WO2015116281A1 - Procédé d'halogénation - Google Patents

Procédé d'halogénation Download PDF

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Publication number
WO2015116281A1
WO2015116281A1 PCT/US2014/064463 US2014064463W WO2015116281A1 WO 2015116281 A1 WO2015116281 A1 WO 2015116281A1 US 2014064463 W US2014064463 W US 2014064463W WO 2015116281 A1 WO2015116281 A1 WO 2015116281A1
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Prior art keywords
formula
ingredient
alternatively
reaction product
scavenging agent
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PCT/US2014/064463
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English (en)
Inventor
Dimitris Katsoulis
John Roberts
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Dow Silicones Corp
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Dow Corning Corp
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    • 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
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes

Definitions

  • Diorganodihalosilanes such as dimethyldichlorosilane
  • halosilanes are produced commercially by the Mueller-Rochow Direct Process, which comprises passing a halide compound over zero-valent silicon (Si 0 ) in the presence of a copper catalyst and various optional promoters. Mixtures of halosilanes are produced by the Direct Process. When an organohalide is used, a mixture of organohalosilanes is produced by the Direct Process.
  • the typical process for making the Si 0 used in the Direct Process consists of the carbothermic reduction of S1O2 in an electric arc furnace. Extremely high temperatures are required to reduce the S1O2, so the process is energy intensive. Consequently, production of Si 0 adds costs to the Direct Process for producing halosilanes. Therefore, there is a need for a more economical method of producing halosilanes that avoids or reduces the need of using Si 0 .
  • diorganodihalosilanes have been produced by the alkylation of silicon tetrachloride and various methylchlorosilanes by passing the vapors of these chlorosilanes together with an alkyl halide over finely divided aluminum or zinc at elevated temperatures.
  • this process results in the production of a large amount of aluminum chloride or zinc chloride, which is costly to dispose of on a commercial scale.
  • tetrahalides such as SiCl4.
  • a method for preparing a reaction product comprises:
  • formula iii) is R 2 -C ⁇ N, where R 2 is an organic group, and
  • the method for preparing a reaction product comprises:
  • M(OR 1 ) x a compound of formula ii): M(OR 1 ) x , or an oligomer thereof, where M is an element selected from the group consisting of Sn, Ge, and Si, each R 1 is independently a monovalent hydrocarbon group, and subscript x has a value from 1 to maximum value of the element selected for M;
  • reaction product comprises a halogenated compound and a side product.
  • the method may optionally further comprise
  • the method may optionally further comprise 3) recovering the scavenging agent.
  • the method may optionally further comprise 4) recycling the recovered scavenging agent in step 1 ).
  • Ingredient a) used in the method is a hydrogen halide of formula i): HX, where X is a halogen atom.
  • X may be fluorine (F), chlorine (CI), bromine (Br), or iodine (I);
  • Ingredient a) is exemplified by HBr and HCI; alternatively HCI.
  • Hydrogen halides are known in the art and are commercially available, for example, from Sigma-Aldrich, Inc., of St. Louis, MO, U.S.A. (Aldrich).
  • the amount of hydrogen halide depends on various factors including the type of reactor used and the compound selected for ingredient b), however the amount of hydrogen halide may be sufficient to provide a mole ratio of ingredient a) to ingredient b) (a:b ratio) of >1 :1 , alternatively 1 :1 to 50:1 , alternatively 2:1 to 25:1 , and alternatively 4:1 to 16:1 .
  • Ingredient b) used in the method is a compound of formula ii): M(OR 1 ) x , or an oligomer thereof, where M is tin (Sn), germanium (Ge), or silicon (Si); each R 1 is independently a monovalent hydrocarbon group; and subscript x has a value from 1 to the maximum valence of the element selected for M.
  • M tin
  • Ge germanium
  • Si silicon
  • each R 1 is independently a monovalent hydrocarbon group
  • subscript x has a value from 1 to the maximum valence of the element selected for M.
  • x when M is Si, x can be 1 to 4.
