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WO1993016085A1 - Procede de fabrication de tetraalcoxysilanes de couleur claire - Google Patents

Procede de fabrication de tetraalcoxysilanes de couleur claire Download PDF

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Publication number
WO1993016085A1
WO1993016085A1 PCT/EP1993/000208 EP9300208W WO9316085A1 WO 1993016085 A1 WO1993016085 A1 WO 1993016085A1 EP 9300208 W EP9300208 W EP 9300208W WO 9316085 A1 WO9316085 A1 WO 9316085A1
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WO
WIPO (PCT)
Prior art keywords
acidic
bleaching
tetraalkoxysilanes
tetramethoxy
carbon atoms
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.)
Ceased
Application number
PCT/EP1993/000208
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German (de)
English (en)
Inventor
Christian Block
Norbert Bialas
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1993016085A1 publication Critical patent/WO1993016085A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C07F7/04—Esters of silicic acids

Definitions

  • the invention is in the field of tetraalkoxysilanes and relates to a process for the preparation of light-colored tetraalkoxysilanes by transesterification of tetramethoxy- or ethoxysilanes with primary higher alcohols in the presence of basic catalysts and subsequent neutralization and bleaching using solid acidic bleaching earth and cation exchangers.
  • Tetraalkoxysilanes which are also called orthosilicic acid esters and correspond to the general formula Si (0R) 4, are known from the prior art.
  • US Pat. No. 2643263 describes silanes of branched alcohols having 8 to 14 carbon atoms, which are accessible either by reacting silicon tetrachloride or by transesterifying tetraethoxysilane with the corresponding higher alcohols.
  • the production via silicon tetrachloride has the disadvantage that the higher acidity of the reaction mixture leads to the undesired hydrolysis of the product.
  • the transesterification for the preparation of the tetraalkoxysilanes is preferred in principle. Since the transesterification is a sequence of VOB 4 equilibrium reactions, the use of catalysts is absolutely necessary. An overview of catalysts that can be used is given by H. Steinmann, G. Tschernko and H. Hamann, Z. Chem. Vol. 17, pages 89-92, 1977. Accordingly, both acids, such as hydrochloric acid, sulfuric acid and p-toluenesulfonic acid, and bases, such as alkali metal hydroxides or alcohols, can be used.
  • acids such as hydrochloric acid, sulfuric acid and p-toluenesulfonic acid
  • bases such as alkali metal hydroxides or alcohols
  • the object of the present invention was to develop a process which delivers light-colored tetraalkoxysilanes in as few process steps as possible.
  • the base-catalyzed transesterification known per se and the dark-colored tetraalkoxysilanes resulting therefrom should be assumed.
  • the processing of the tetraalkoxysilanes should deliver products that are as pure as possible in a short time.
  • the present invention relates to a process for the preparation of light-colored tetraalkoxysilanes by transesterification of tetramethoxy or tetraethoxysilanes with primary alcohols in the presence of basic catalysts, characterized in that a) tetramethoxy or tetraethoxysilanes with primary alcohols having 3 to 38 carbon atoms in molar amounts of 1: 4 to 1: 6 in the presence of 0.01 to 0.1 mol% of alcoholate - based on tetramethoxy or tetraethoxysilane - transesterified with constant removal of the methanol or ethanol formed and then the reaction mixture with b) solid acidic bleaching earth or solid acidic cation exchangers and acidic bleaching earth are added, mixed and filtered off.
  • Tetraethoxy and tetra ethoxysilane are commercially available products that are accessible from tetrachlorosilane and methanol or ethanol.
  • Suitable alcohols are aliphatic saturated and / or unsaturated alcohols, as can be obtained from natural oils and fats or after oxo synthesis, as are the Guerbet alcohols branched in the ⁇ -position, obtainable by the Guerbet process.
  • Suitable Guerbet alcohols are those with 12 to 38 carbon atoms, such as 2-n-butyl-n-octanol, 2-n-hepty-n-undecanol, 2-n-octyl-n-dodecanol and 2-n-dodecyl- n-hexadecanol.
  • the transesterification is preferably carried out in a molar ratio of tetra methoxy or tetraethoxysilane to the primary alcohols of 1: 4.2 to 1: 4.8.
  • Alkali salts of lower alcohols having 1 to 4 carbon atoms, preferably sodium methoxide, are preferably present as basic catalysts.
  • the catalysts and the amounts used correspond to the known prior art.
  • the tetramethoxy or ethoxysilanes, primary alcohols and the basic catalyst are heated together, the methanol and / or ethanol formed being removed continuously.
