EP2493900A1 - Verfahren zur herstellung von organosilanen - Google Patents

Verfahren zur herstellung von organosilanen

Info

Publication number
EP2493900A1
EP2493900A1 EP10765648A EP10765648A EP2493900A1 EP 2493900 A1 EP2493900 A1 EP 2493900A1 EP 10765648 A EP10765648 A EP 10765648A EP 10765648 A EP10765648 A EP 10765648A EP 2493900 A1 EP2493900 A1 EP 2493900A1
Authority
EP
European Patent Office
Prior art keywords
general formula
mixture
radical
hydrogen
chlorobenzene
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.)
Withdrawn
Application number
EP10765648A
Other languages
German (de)
English (en)
French (fr)
Inventor
Michael Stepp
Tobias Weiss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP2493900A1 publication Critical patent/EP2493900A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07F7/12—Organo silicon halides
    • 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
    • C07F7/12—Organo silicon halides
    • C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
    • C07F7/122—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-C linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • 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
    • C07F7/12—Organo silicon halides
    • C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
    • C07F7/123—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-halogen linkages
    • 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
    • C07F7/12—Organo silicon halides
    • C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
    • C07F7/125—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving both Si-C and Si-halogen linkages, the Si-C and Si-halogen linkages can be to the same or to different Si atoms, e.g. redistribution reactions