  • x 4.
  • M Ge
  • x can be 1 to 4.
  • M Sn
  • M is Ge or Si.
  • M is Si.
  • the monovalent hydrocarbon group for R 1 may be an alkyl group, an alkenyl group, or an alkynyl group. Alternatively, R 1 may be an alkyl group. Alternatively, R 1 may be an alkyl group of 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms. Alternatively, R 1 may be
  • M is Si
  • x is 4, and R 1 is alkyl of 1 to 4 carbon atoms.
  • Compounds of formula ii) and oligomers thereof are known in the art and may be prepared, for example, as described in U.S. Patent 5,183,914 to Yeh, et al. Examples of compounds of formula ii) include Sn(OMe)2, Ge(OMe)4, Si(OMe)4, and Si(OEt)4. Alternatively, the compound of formula ii) may be an orthosilicate such as tetramethoxysilane or tetraethoxysilane.
  • oligomers include silicone oligomers of formula: R 1 0)3Si-0-Si(OR 1 )3, and/or formula:
  • R 1 is alkyl, such as Me or
  • Ingredient c) used in the method is a scavenging agent that can remove R 1 OH, which is produced as a side product of the reaction of ingredients a) and b), from the reaction mixture.
  • Ingredient c) may be a nitrile-functional compound of formula iii): R 2 -C ⁇ N, where R 2 is an organic group.
  • R 2 may be a hydrocarbon group, such as an alkyl group or an alkenyl group of 1 to 10 carbon atoms, alternatively 1 to 6 carbon atoms, and alternatively 1 to 4 carbon atoms.
  • nitrile-functional compounds suitable for ingredient c) include acetonitrile, propionitrile, trimethyl acetonitrile, hexanenitrile, 5- hexynenitrile.
  • Suitable nitrile-functional compounds are known in the art and are commercially available from Aldrich.
  • R 3 may be a hydrocarbon group, such as an alkyl group or an alkenyl group, of 1 to 10 carbon atoms, alternatively 1 to 6 carbon atoms, and alternatively 1 to 4 carbon atoms.
  • isocyanate functional compounds suitable for ingredient c) include methyl isocyanate, ethyl isocyanate, butyl isocyanate, 3-methyl-2-butyl isocyanate, hexyl isocyanate, 2-heptyl isocyanate, 2-octyl isocyanate, and allyl isocyanate.
  • Suitable isocyanate functional compounds are known in the art and are commercially available from Aldrich.
  • ingredient c) may be selected from acetonitrile and ethyl isocyanate.
  • the amount of ingredient c) depends on various factors including the reactivity of the scavenger selected as ingredient c) and the compound selected for ingredient b), however the amount of ingredient c) may be sufficient to provide a mole ratio of ingredient c) to ingredient b) (c:b ratio) of >1 :1 , alternatively 1 :1 to 50:1 , alternatively 2:1 to 25:1 , and alternatively 4:1 to 16:1 .
  • Ingredient d) used in the method is a catalyst that catalyzes the reaction of ingredients a) and b).
  • Ingredient d) may be a Lewis acid or a Lewis base.
  • Suitable Lewis acids for ingredient d) may be metal halides, such as metal chlorides and metal bromides, or metal triflates.
  • the Lewis acid may be a metal chloride selected from FeCl3, ZnCl2 and LiCI; alternatively the Lewis acid may be FeC ⁇ .
  • Suitable Lewis bases for ingredient d) include pyridines, tertiary amines, phosphines, phosphine oxides, sulfoxides, or combinations thereof.
  • An exemplary Lewis base includes hexamethyl phosphoramide (HMPA).
  • the amount of ingredient d) depends on various factors including the type of catalyst selected for ingredient d) and the reactivity of ingredients a) and b), however the amount of ingredient d) may be 10 mol% to 1 mol% based on the amount of ingredient b).
  • ingredients a) and b) react to form the halogenated compound of average formula M(OR 1 )(4 -y )Xy.
  • M, R 1 and X are as described above, and subscript y is 1 to 4.
  • the reaction of ingredients a) and b) also produces a side product.
  • the side product includes R 1 OH.
  • Ingredient c) is a scavenging agent that reacts with R 1 OH.
  • reaction product may have a mixture of compounds, e.g., when the maximum valence of M is 4, the reaction product includes one or more of
  • the method is preferably performed under conditions so as to maximize the amount of MX y .
  • the halogenated compound include SiCI 3 (OMe), SiCI 3 (OMe) 2 , SiCI 3 (OMe) 3 , and SiCI 4 .
  • One object of the present invention is to produce a reaction product comprising S1CI4, when M is Si.
  • the fully halogenated compound e.g., S1CI4, when M is Si and X is CI