  • the transesterification is preferably carried out at temperatures in the range from 80 to 250 ° C., with slow heating at a constant temperature heating rate, in particular from 0.1 to 5 ° C. per minute, being recommended.
  • the reaction is preferably carried out until - in relation to the amount of methanol or affiliated abdesti Eth 'anol - an environmental of esterification of 50 to 100%, preferably 85 to 95% is achieved.
  • the degree of esterification is a percentage which results from the quotient of the actual amount of alcohol distilled off and the theoretically achievable amount of alcohol.
  • the tetraalkoxysilanes resulting from the transesterification are dark brown products that have to be worked up.
  • the workup includes both the neutralization of the bakery alcoholate catalyst present in the reaction mixture and the bleaching.
  • Solid acidic bleaching earths or solid acidic cation exchangers can be used for neutralization.
  • the term acidic bleaching earth in the sense of the invention encompasses both the activation of the bleaching earth with acids and the fact that the aqueous suspensions of the bleaching earth have a pH below 6.
  • Acidic bleaching earths are particularly preferred which, as an aqueous suspension, have a pH between 1 and 4, since they have a higher exchange capacity for neutralization.
  • Suitable solid acidic bleaching earths are, for example, specially prepared bleaching earths of the montmorillonite type, such as those from Süd-Chemie AG, Kunststoff under the name K catalysts, for example KP 10, KSF, KSF / 0, KA / 0 or under the name Tonsil, for example Tonsil COG, Tonsil Optimum FF, Tonsil Standard, Tonsil Supreme or Tonsil ACC.
  • K catalysts for example KP 10, KSF, KSF / 0, KA / 0
  • Tonsil for example Tonsil COG, Tonsil Optimum FF, Tonsil Standard, Tonsil Supreme or Tonsil ACC.
  • Acidic cation exchangers based on synthetic resin ion exchangers are also very suitable. These products represent highly polymeric spatial networks made of carbon chains in a gel structure, which contain -S03 "groups or SO3 ⁇ and --0" groups as charge-carrying groups.
  • these are cation exchangers based on polystyrene sulfonic acid resins or phenolsulfonic acid resins, which are known, for example, under the following trade names: Lewatit S10 ⁇ ( R ), Lewatit SC 102 ( R ), Lewatit SC 108 ( R ), Lewatit SPC 118 ( R ), Lewatit SP 108 ⁇ ( R ), Lewatit SP 12 ⁇ ( R ), Lewatit S 115 ( R ), Amberlite IR 12 ⁇ ( R ), Amberlite IR 20 ⁇ ( R ), A berlyst l ⁇ ( R ) ( Permutit RS 12 ⁇ ( R ), Per utit RSP 12 ⁇ ( R ), Dowex 5 ⁇ ( R ), Wofatit F ( R ), Wofatit F ( R ), Wofatit D ( R ), Wofatit KPS 20 ⁇ ( R ), Duolite C-3 ( R ), Duolite C-l ⁇ ( R ), Duolite C-
  • the acidic bleaching earths and cation exchangers are preferably used free of water or with the smallest possible amount of water. This is not a problem for acidic bleaching earths, since they are commercially available as a solid with only a small amount of water. In contrast, the acidic cation exchangers of the type described must be swollen with water in order to activate the exchange capacity. The water not required for hydration can now be minimized by drying after swelling.
  • the amount of acidic bleaching earth or cation exchanger required depends strongly on their (proton) capacity for the exchange and the amount of alcoholate used. Random checks of the pH value quickly reveal the quantities required.
  • the amount is preferably for neutralization per mole of alcoholate in the range of 2 to 3 kg of the acid bleaching earth Tonsil or 0.8 to 3 kg of acidic cation exchanger.
  • the acidic bleaching earths described must also be added for bleaching, preferably in amounts of 1 to 10% by weight, based on the reaction mixture.
  • treatment with activated carbon can be carried out in a known manner.
  • the treatment with the solid bleaching earth or the cation exchangers is carried out by adding them alone or in a mixture or in succession to the reaction mixture and mixing them together for at least 30 minutes, preferably 1 to 2 hours, and then filtering them off.
  • the dark brown reaction mixture cooled to 50 ° C., is mixed with 20 g of acidic bleaching earth (Tonsil R COG 15/30 esh from Südchemie) and with 1 g of activated carbon and stirred for 2 hours at 70 ° C. in a water jet vacuum.
  • Example 2 Analogously to Example 2, 22.8 g (0.15 mol) of tetramethoxysilane and 0.135 g of sodium methoxide (as a methanol solution) were added to 164 g of the technical 2-hexyl decanol. The reaction mixture was treated with 9 g of the acid bleaching clay Tonsil COG 15/30 mesh; Südchemie, offset and worked up analogously to Example 1.
  • Table 1 shows whether neutralization was achieved under the specified conditions and the color of the product. % By weight relate to crude product. Table 1 Neutralization and color