Definitions

  • the invention relates to a process for the preparation of
  • Organosilanes of hydrogen silanes and halogenated hydrocarbons in the presence of a radical initiator Organosilanes of hydrogen silanes and halogenated hydrocarbons in the presence of a radical initiator.
  • Laid-open publication is i.a. the production of
  • the object of the invention is to provide a process for the preparation of diorganyldihalogens lanen with high specific yield, which forms little unwanted by-products and which is safe to handle.
  • the invention relates to a process for the preparation of diorganyldihalosilanes of the general formula (1)
  • a free radical initiator which is selected from alkanes reacted, diazenes and organodisilanes, wherein R is a monovalent C] _-C] _g hydrocarbon radical,
  • R ' is a monovalent Ci-Cig hydrocarbon radical, hydrogen or halogen
  • X is halogen
  • Trichlorosilane fall e.g. as distillates in the
  • Chlorosilane production for the production of hyperpure silicon for the semiconductor or photovoltaic industry in large quantities If one uses these chlorosilane mixtures, we obtain by the inventive method by reaction with
  • Radical initiators which are used at 500 ° C. for at least 5 seconds, in particular
  • R 1 and R 4 are phenyl and R 2 , R 3 , R 5 and R 6 are hydrogen or alkyl or R 1 and R 4 are phenyl and R 2 and R 5 are phenyl or alkyl and R 3 and R ⁇ Trialkoxysiloxyrest or
  • R ⁇ , R 2 , R 4 and R 5 are phenyl and R 3 and R 6 are hydrogen
  • R 7 -N NR 8 (6), wherein R7 and R ° C] _-C] _ Q hydrocarbyl may be este, or organodisilanes of the general formula
  • alkyl radicals here are C 1 -C -alkyl radicals
  • R and C are preferably alkyl, aryl or aralkyl radicals.
  • R 1 and R 2 are preferably C 2 -C 5 -alkyl radicals, in particular the methyl or ethyl radical or chlorine.
  • Particularly good results are obtained with 1,2-diphenylethane, 2,3-diphenyl-2, 3-dimethylbutane, 1, 1, 2, 2-tetraphenylethane, 3,4-dimethyl-3-diphenylhexane, dicyclohexyl diazene and di-t-butylamine. achieved by butyl diazene.
  • X and R 'in the meaning of halogen are preferably fluorine,
  • Chlorine and bromine especially chlorine.
  • Particularly preferred is it is the silane of the general formula (2) to dichlorosilane.
  • radicals R ' are preferably phenyl radicals or C 1 -C -alkyl radicals, in particular methyl or ethyl radicals or chlorine.
  • Preferred compounds of the general formula (3) are
  • the silane is the
  • the radicals R are preferably alkenyl radicals preferably having 2 to 6 carbon atoms, such as vinyl-allyl, methallyl, 1-propenyl, 5-hexenyl, ethynyl, butadienyl, hexadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, preferably vinyl and
  • Aryl radicals such as phenyl radicals; Alkaryl radicals, aralkyl, alkenylaryl or arylalkenyl radicals; Phenylalkenyl radicals.
  • Halogenobenzene especially chlorobenzene.
  • the halohydrocarbon of the general formula (4) is reacted with the mixture of the hydrosilanes of the general formulas (2) and (3) in a molar ratio of halogen: Si-bonded hydrogen of not more than 4: 1, in particular not more than 1.5: 1, 0 and at least 1: 4, more preferably at most 3: 1 reacted.
  • the amount of alkane or diazene used as radical initiator is preferably at least 0.005 wt .-%, in particular at least 0.01 wt .-% and at most 3% by weight, in particular not more than 0.5% by weight, based on the mixture of halohydrocarbon used
  • organodisilanes in particular disilanes (for example the high-boiling fraction from the distillation residue of ochow synthesis of .sup.4) and hydrogensilanes of the general formulas (2) and (3)
  • Dichlorodimethylsilane as a radical initiator are preferably at least 1% by weight, in particular at least 2% by weight and at most 15% by weight, in particular at most 10% by weight, based on the mixture of halohydrocarbon of the general formula (4) and hydrogensilanes used the general
  • diphenyldichlorosilane is prepared from dichlorosilane by reaction with chlorobenzene by the process according to the invention.
  • Dichlorosilane and trichlorosilane in proportions up to preferably not more than 50% other chlorosilanes from the Chlorsilansynthese starting from metallurgical silicon and hydrogen chloride, preferably tetrachlorosilane and methyldichlorosilane.
  • metal chlorides such as
  • the inventive method is preferably at
  • the inventive method is preferably in a
  • mixture of chlorobenzene, and dichlorosilane with trichlorosilane and free-radical initiator is preferably fed in vapor.
  • these are preferably the liquid
  • Components - which are either premixed in a mixing unit (static or active mixer) in the desired ratio or produced directly as a mixture in a process - by an evaporator and the vapors then by a Heat exchanger sent / thus with approximately
  • Reaction temperature enter the reactor zone.
  • Room temperature solid radical initiators are used in a preferred embodiment in the form of a solution in chlorobenzene.
  • the residence time of the reaction mixture in the reactor is preferably at least 2 seconds, in particular at least 5 seconds and at most 80 seconds, in particular at most 50 seconds,
  • Reaction mixture is preferably carried out after removal of the volatile constituents, in particular of the hydrogen halide formed in the reaction, by distillation or
  • the hydrogen halide formed is preferably bound in a scrubbing system and optionally neutralized or, more preferably, recycled
  • the process according to the invention is preferably carried out continuously. It can be e.g. to
  • Phenyldichlorosilane which isolated by distillation in a mixture with the educt mixture can be fed back into the reactor.
  • the materials in the components must be resistant to the
  • Reactor design (volume, pressure loss) can be variably set within limits and can be optimized from an economic point of view. For example, it may be useful to reduce the throughput and thus increase the residence time, if this is to achieve a better space-time yield. Conversely, this can result in undesirable reactions that can lead to the separation of solids in the reactor system.
  • Reactions are carried out at an ambient pressure of 0.10 MPa (abs.) And an ambient temperature of 20 ° C.
  • a quartz glass apparatus consisting of evaporator flask with an argon or nitrogen inlet valve, attached tube with heating mantle as reaction zone, bridge with cooling jacket, sampling flask for the condensable reaction products and Reactions of dichlorosilane and mixtures of trichlorosilane and dichlorosilane with chlorobenzene can be carried out under different conditions.
  • Evaporator flask is heated to 170 ° C, the cooling
  • Thermocouple determines which projects into the hot reaction zone.
  • the sample is taken from the sampling flask via the bottom valve by means of an evacuated sample vessel and analyzed by gas chromatography.
  • the quartz tube After inerting with argon, the quartz tube is brought to the desired temperature with an electric heater. From a storage container is the
  • Metered evaporator flask The liquid is metered at a rate such that the metered amount evaporates completely as soon as possible.
  • the metered amount evaporates completely as soon as possible.
  • Inertization 5 1 / h argon introduced.
  • the condensate collects after a few seconds in the sampling flask, Once a representative amount has accumulated, the dosage is interrupted and a sample of the liquid condensate taken under argon and in a
  • Reaction zone was 600 ° C, the residence time at 10 seconds, After half an hour, the dosage was terminated. About 40 g of yellowish condensate had collected in the receiver flask. According to gas chromatographic analysis, the condensate contained not only unreacted dichlorosilane (0.28%), trichlorosilane (4.11%) and chlorobenzene (68.9%).
  • Reaction zone was 650 ° C, the residence time at 10 seconds. After half an hour, the dosage was stopped. 37 g of yellowish condensate had collected in the receiver flask. According to gas chromatographic analysis, the condensate contained not only unreacted dichlorosilane (0.03%), trichlorosilane (1.22%) and chlorobenzene (60%).
  • Reaction zone was 600 ° C, the residence time at 8 seconds. After half an hour, the dosage was stopped. 48 g of yellowish condensate had collected in the receiver flask. According to gas chromatographic analysis, the condensate contained not only unreacted dichlorosilane (0.45%), trichlorosilane (5.29%) and chlorobenzene (68.4%).
  • Reaction zone was 600 ° C, the residence time at 8 seconds. After half an hour, the dosage was stopped. 48 g of yellowish condensate had collected in the receiver flask. According to gas chromatographic analysis, the condensate contained not only unreacted dichlorosilane (1.15%), trichlorosilane ⁇ 1.83% ⁇ and chlorobenzene (73.54%).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
EP10765648A 2009-10-28 2010-10-19 Verfahren zur herstellung von organosilanen Withdrawn EP2493900A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009046121A DE102009046121A1 (de) 2009-10-28 2009-10-28 Verfahren zur Herstellung von Organosilanen
PCT/EP2010/065668 WO2011051133A1 (de) 2009-10-28 2010-10-19 Verfahren zur herstellung von organosilanen