  • partially chlorinated compounds e.g., SiCI(OMe) 3 , SiCl2(OMe)2, and/or
  • Step 1 ) of the method is performed under conditions that form the reaction product comprising the halogenated compound and the side product.
  • Step 1 ) may be performed at a temperature less than room temperature (RT) of 25 to the freezing temperature of the compound selected for c).
  • step 1 ) may be performed at 20 °C to -40 °C, alternatively 15 °C to -30 °C, alternatively 10 °C to -15 °C alternatively 0 °C.
  • Step 1 may be performed at ambient pressure, or above ambient pressure.
  • the pressure may range from 0 kPag to 413.8 kPag, alternatively 0 kPag to 206.7 kPag.
  • step 1 may be selected so as to optimize solubility of ingredient a) in the reaction mixture with ingredients b), c) and d). It is thought that temperatures lower than RT and pressures above atmospheric pressure may optimize solubility of ingredient a). It was surprisingly found that solvents, both polar and nonpolar, may negatively impact conversion in step 1 ). Therefore, step 1 ) may be performed neat; in the absence of polar solvents and in the absence of nonpolar solvents.
  • the method may optionally further comprise 2) recovering the halogenated compound.
  • solid and liquid components in the reaction mixture may be separated by any convenient means, such as filtration.
  • the halogenated compound may be removed from the liquid components of the reaction mixture by conventional techniques such as stripping and/or distillation.
  • the method may optionally further comprise 3) recovering the scavenging agent.
  • the scavenging agent may be recovered by precipitating the salt thereof from solution using conventional techniques, such as adding an acid, concentrating the reaction mixture via stripping and/or distillation, or dropping the temperature of the reaction mixture.
  • a non-polar solvent may be used to cause the scavenging agent to precipitate from solution.
  • the salt may then be converted to re-form the scavenging agent (e.g., to MeCN) and by-products (e.g., MeOH and HCI) in the following sequence.
  • an imidate salt when it is present, it can be removed from the reaction mixture by conventional techniques, such as filtration. Once removed from the reaction mixture, the imidate salt can be hydrolyzed to MeOH, HCI, and acetamide by addition of water to the imidate salt.
  • the HCI and MeOH can be removed and separated by stripping and/or distillation, and the acetamide can be recycled to MeCN by conventional techniques, such as dehydration over metal oxide catalysts.
  • the method may optionally further comprise 4) recycling the recovered scavenging agent in step 1 ).
  • the recovered scavenging agent from step 3) may be recycled in step 1 ).
  • FeCl3 was anhydrous, > 99% iron trichloride from Aldrich, HMPA was 99% hexamethyl phosphoramide from Aldrich, CH3CN was 95% acetonitrile from Aldrich, 95%, SiEt4 was 99% tetraethylsilane from Gelest, Sn(OMe)2 was 99% tin dimethoxide from Alfa
  • Aesar, Ge(OMe)4 was 99% germanium tetramethoxide from Aldrich, CDCI3 was deuterated chloroform, and HCI was 99% Hydrogen Chloride from Aldrich. All materials were used as received.
  • FeCl3 (1 .37g, 8.45 mmol) was added to a stirred solution of Si(OMe)4 (25 ml, 169 mmol) and toluene (75 ml). The solution was warmed to 130°C and then a stream of HCI (40 seem) was sparged through the solution and through a Dean-Stark trap. The resulting reaction mixture was stirred for three hours. A biphasic mixture began to form in the Dean- Stark trap. The more dense layer was shown to be a mixture of methanol and Si(OMe)4.
  • HMPA HMPA (0.48 ml, 2.73 mmol) was added to a stirred solution of Sn(OMe)2 (5 g, 27.35 mmol) and acetonitrile (23.4 ml, 437.6 mmol). The reaction mixture was cooled to 0°C and then HCI gas (25 seem) was sparged through the reaction mixture. The reaction mixture was stirred in this manner for 6 hours. After 3 hours SnCl4 was the only observed
  • HMPA (0.48 ml, 2.73 mmol) was added to a stirred solution of Ge(OMe)4 (4.06,
  • HMPA HMPA (0.38 ml, 2.2mmol) was added to a stirred solution of Si(OMe)4 (22 ml, 22 mmol) and ethyl isocyanate (25g ml, 351 .7 mmol).
  • the reaction mixture was cooled to 0 °C and then HCI gas (25 seem) was sparged through the reaction mixture.
