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WO1992011266A1 - Silanes tetraalcoxiliques, leur procede de production et leur utilisation - Google Patents

Silanes tetraalcoxiliques, leur procede de production et leur utilisation Download PDF

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Publication number
WO1992011266A1
WO1992011266A1 PCT/EP1991/002426 EP9102426W WO9211266A1 WO 1992011266 A1 WO1992011266 A1 WO 1992011266A1 EP 9102426 W EP9102426 W EP 9102426W WO 9211266 A1 WO9211266 A1 WO 9211266A1
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WO
WIPO (PCT)
Prior art keywords
transesterification
general formula
tetramethoxy
double
hydrotalcite
Prior art date
Application number
PCT/EP1991/002426
Other languages
German (de)
English (en)
Inventor
Christian Block
Wolfgang Breuer
Helmut Endres
Johannes Hachgenei
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1992011266A1 publication Critical patent/WO1992011266A1/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/04Esters of silicic acids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D19/00Degasification of liquids
    • B01D19/02Foam dispersion or prevention
    • B01D19/04Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0409Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585Organosilicon compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49Esterification or transesterification

Definitions

  • the invention relates to tetraalkoxysilanes from Guerbet alcohols, a process for the preparation of light-colored tetraalkoxysilanes of the general formula Si (0R . 4 by transesterification of tetramethoxy or tetraethoxysilane with an alcohol in the presence of catalytic amounts of at least one double-layer hydroxide compound with continuous removal of methanol or ethanol, and the like Use of the light-colored tetraalkoxysilanes as cosmetic ingredients, cooling lubricants, hydraulic fluids, heat transfer fluids or defoamers.
  • Tetraalkoxysilanes of the general formula Si (0R) 4 which are also referred to as silica tetraesters, are derived from long-chain fatty alcohols and are known, for example, as textile treatment agents.
  • silicic acid esters of unsaturated straight-chain fatty alcohols give textiles a soft feel.
  • textile materials that have been treated with these silicic acid esters at higher temperatures show a yellowing that is unacceptable for light textiles.
  • Oxo alcohols of this type are essentially saturated and also have 35 to 65% by weight, branched alcohols such as 2-methylundecanol, 2-n-octyldecanol and 2-n-hexyltridecanol. Despite the high proportion of branched alcohols, the hydrolysis stability of their aqueous ones Emulsions are not sufficient if the emulsion is still free
  • a further disadvantage is that, owing to the production process, the tetraalkoxysilanes can already have their own color or that corrosive hydrochloric acid is produced in the production process.
  • the tetraalkoxysilanes can be prepared either by direct alcoholysis of tetrachlorosilane or by transesterification of tetramethoxy or tetraethoxysilane with the corresponding alcohols.
  • the transesterification reactions of alkoxysilanes with alcohols have been known in the art for some time (see, for example, in H. Steinmann, G. Tschernko and H. Hamann, Z. Che. Vol. 17, pp. 89-92, 1977).
  • Transesterification catalysts have hitherto generally been used both acids, such as hydrogen chloride, hydrogen fluoride, sulfuric acid, trifluoroacetic acid or p-toluenesulfonic acid, and bases, such as alkali metal hydroxides, methanolates or ethanolates.
  • acids such as hydrogen chloride, hydrogen fluoride, sulfuric acid, trifluoroacetic acid or p-toluenesulfonic acid
  • bases such as alkali metal hydroxides, methanolates or ethanolates.
  • bases such as alkali metal hydroxides, methanolates or ethanolates.
  • tetraalkoxysilanes can no longer be purified from higher alcohols with a chain length of more than 12 carbon atoms by distillation.
  • the basic catalyst must first be neutralized and then the salt formed must be separated off, which means an additional process step.
  • the object of the present invention was to provide a new process for the preparation of tetraalkoxysilanes by transesterification of the easily accessible tetramethoxysilane or tetraethoxysilanes with higher alcohols, which, using a suitable catalyst, had the shortest possible reaction times with a high degree of esterification leads to high-purity, light-colored tetraalkoxysilanes.
  • Another object of the present invention was to provide tetraalkoxysilanes which show improved hydrolysis stabilities.
  • the present invention accordingly relates to a process for the preparation of light-colored tetraalkoxysilanes of the general formula Si (0R) 4, in which R represents a straight-chain and / or branched-chain, saturated and / or unsaturated, aliphatic hydrocarbon radical, by transesterification of Tetramethoxy or tetraethoxysilane with at least one alcohol in the presence of a catalyst, characterized in that the transesterification at temperatures of 80 to 250 ° C in the presence of at least one double-layer hydroxide compound of the general formula
  • B represents an equivalent of an inorganic anion, from the group formed by carbonate, hydrogen carbonate, sulfate, nitrate, nitrite, phosphate, hydroxide and halides, and in which the conditions 0.1 _ x _ 0.5, 0 ⁇ a ⁇ 0.5, 0 _ b _ 0.5, 0 ⁇ a + b _ 0.5 and 0 _ z _ 10 are considered to be heterogeneous catalysts and the methanol or ethanol is continuously removed from the reaction mixture.
