DK161696B - PROCEDURE FOR MAKING SILICON HYDROGEN COMPOUNDS ISAER SILAN - Google Patents
PROCEDURE FOR MAKING SILICON HYDROGEN COMPOUNDS ISAER SILAN Download PDFInfo
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- DK161696B DK161696B DK590083A DK590083A DK161696B DK 161696 B DK161696 B DK 161696B DK 590083 A DK590083 A DK 590083A DK 590083 A DK590083 A DK 590083A DK 161696 B DK161696 B DK 161696B
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- Prior art keywords
- magnesium
- hydride
- magnesium hydride
- reaction
- halide
- Prior art date
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 22
- -1 SILICON HYDROGEN COMPOUNDS Chemical class 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 title claims description 5
- 239000010703 silicon Substances 0.000 title claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910012375 magnesium hydride Inorganic materials 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229910000077 silane Inorganic materials 0.000 claims abstract description 16
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 239000012190 activator Substances 0.000 claims abstract description 10
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000004820 halides Chemical class 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 4
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 239000005046 Chlorosilane Substances 0.000 claims description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000010923 batch production Methods 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229910052987 metal hydride Inorganic materials 0.000 description 4
- 150000004681 metal hydrides Chemical class 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910003910 SiCl4 Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012280 lithium aluminium hydride Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XMIJDTGORVPYLW-UHFFFAOYSA-N [SiH2] Chemical compound [SiH2] XMIJDTGORVPYLW-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003756 stirring Methods 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
- 101100494265 Caenorhabditis elegans best-15 gene Proteins 0.000 description 1
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910003828 SiH3 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 244000309464 bull Species 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical group [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 description 1
- 229910021338 magnesium silicide Inorganic materials 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
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- OLRJXMHANKMLTD-UHFFFAOYSA-N silyl Chemical compound [SiH3] OLRJXMHANKMLTD-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 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
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)
- Mechanical Treatment Of Semiconductor (AREA)
- Catalysts (AREA)
Abstract
Description
iin
DK 161696 BDK 161696 B
Den foreliggende opfindelse angår en fremgangsmåde til fremstilling af siliciumhydrogen-forbindelser, især silan (SiH^), der finder teknisk anvendelse til fremstilling af højrent silicium.The present invention relates to a process for the preparation of silicon hydrogen compounds, especially silane (SiH 2), which finds technical use in the production of high purity silicon.
5 Af de to gængse metoder til syntese af silan, den protolyti- ske dekomponering af magnesiumsilicid (f^Si) og omsætningen af tetrachlorsilan med metalhydrider (Gmelin's Handbuch d. Anorg.Chem., Si, Suppl. B 1, S. 59 (1982), har sidstnævnte bl.a den fordel, at silanen kan udvindes uden uønskede foru-10 reningen, især forureninger af højere silaner.5 Of the two common methods of synthesis of silane, the protolytic decomposition of magnesium silicide (f ^ Si) and the reaction of tetrachlorosilane with metal hydrides (Gmelin's Handbuch d. Anorg.Chem., Si, Suppl. B 1, p. 59) 1982), the latter has the advantage, inter alia, that the silane can be recovered without undesirable pollution, especially higher silane contaminants.
