, 16764; Junker, Chemiker Zig. 85, 264-72 [1961]) and hydrides of boron or aluminum German Pat. 1 085 505, KIWI. 21505 [1961]; German Pat. 1 096 341, KIWI. 26388 [1961]) have also been proposed catalysts of activators for the manufacture of Sue from Seiko and Nay, although this en-tails the risk of contaminating the resulting Solon with us-desired alkyd sullenness (as activators in the case of Allure) or boron compounds (in the case of boron activators). USSR
Patent 126 672, KIWI. 84, 166821 (1976) admittedly avoids these drawbacks by employing Noel as an activator.
Special note should be made of the experimental production of Solon with magnesium hydrides disclosed in GO
Patent 909 950, which expressly declares magnesium hydrides to be unsuited to the preparation of high-purity Solon by reaction with halogensilanes.
It will be obvious from the above that a simple and cost-effective industrial-scale method of employing binary metal hydrides to manufacture Solon by reaction with halo-gensilanes does not as yet exist.
European Patent 0 003 564 discloses a method em-plying homogeneous transition metal catalysts to hydrogenate metallic magnesium subject to mild reaction conditions into magnesium hydrides that, in contrast to a hydrides prepared by the conventional method of high-temperature hydrogenation, is highly reactive. In this method, the magnesium is converted with hydrogen in the presence of a catalyst consisting of a halide of a metal of Subgroups IV-VIII of the periodic table ~Z~88;Z~8 and an organomagnesium compound or a magnesium hydrides and optionally in the presence of a polycyclic aromatic compound or a tertiary amine and optionally in the presence of a mug-noisome halide, MgX2 in which X = Of, Bra or I.
It has now been discovered, surprisingly, that the magnesium hydrides this method makes so easy to obtain is out-standingly suited to the manufacture of sullenness from twitter-chlorosilane or other chlorosilanes without any additional catalysts or activators.
The reaction occurs, even at room temperature or slightly higher (50-70C), in a cyclic or linear ether or in a polyether like THY or 1,2-dimethyoxyethane as a solvent and results in a high yield of the corresponding Solon.
In combination with the above-mentioned synthesis of magnesium hydrides this results in a two-stage synthesis of Solon from the inexpensive raw materials My, Ho, and Seiko:
catalyst My + Ho ~~~~~~~~~ MgH2 activator and 2MgH2 + Sill -------I Six + 2 McCauley - or Jo - 5 -~L21~8;~8 Another advantage of this method is that the mug-noisome can be hydrogenated and the MgH2 subsequently reacted with the Seiko in a single vessel with THY as the reaction medium.
MgH2 obtained by the method disclosed in European Patent 0 003 564 can also be isolated in solid form and then reacted with a chlorosilane, Seiko for example, in another appropriate solvent.
The invention will now be specified with reference to the following examples but without being restricted to them.
Example 1 The apparatus consisted of a three-necked 100-m~
flask equipped with a dropping funnel, internal thermometer, magnetic stirrer, and cold finger ( 78C) and connected to a mercury-filled gas burette. 0.68 g of magnesium hydrides pro-pared by the method disclosed in European Patent 0 003 564 (according to example 1, but using Tokyo instead of Crook) with the titanium catalyst were placed in an argon atmosphere in the apparatus and covered with a layer of 20 my of Abe solute THY. A solution of 1.04 g (0.7 my , 6.1 moles) of Seiko in 20 my of THY was dripped into the suspension of MgH2 while it was being stirred at room temperature. The reaction mixture was slowly heated. Gas started to form at about 40C
and its volume was determined with the burette. Reaction heat temporarily increased the temperature of the reaction mixture I; - 6 -~2~81328 to 65C. 134 my of gas (20C and 1 bar) had formed by the end of the reaction. Mass spectrometer of the gas revealed that it contained 20.9 mole Sue (the remainder being argon). In terms of the total volume of the apparatus, the yield of Sue was 80%.
Example 2 The test was conducted as in Example 1 with a sup-pension of MgH2 in THY that had been prepared in situ (lit-annum catalyst). The MgH2 started to react with the Seiko to form Sue at temperatures as low as 25-28C. The yield of Sue was 76~.
Example 3 The apparatus consisted of a three-necked I flask equipped with a dropping funnel, internal thermometer, mug-netic stirrer, and reflex condenser (methyl alcohol, 10C) and connected to a cold trap (-78C). 18.56 g of magnesium hydrides prepared by the method disclosed in European Patent 0 003 564 (according to example 1, but using Tokyo instead of Crook) with the titanium catalyst were placed in an argon at-misfire in the apparatus and covered with a layer of 250 ml of absolute 1,2-dimethoxyethane. A solution of 107.20 g (126 my , 0.99 moles) of (CH3)SiCl in 100 my of 1,2-dimethoxy-ethanes was dripped for 3 hours into the suspension of MgH2 while it was being stirred. The temperature of the mixture increased to 25-27C. When all the (CH3)SiCl had been added, I
~Z1~38Z13 the reaction mixture was briefly heated to the boiling point within the current of argon. The yield of trimethylsilane by = 6.7C) condensing in the cold trap was 80%.