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention a trait au domaine des tétraalcoxysilanes et concerne un procédé de fabrication de tétraalcoxysilanes par transestérification de tétraméthoxy- ou éthoxysilanes avec des alcools primaires supérieurs en présence de catalyseurs basiques, puis par neutralisation et décoloration au moyen de terres décolorantes acides compactes et d'échangeurs de cations.
PCT/EP1993/000208 1992-02-06 1993-01-29 Procede de fabrication de tetraalcoxysilanes de couleur claire Ceased WO1993016085A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4203352.7 1992-02-06
DE4203352A DE4203352A1 (de) 1992-02-06 1992-02-06 Verfahren zur herstellung von hellfarbigen tetraalkoxysilanen

Publications (1)

Publication Number Publication Date
WO1993016085A1 true WO1993016085A1 (fr) 1993-08-19

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ID=6451051

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/000208 Ceased WO1993016085A1 (fr) 1992-02-06 1993-01-29 Procede de fabrication de tetraalcoxysilanes de couleur claire

Country Status (2)

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DE (1) DE4203352A1 (fr)
WO (1) WO1993016085A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998003514A1 (fr) * 1996-07-23 1998-01-29 Wacker-Chemie Gmbh Procede de preparation d'alcoxysilanes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2643263A (en) * 1950-09-22 1953-06-23 California Research Corp Higher secondary-alkyl orthosilicates
US2814634A (en) * 1952-10-16 1957-11-26 Pierce John B Foundation Process of making silicates
EP0223210A2 (fr) * 1985-11-14 1987-05-27 Toray Silicone Co., Ltd. Méthode de purification d'alcoxysilanes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2643263A (en) * 1950-09-22 1953-06-23 California Research Corp Higher secondary-alkyl orthosilicates
US2814634A (en) * 1952-10-16 1957-11-26 Pierce John B Foundation Process of making silicates
EP0223210A2 (fr) * 1985-11-14 1987-05-27 Toray Silicone Co., Ltd. Méthode de purification d'alcoxysilanes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN Bd. 61, Nr. 11, 1988, Seiten 4087 - 4092 HASEGAWA, I. ET AL. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998003514A1 (fr) * 1996-07-23 1998-01-29 Wacker-Chemie Gmbh Procede de preparation d'alcoxysilanes
US6005132A (en) * 1996-07-23 1999-12-21 Wacker-Chemie Gmbh Method of preparing alkoxy silanes
JP3204987B2 (ja) 1996-07-23 2001-09-04 ワツカー―ケミー ゲゼルシヤフト ミツト ベシユレンクテル ハフツング アルコキシシランの製法

Also Published As

Publication number Publication date
DE4203352A1 (de) 1993-08-12

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