Siden opdagelsen af lithiumaluminiumhydrid og dettes anvendelse til syntese af metalr eller grundstofhydrider (Finholt, Bond, Wilzbach og Schlesinger, J.Amer.Chem.Soc. (>9, 2962 (1947)) anses omsætningen af SiCl^ med LiAlH^ som den bedste 15 og simpleste laboratoriemetode til dannelse af silan (Norman,Since the discovery of lithium aluminum hydride and its use in the synthesis of metal or elemental hydrides (Finholt, Bond, Wilzbach and Schlesinger, J.Amer.Chem.Soc. (> 9, 2962 (1947)), the reaction of SiCl3 with LiAlH4 is considered the best 15 and simplest laboratory method for silane formation (Norman,
Webster, Jolly, Inorg.Syn. 1_1, 170 (1968)). Den ifølge denne metode fremstillede silan egner sig til dannelse af silicium til halvleder- og solcelleindustrien, da den dannes uden indhold af borhydrogenforbindelser og højere silaner (Gmelin's 20 Handbuch, loc.cit S 63). Til den tekniske anvendelse af denne reaktion i større målestok virker den relativt høje pris på lithiumaluminiumhydrid imidlertid uheldig. Det har derfor i de sidste 20-25 år ikke manglet på forsøg på at erstatte det til formålet egnede, men dyrere LialH^ med mere prisgun-25 stige, eventuelt komplekse metalhydrider. IfølgeWebster, Jolly, Inorg.Syn. 1_1, 170 (1968)). The silane prepared according to this method is suitable for the formation of silicon for the semiconductor and solar cell industries as it is formed without the content of boron hydrogen compounds and higher silanes (Gmelin's 20 Handbuch, loc.cit S 63). However, for the technical application of this reaction on a larger scale, the relatively high price of lithium aluminum hydride seems unfortunate. For the last 20-25 years, therefore, it has not been lacking in attempts to replace the suitable but more expensive LialH ^ with more affordable, possibly complex metal hydrides. According to
Zakharkin et al. (Bull.Acad.Sci. (UdSSR), Div.Chem.Sci. 1962, 1784) og Antipin et al. (J.Appl.Chem.(UdSSR) 42. 416 (1969)) reagerer SiCl^, HSiCl^ og alkoxysilaner med NaAlH^ eller KAlH^ i THF eller diglyme allerede ved lave temperaturer under dan-30 nelse af silan i gode udbytter. Om den tekniske anvendelse af denne metode til syntese af silan er intet kendt.Zakharkin et al. (Bull.Acad.Sci. (USSR), Div.Chem.Sci. 1962, 1784) and Antipin et al. (J. Appl.Chem. (USSR) 42, 416 (1969)) SiCl3, HSiCl4 and alkoxysilanes react with NaAlH2 or KAlH2 in THF or diglyme already at low temperatures to form silane in good yields. Nothing is known about the technical application of this method for the synthesis of silane.
I sammenhæng med den foreliggende opfindelse er den kendsgerning af betydning, at de simple, binære hydrider af alka li- og jordalkalimetallerne, såsom NaH, Mgi^ og Ca^» hidtil 35 ikke som sådanne, men kun efter omdannelse til komplekshydri- 2In the context of the present invention, the fact that the simple, binary hydrides of the alkali and alkaline earth metals, such as NaH, Mg 2, and Ca 2, are hitherto not as such, but only after conversion to complex hydrates.
DK 161696 BDK 161696 B
der af aluminium (ved omsætning med AlCl^: GB-A 832 333, C.A. 16765 (1960), Vit et al., Czech. 126672 (1962/68), C.A. 70, 39392 (1969)) eller i nærværelse af aktivatorer eller katalysatorer har kunnet anvendes til fremstilling af silan.aluminum (by reaction with AlClCl: GB-A 832 333, CA 16765 (1960), Vit et al., Czech. 126672 (1962/68), CA 70, 39392 (1969)) or in the presence of activators or catalysts have been used to produce silane.