  • the reaction mixture was stirred in this manner for 6 hours. After 6 hours the contents of the cold trap were re-introduced to the reactor and an internal standard (SiEt.4, 1 ml, 5.29 mmol) was added. An aliquot was taken, diluted with CDCI3, and 29 Si and 3 C NMR were immediately taken.
  • the reaction product contained 14 mole % of S1CI4, along with 57 mole % of SiCl3(OMe) and 14 mole % of SiCl2(OMe)2.
  • ranges includes the range itself and also anything subsumed therein, as well as endpoints.
  • disclosure of a range of 2.0 to 4.0 includes not only the range of 2.0 to 4.0, but also 2.1 , 2.3, 3.4, 3.5, and 4.0 individually, as well as any other number subsumed in the range.
  • disclosure of a range of, for example, 2.0 to 4.0 includes the subsets of, for example, 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7, and 3.8 to 4.0, as well as any other subset subsumed in the range.
  • any Markush groups relied upon herein for describing particular features or aspects of various embodiments, it is to be appreciated that different, special, and/or unexpected results may be obtained from each member of the respective Markush group independent from all other Markush members.
  • Each member of a Markush group may be relied upon individually and or in combination with any other member or members of the group, and each member provides adequate support for specific embodiments within the scope of the appended claims.
  • disclosure of the Markush group: alkyl, aryl, and carbocyclic includes the member alkyl individually; the subgroup alkyl and aryl; and any other individual member and subgroup subsumed therein.
  • any ranges and subranges relied upon in describing various embodiments of the present disclosure independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein.
  • the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present disclosure, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on.
  • a range "of 20 to -40" may be further delineated into a lower third, i.e., from -20 to 0, a middle third, i.e., from 0 to +20, and an upper third, i.e., from +20 to +40, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims.
  • a range such as "at least,” “greater than,” “less than,” “no more than,” and the like, it is to be understood that such language includes subranges and/or an upper or lower limit.
  • a range of "at least 0.1 %” inherently includes a subrange from 0.1 % to 35%, a subrange from 10% to 25%, a subrange from 23% to 30%, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims.
  • an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims.
  • a range of "1 to 6" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1 , which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.
  • a method for preparing a reaction product comprises: 1 ) reacting a composition comprising
  • M(OR 1 ) x a compound of average formula ii): M(OR 1 ) x , or an oligomer thereof, where M is an element selected from Sn, Ge, or Si, and each R 1 is independently a monovalent hydrocarbon group, and subscript x has a value from 1 to maximum valence of the element selected for M;
  • formula iii) is R 2 -C ⁇ N, where R 2 is an organic group, and
  • reaction product comprises a halogenated compound and a side product.
  • step 1 is performed neat.
  • ingredient a) used in the first embodiment comprises HCI.
  • ingredient b) used in the fourth embodiment comprises an orthosilicate.
  • ingredient c) used in the first embodiment comprises acetonitrile or ethyl isocyanate.
  • ingredient d) used in the first embodiment comprises a Lewis acid.
  • the Lewis acid of the seventh embodiment is selected from selected from FeCkj, ZnCl2 and LiCI.
  • ingredient d) used in the first embodiment comprises a Lewis base.
  • the Lewis base used in the ninth embodiment comprises hexamethyl phosphoramide.
  • step 1 ) in the first embodiment is performed at a temperature from 20 °C to -40 °C.
  • step 1 ) in the first embodiment is performed at a pressure from 0 kPag to 206.7 kPag.
  • the method of the first embodiment further comprises step 2), recovering the halogenated compound.
  • the halogenated compound produced in the first embodiment comprises a halosilane.
  • the halosilane of the fourteenth embodiment comprises S1CI4.
  • the method of the first embodiment further comprises 3) recovering the scavenging agent.
  • the method of the first embodiment further comprises 4) recycling the scavenging agent recovered in step 3) in step 1 ).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)