It will be understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art.
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing a silane from a halogen-silane comprising reacting the halogensilane, in a solvent with magnesium hydride obtained by reacting magnesium with hydrogen in the presence of a catalyst consisting of a halide of a metal of Subgroups IV-VIII of the periodic table and an organomagnesium compound or a magnesium hydride.
2. A process according to claim 1 wherein a polycyclic aromatic compound or a tertiary amine is also present in said reaction of magnesium with hydrogen.
3. A process according to claim 1 where n a magnesium halide, MgX2, in which X = Cl, Br, or I, is also present in said reaction of magnesium with hydrogen.
4. A process according to claim 1, in which the solvent is an ether.
5. A process according to claim 4, wherein the solvent is THF or 1,2-dimethoxyethane.
6. A process according to claim 1, wherein the reaction is effected at a temperature from about 0 to 150°C.
7. A process according to claim 1, wherein the reaction is effected at a temperature from about 20 to 70°C.
8. A process according to claim 1, wherein the reaction is effected in the same vessel in which the magnesium hydride is produced.
9. A process according to claim 1, wherein the halogensilane is tetrachlorosilane.
10. A process according to claim 8, wherein the halogensilane is tetrachlorosilane, the solvent is THF or 1,2-dimethoxyethane, and the reaction is effected at a temperature from about 20 to 70°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3247362.1 | 1982-12-22 | ||
| DE19823247362 DE3247362A1 (en) | 1982-12-22 | 1982-12-22 | METHOD FOR PRODUCING SILICON HYDROGEN COMPOUNDS, ESPECIALLY THE SILANE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1218828A true CA1218828A (en) | 1987-03-10 |
Family
ID=6181324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000443887A Expired CA1218828A (en) | 1982-12-22 | 1983-12-21 | Method of preparing compounds of silicon and hydrogen, especially silane |
Country Status (9)
| Country | Link |
|---|---|
| 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) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5061470A (en) * | 1990-08-03 | 1991-10-29 | Ethyl Corporation | Silane production from hydridomagnesium chloride |
| 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 |
| TWI486307B (en) * | 2010-12-23 | 2015-06-01 | Memc Electronic Materials | Methods and systems for producing silane |
Families Citing this family (11)
| 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 |
| 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 |
Family Cites Families (4)
| 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 |
-
1982
- 1982-12-22 DE DE19823247362 patent/DE3247362A1/en not_active Withdrawn
-
1983
- 1983-12-20 AT AT83112798T patent/ATE40815T1/en not_active IP Right Cessation
- 1983-12-20 EP EP83112798A patent/EP0111924B1/en not_active Expired
- 1983-12-20 DE DE8383112798T patent/DE3379199D1/en not_active Expired
- 1983-12-21 CA CA000443887A patent/CA1218828A/en not_active Expired
- 1983-12-21 ES ES528246A patent/ES8406982A1/en not_active Expired
- 1983-12-21 JP JP58243066A patent/JPS59131519A/en active Granted
- 1983-12-21 AU AU22755/83A patent/AU577035B2/en not_active Ceased
- 1983-12-21 DK DK590083A patent/DK161696C/en not_active IP Right Cessation
- 1983-12-21 IE IE3016/83A patent/IE56457B1/en not_active IP Right Cessation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5061470A (en) * | 1990-08-03 | 1991-10-29 | Ethyl Corporation | Silane production from hydridomagnesium chloride |
| 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 |
| US8974761B2 (en) | 2010-12-23 | 2015-03-10 | Sunedison, Inc. | Methods for producing silane |
| US9011803B2 (en) | 2010-12-23 | 2015-04-21 | Sunedison, Inc. | Systems for producing silane |
| TWI486307B (en) * | 2010-12-23 | 2015-06-01 | Memc Electronic Materials | Methods and systems for producing silane |
| US9487406B2 (en) | 2010-12-23 | 2016-11-08 | Sunedison, Inc. | Systems for producing silane |
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 |
| IE833016L (en) | 1984-06-22 |
| 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 |
| DE3379199D1 (en) | 1989-03-23 |
| ES8406982A1 (en) | 1984-08-16 |
| DE3247362A1 (en) | 1984-06-28 |
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