5 Årsagen hertil ligger formodentlig i den ringe opløselighed og/eller reaktivitet af de ved høje temperaturer og tryk af grundstofferne fremstillede binære metalhydrider. Som katalysatorer for omsætningen af NaH, Ca^ eller Mgi^ med SiCl^ anbefaledes zinkhalogenider, -hydrider og -alkylforbindelser 10 eller zinkoxid (GB-A 909 950, C.A. 58 (1963) 2185 eller zink metal eller zinklegeringer (US-A 3 050 366), C.A 58, (1960) 280). Det til omsætningen af SiCl^ med f.eks. NaH i THF som "katalysator" krævede ZnC^ anvendes herved imidlertid i molforholdet ZnCl2 : SiCl^ =1:2, dvs. i praktisk taget stø-15 kiometrisk mængde. Til anvendelsen af NaH til dannelse afThe reason for this is probably due to the poor solubility and / or reactivity of the binary metal hydrides produced at high temperatures and pressures. As catalysts for the reaction of NaH, Ca 2, or Mg 2 366), CA 58 (1960) 280). That for the reaction of SiCl 2 with e.g. However, NaH in THF as "catalyst" required ZnCl 2 is hereby used in the molar ratio ZnCl 2: SiCl 2 = 1: 2, i.e. in virtually castiometric amount. For the use of NaH to form
SiH^ udfra SiCl4 anbefales som katalysatorer eller aktivatorer desuden bor- eller aluminiumalkylforbindelser (DE-c 1 034 159), C.A. 5(>, 16764: Jenkner, Chemiker Ztg. R5, 264/74 (1961) samt bor- eller aluminiumhydrider (DE-C 1 085 505, 20 C.A. 21505 (1961) og DE-C 1 096 341, C.A. 26388 (1961)), hvorved den risiko foreligger, at den derved opnåede silan indeholder de uønskede alkylsilaner (i tilfælde af AlR^ som aktivatorer) eller borforbindelser (i tilfælde af boraktivatorer) som forureninger. Ifølge SU-A 126 672, C.A. 84, 25 166812 (1976) bortfalder ganske vist disse ulemper ved anven delse af NaAlH^ som aktivator.SiH4 from SiCl4 is also recommended as catalysts or activators for boron or aluminum alkyl compounds (DE-c 1,034,199), C.A. 5 (>, 16764: Jenkner, Chemiker Ztg. R5, 264/74 (1961) as well as boron or aluminum hydrides (DE-C 1,085,505, CA CA 21505 (1961) and DE-C 1,096341, CA 26388 (1961) ), whereby there is the risk that the resulting silane contains the undesirable alkylsilanes (in the case of AlR 2 as activators) or boron compounds (in the case of boron activators) as contaminants. According to SU-A 126 672, CA 84, 25 166812 ( 1976), admittedly, these disadvantages are eliminated by the use of NaAlH 2 as activator.
Der skal især henvises til forsøgene på fremstilling af silan SiH^ under anvendelse af magnesiumhydrid, der er beskrevet i GB-A 909 950. Det fastslås imidlertid deri udtrykkeligt, 30 at magnesiumhydrider ikke egner sig til fremstilling af høj rent silan ved omsætning med halogensilaner.In particular, reference should be made to the experiments on the preparation of silane SiH 2 using magnesium hydride described in GB-A 909 950. However, it is expressly stated therein that magnesium hydrides are not suitable for the production of high pure silane in reaction with halogen silanes.
Af det anførte fremgår, at til anvendelse af binære metalhydrider med henblik på dannelse af silan ved omsætning med halogensilaner har der hidtil ikke foreligget nogen enkel 35 og omkostningsgunstig teknisk løsning.From the above it can be seen that for the use of binary metal hydrides for the formation of silane by reaction with halogen silanes, there has so far been no simple and cost-effective technical solution.
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Ifølge det europæiske patentskrift nr. 0 003 564 kan imidlertid metallisk magnesium ved hjælp af homogene overgangsmetal-katalysatorer under milde reaktionsbetingelser hydrogeneres til magnesiumhydrid, som i modsætning til magnesiumhydrid, 5 der er fremstillet ved den sædvanlige metode (højtemparatur hydrogenering), udviser en høj reaktivitet.However, according to European Patent No. 0 003 564, metallic magnesium can be hydrogenated to magnesium hydride by means of homogeneous transition metal catalysts under mild reaction conditions, which, in contrast to magnesium hydride produced by the usual method (high temperature hydrogenation), exhibits a high reactivity. .