Publications (1)

Publication Number Publication Date
EP2493900A1 true EP2493900A1 (de) 2012-09-05

Family

ID=43333337

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10765648A Withdrawn EP2493900A1 (de) 2009-10-28 2010-10-19 Verfahren zur herstellung von organosilanen

Country Status (7)

Country Link
US (1) US20120296106A1 (ja)
EP (1) EP2493900A1 (ja)
JP (1) JP5426033B2 (ja)
KR (1) KR20120048036A (ja)
CN (1) CN102596971A (ja)
DE (1) DE102009046121A1 (ja)
WO (1) WO2011051133A1 (ja)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107206355B (zh) * 2015-02-06 2020-07-07 美国陶氏有机硅公司 制备有机卤代硅烷的方法
US9908903B2 (en) * 2015-02-06 2018-03-06 Dow Corning Corporation Method of producing organohalosilanes
CN112920214A (zh) * 2019-12-05 2021-06-08 新特能源股份有限公司 一种苯基氯硅烷、制备方法及装置

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04198186A (ja) * 1990-11-28 1992-07-17 Mitsui Toatsu Chem Inc 有機ケイ素化合物の製造方法
US5136071A (en) * 1991-12-16 1992-08-04 Dow Corning Corporation Sodium borohydride as activator for phenylborane catalyzed disproportionation of arylsilanes
KR100306574B1 (ko) * 1999-04-13 2001-09-13 박호군 탈할로겐화수소 반응으로 유기할로겐 화합물에 실란을 결합시키는 방법
US6251057B1 (en) * 1999-04-13 2001-06-26 Korea Institute Of Science And Technology Dehydrohalogenative coupling reaction of organic halides with silanes
JP2003212884A (ja) * 2002-01-24 2003-07-30 Toagosei Co Ltd フェニルシランの製造方法
JP2004284963A (ja) * 2003-03-19 2004-10-14 Asahi Glass Co Ltd 芳香族シラン化合物の製造方法
DE10349286A1 (de) * 2003-10-23 2005-05-25 Wacker-Chemie Gmbh Verfahren zur Herstellung von Organosilanen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011051133A1 *

Also Published As

Publication number Publication date
JP2013508433A (ja) 2013-03-07
US20120296106A1 (en) 2012-11-22
JP5426033B2 (ja) 2014-02-26
DE102009046121A1 (de) 2011-05-05
WO2011051133A1 (de) 2011-05-05
KR20120048036A (ko) 2012-05-14
CN102596971A (zh) 2012-07-18

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