Abstract

Cette invention concerne un procédé de préparation d'un produit réactionnel comprenant a) un halogénure d'hydrogène de formule i) : HX, où X est un atome d'halogène, et b) un composé de formule moyenne ii) : M(OR1 )x, ou un oligomère de celui-ci, où M est un élément choisi parmi Sn, Ge, ou Si, et chaque R1 est indépendamment un groupe hydrocarbure monovalent, et l'indice x a une valeur variant de 1 à la valence maximale de l'élément choisi pour M; en présence de c) un agent piégeur de formule iii) ou de formule iv), où formule iii) est R2-CEN, R2 étant un groupe organique, et formule iv) est O=C=N-R3, R3 étant un groupe organique, et d) un catalyseur. Le produit réactionnel contient un composé halogéné et un sous-produit.
PCT/US2014/064463 2014-01-30 2014-11-07 Procédé d'halogénation Ceased WO2015116281A1 (fr)

Applications Claiming Priority (2)

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US201461933418P 2014-01-30 2014-01-30
US61/933,418 2014-01-30

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WO2015116281A1 true WO2015116281A1 (fr) 2015-08-06

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4448981A (en) * 1983-05-13 1984-05-15 General Electric Company Method of making organosiloxanes and alkyl halides from dialkyldialkoxysilanes
US6069220A (en) * 1998-01-02 2000-05-30 Huels Silicone Gmbh Continuous method for producing polyorganosiloxanes
US20120261269A1 (en) * 2009-12-22 2012-10-18 Wataru Kagohashi Process for production of polysilicon and silicon tetrachloride
EP2639236A1 (fr) * 2012-03-15 2013-09-18 Dow Corning Corporation Procédés alternatifs pour la synthèse de composés d'organosilicone

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4448981A (en) * 1983-05-13 1984-05-15 General Electric Company Method of making organosiloxanes and alkyl halides from dialkyldialkoxysilanes
US6069220A (en) * 1998-01-02 2000-05-30 Huels Silicone Gmbh Continuous method for producing polyorganosiloxanes
US20120261269A1 (en) * 2009-12-22 2012-10-18 Wataru Kagohashi Process for production of polysilicon and silicon tetrachloride
EP2639236A1 (fr) * 2012-03-15 2013-09-18 Dow Corning Corporation Procédés alternatifs pour la synthèse de composés d'organosilicone

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MASAOKA, SHIN ET AL.: "The synthesis of chlorosilanes from alkoxysilanes, silanols and hydrosilanes with bulky substituents", JOURNAL OF ORGANOMETALLI CHEMISTRY, vol. 691, no. 1-2, 2006, pages 174 - 181, XP028047992 *

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