Der er her tale om en fremgangsmåde, ved hvilken man i nærværelse af en katalysator bestående af et halogenid af et metal fra IV. til VIII. sidegruppe i det periodiske system 10 og en organisk magnesiumforbindelse eller et magnesiumhydrid samt evt. i nærværelse af en polycyklisk aromatisk forbindelse eller en tertiær amin samt eventuelt i nærværelse af et magne-siumhalogenid MgX2, hvor X = Cl, Br, J, omsætter magnesium med hydrogen.This is a process in which, in the presence of a catalyst consisting of a halide of a metal from IV. to VIII. side group of the periodic system 10 and an organic magnesium compound or a magnesium hydride as well as any. in the presence of a polycyclic aromatic compound or a tertiary amine and optionally in the presence of a magnesium halide MgX2 where X = Cl, Br, J, react magnesium with hydrogen.
15 Det har nu overraskende vist sig, at det ifølge denne metode let tilgængelige magnesiumhydrid på fremragende måde egner sig til dannelse af silaner udfra tetrachlorsilan eller andre chlorsilaner, hvorved ingen yderligere katalysatorer eller aktivatorer er nødvendige.Surprisingly, it has now been found that, by this method, readily available magnesium hydride is excellent in forming silanes from tetrachlorosilane or other chlorosilanes, whereby no additional catalysts or activators are needed.
20 Fremgangsmåden ifølge opfindelsen er kendetegnet ved, at man lader halogensilaner, især tetrachlorsilan, reagere med magnesiumhydrid i et opløsningsmiddel i fravær af yderligere katalysatorer og/eller aktivatorer, hvilket magnesiumhydrid opnås ved, at man i nærværelse af en katalysator be-25 stående af halogenid af et metal fra IV. til VIII. sidegruppe i det periodiske system og en organisk magnesiumforbindelse eller et magnesiumhydrid samt eventuelt i nærværelse af en polycyklisk aromatisk forbindelse eller en tertiær amin samt eventuelt i nærværelse af et magnesiumhalogenid MgX2? hvor 30 X = Cl, Br, J, omsætter magnesium med hydrogen.The process of the invention is characterized in that halogen silanes, especially tetrachlorosilane, are reacted with magnesium hydride in a solvent in the absence of additional catalysts and / or activators, which magnesium hydride is obtained by the presence of a catalyst of halide. of a metal from IV. to VIII. side group in the periodic table and an organic magnesium compound or a magnesium hydride and optionally in the presence of a polycyclic aromatic compound or a tertiary amine and optionally in the presence of a magnesium halide MgX2? where 30 X = Cl, Br, J, react magnesium with hydrogen.
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Reaktionen forløber i en cyklisk eller lineær ether eller i en polyether, såsom THF eller glyme som opløsningsmiddel allerede ved stuetemperatur eller ved let forhøjet temperatur (50-70°C) og fører til de tilsvarende silaner i høje udbytter.The reaction proceeds in a cyclic or linear ether or in a polyether such as THF or glyme as a solvent already at room temperature or at slightly elevated temperature (50-70 ° C) and leads to the corresponding silanes in high yields.
5 I kombination med den nævnte syntese af magnesiumhydrid opnås dermed en totrinssyntese af silan udfra de billige råstoffer Mg, H2 og f.eks. SiCl4:Thus, in combination with the said synthesis of magnesium hydride, a two-step synthesis of silane is obtained from the cheap raw materials Mg, H2 and e.g. SiCl4:
Katalysatorcatalyst
Mg + H2 -> MgH2 10 Aktivator 2 MgH2 + SiCl4-5> SiH4 + 2 MgCl2·Mg + H2 -> MgH2 Activator 2 MgH2 + SiCl4-5> SiH4 + 2 MgCl2 ·
En yderligere fordel ved denne metode er, at hydrogeneringen af magnesium og den påfølgende omsætning af MgH2 med SiCl4 kan gennemføres i en batchproces i f.eks. THF som reaktions-15 medium.A further advantage of this method is that the hydrogenation of magnesium and the subsequent reaction of MgH2 with SiCl4 can be carried out in a batch process in e.g. THF as a reaction medium.
Der foreligger imidlertid også den mulighed, at det i henhold til europapatentskriftet nr. 0 003 564 fremstillede MgH2 isoleres i fast form og derpå i et andet passende opløsningsmiddel anvendes til omsætning med chlorsilaner, f.eks. SiCl4- 20 Opfindelsen forklares nærmere i de følgende eksempler.However, there is also the possibility that the MgH 2 prepared according to European Patent No. 0 003 564 is isolated in solid form and then used in another suitable solvent for reaction with chlorosilanes, e.g. The invention is further explained in the following examples.
Eksempel 1 I et apparatur bestående af en 100 ml trehalset kolbe, der var udrustet med en tildrypningstrakt, indre termometer, mag-netomrører og kølefinger (-78°C), hvilket apparatur var til-25 sluttet en med kviksølv fyldt gasburette, blev påfyldt 0,68 g af det ifølge europæisk patentskrift nr. 0 003 564Example 1 In an apparatus consisting of a 100 ml three-neck flask equipped with a drip funnel, internal thermometer, magnetic stirrer and cooling finger (-78 ° C), which apparatus was connected to a gas burette filled with mercury. 0.68 g of it according to European Patent No. 0 003 564
DK 161696 BDK 161696 B
5 med Ti-katalysatoren fremstillede magnesiumhydrid under argon, som blev dækket med 20 ml absolut THF. En opløsning af 1,04 g (0,7 ml, 6,1 mmol) SiCl^ i 20 ml THF blev ved stuetemperatur og under omrøring tildryppet til MgH2-suspensionen.5 with the Ti catalyst produced magnesium hydride under argon, which was covered with 20 ml of absolute THF. A solution of 1.04 g (0.7 ml, 6.1 mmol) of SiCl 2 in 20 ml of THF was added dropwise to the MgH2 suspension at room temperature and with stirring.
5 Reaktionsblandingen blev langsomt opvarmet, hvorved gasudviklingen satte ind fra ca. 40°C, hvilken gasudvikling blev målt ved hjælp af gasburetten. Som følge af reaktionsvarmen steg reaktionsblandingens temperatur forbigående til 65°C. Efter reaktionens afslutning androg gasudviklingen 134 ml (20°C, 10 1 bar). MS-analyse af gassen viste en SiH^-mængde på 20,9 mol-% (resten argon). Under hensyntagen til apparaturets samlede volumen udregnedes deraf et SiH^-udbytte på 80%.The reaction mixture was slowly heated, thereby initiating gas evolution from ca. 40 ° C, which gas evolution was measured by the gas burette. Due to the heat of the reaction, the temperature of the reaction mixture transiently rose to 65 ° C. After completion of the reaction, the gas evolution was 134 ml (20 ° C, 10 l bar). MS analysis of the gas showed an SiH₂ amount of 20.9 mol% (residue argon). Therefore, taking into account the total volume of the apparatus, an SiH₂ yield of 80% was calculated.
Eksempel 2Example 2
Forsøget blev gennemført analogt med eksempel 1, hvorved der 15 blev anvendt en insitudannet suspension af MgH2 i THF (Ti-katalysator). Omsætningen af MgH2 med SiCl^ under dannelse af SiH^ forløb i dette tilfælde allerede ved 25-28°C. Udbyttet af SiH4 androg 76%.The test was conducted analogously to Example 1, using an insituated suspension of MgH2 in THF (Ti catalyst). The reaction of MgH2 with SiCl3 to form SiH3 in this case was already carried out at 25-28 ° C. The yield of SiH4 was 76%.
Eksempel 3 20 I et apparatur bestående af en 1 1 trehalset kolbe, der var udrustet med en tildrypningstragt, indre termometer, magnet-omrører og tilbagesvaler (methanol 10°C) samt tilsluttet en kølefælde (-78°C), placeredes 18,56 g af det ifølge europæisk patentskrift nr. 0 003 564 (Ti-katalysator) fremstillede mag-25 nesiumhydrid under argon og blev dækket med 250 ml absolut glyme. En opløsning af 107,20 (126 ml, 0,99 mol) (CH^SiCl i 100 ml glyme blev tildryppet i løbet af 3 timer og under omrøring af MgH2~suspensionen, hvorved blandingens temperatur steg til 25-27°C. Efter afsluttet (CH^)SiCl-tilsætning 30 blev reaktionsblandingen kortvarigt opvarmet til kogetemperatur i argonstrømmen. Udbyttet af den i kølefælden kondenserede trimethylsilan (kogepunkt 6,7°C) androg 80%.Example 3 In an apparatus consisting of a 1 liter three-neck flask equipped with a drip funnel, internal thermometer, magnetic stirrer and reflux (methanol 10 ° C) and connected to a cooling trap (-78 ° C) was placed 18.56 g of the magnesium hydride produced under argon according to European Patent No. 0,003,564 (Ti catalyst) and covered with 250 ml of absolute glyme. A solution of 107.20 (126 mL, 0.99 mol) (CH 2 SiCl in 100 mL glyme) was added dropwise over 3 hours and with stirring the MgH 2 suspension, raising the temperature of the mixture to 25-27 ° C. After the (CH 2) SiCl addition 30, the reaction mixture was briefly heated to boiling temperature in the argon stream.The yield of the trimethylsilane condensed in the cooling trap (boiling point 6.7 ° C) was 80%.
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3247362 | 1982-12-22 | ||
| DE19823247362 DE3247362A1 (en) | 1982-12-22 | 1982-12-22 | METHOD FOR PRODUCING SILICON HYDROGEN COMPOUNDS, ESPECIALLY THE SILANE |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| DK590083D0 DK590083D0 (en) | 1983-12-21 |
| DK590083A DK590083A (en) | 1984-06-23 |
| DK161696B true DK161696B (en) | 1991-08-05 |
| DK161696C DK161696C (en) | 1992-01-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK590083A DK161696C (en) | 1982-12-22 | 1983-12-21 | PROCEDURE FOR MAKING SILICON HYDROGEN COMPOUNDS ISAER SILAN |
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) | ES528246A0 (en) |
| IE (1) | IE56457B1 (en) |
Families Citing this family (15)
| 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 |
| US4725419A (en) * | 1985-05-17 | 1988-02-16 | Ethyl Corporation | Silane production from magnesium hydride |
| EP0316472A1 (en) * | 1987-11-17 | 1989-05-24 | 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 |
| CN103384640B (en) * | 2010-12-23 | 2016-03-02 | Memc电子材料有限公司 | For the preparation of the method and system of silane |
| US8821825B2 (en) | 2010-12-23 | 2014-09-02 | Sunedison, Inc. | Methods for producing silane |
| US8388914B2 (en) | 2010-12-23 | 2013-03-05 | Memc Electronic Materials, Inc. | Systems for producing silane |
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 IE IE3016/83A patent/IE56457B1/en not_active IP Right Cessation
- 1983-12-21 DK DK590083A patent/DK161696C/en not_active IP Right Cessation
- 1983-12-21 CA CA000443887A patent/CA1218828A/en not_active Expired
- 1983-12-21 ES ES528246A patent/ES528246A0/en active Granted
- 1983-12-21 JP JP58243066A patent/JPS59131519A/en active Granted
- 1983-12-21 AU AU22755/83A patent/AU577035B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| ATE40815T1 (en) | 1989-03-15 |
| DK590083A (en) | 1984-06-23 |
| DK161696C (en) | 1992-01-27 |
| ES8406982A1 (en) | 1984-08-16 |
| DE3247362A1 (en) | 1984-06-28 |
| AU577035B2 (en) | 1988-09-15 |
| DK590083D0 (en) | 1983-12-21 |
| IE833016L (en) | 1984-06-22 |
| EP0111924A3 (en) | 1986-10-29 |
| EP0111924A2 (en) | 1984-06-27 |
| ES528246A0 (en) | 1984-08-16 |
| JPH0553727B2 (en) | 1993-08-10 |
| DE3379199D1 (en) | 1989-03-23 |
| CA1218828A (en) | 1987-03-10 |
| JPS59131519A (en) | 1984-07-28 |
| EP0111924B1 (en) | 1989-02-15 |
| AU2275583A (en) | 1984-06-28 |
| IE56457B1 (en) | 1991-08-14 |
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