  • the divalent metal cation of the formula (I) is preferably selected from magnesium, calcium, manganese, zinc and copper.
  • the trivalent metal cation of formula (I) is preferably selected from iron and aluminum. If the above - in connection with the explanation of the general formula (I) - is spoken of at least one divalent and trivalent metal cation, this means that in such double-layer hydroxide compounds there may be several divalent or trivalent metal cations next to each other can be present.
  • Double-layer hydroxide compounds Two-dimensional inorganic polycations with intra-crystalline charge balancing by means of movable interlayer anions are also known under the name “double-layer hydroxide compounds” and have been described several times in the literature. Is referred to, for. B. on R. Allmann, "Double-layer structures with brucite-like layered ions", Chimia 24, 99 to 108 (1970). Chemical pose these compounds are mixed hydroxy salts of 2- and 3-valent metal ions and can be characterized by the general formula II:
  • hydrotalcite which occurs as a mineral in nature.
  • hydrotalcites which are described, for example, in DE-C-1 592 126, DE-A-3 346 943, DE-A-3 306 822 and EP-A-207 811.
  • Hydrotalcite is a natural mineral with the ideal formula [Mg6Al 2 (0H) i5] C03.4H 2 0, whose structure is derived from that of brucite (Mg (0H) 2 ).
  • Brucite crystallizes in a layer structure with the metal ions in octahedral gaps between two layers of densely packed hydroxyl ions, only every second layer of the octahedral gaps being occupied.
  • some magnesium ions are replaced by aluminum ions, which means that the shift package receives a positive charge. This is compensated for by the anions which are located in the intermediate layers together with zeolitic crystal water.
  • calcined double-layer hydroxide compounds of the general formula (I) can also be used in the process according to the invention.
  • the calcined compounds of the general formula (I) are obtained by heating or calcining by continuously releasing water. In general, the crystal water is completely released at temperatures around 200 ° C. A further increase in temperature leads both to the elimination of water from the hydroxide structure and of carbon dioxide from the carbonate which is usually present as a counter anion.
  • a prototype of such compounds is the calcined hydrotalcite, of which, for example from DE-A-30 19 632, the anion reuptake is known, with reformation of the layer structure.
  • the double-layer hydroxide compounds of the general formula (I) used can be the hydrophobic double-layer hydroxide compounds described in the not yet published German patent applications P 40 10 606.3 and P 40 34 305.7 of the applicant.
  • the hydrophobic double-layer hydroxide compounds are reacted in a low-boiling organic solvent, preferably alcohols with 1 to 6 carbon atoms, open-chain and cyclic ethers and / or ketones, by reacting monocarboxylic acids and / or dicarboxylic acids with double-layer hydroxide.
  • a low-boiling organic solvent preferably alcohols with 1 to 6 carbon atoms, open-chain and cyclic ethers and / or ketones
  • the hydrophobization is particularly preferably carried out in isopropanol, diethyl ether, tetrahydrofuran and / or acetone.
  • hydrophobicized double-layer hydroxide compounds of the general formula I can also be obtained by direct reaction of double-layer hydroxide compounds of the general formula II with mono- and / or dicarboxylic acids without the addition of a solvent using any stirring tool, preferably a kneader.
  • the compounds of the general formula I can also be analogous to the process known from the teaching of DE-A-3731 919 by reacting double-layer hydroxide compounds with an aqueous suspension of an alkali metal and / or alkaline earth metal salt, preferably sodium salts Produce mono- and / or dicarboxylic acid.
  • hydrophobicized double layer hydroxide compounds can also be obtained from calcined double layer hydroxide compounds by reacting them with the mono- or dicarboxylic acids be preserved; carbonate-free or carbonate-containing products can be obtained with the exclusion of air or COg or in the presence of carbon dioxide.
  • the stoichiometric water content of the hydrophobic double-layer hydroxide compounds can - depending on the type of production and the drying conditions - be in the range from 0 to 10 molecules; a range from 0 to 4 molecules is preferred, which is generally obtained if the hydrophobic double-layer hydroxide compounds are dried to constant weight at temperatures in the range from 100 to 250 ° C., preferably from 150 to 220 ° C., so that a particularly high catalytic activity can be guaranteed.
  • compounds derived from hydrotalcite are used as double-layer hydroxide compounds of the general formula I.
  • the reaction mixture containing tetramethoxy or tetraethoxysilane, at least one alcohol and at least one catalyst of the general formula (I) is raised to 80 at a temperature of from 2 to 5 ° C. per minute to 140 ° C, preferably 110 to 130 ° C, heated and then with continuous removal of the methanol or ethanol formed at a reduced temperature heating rate of 0.1 to 2 ° C, preferably 0.3 to 1 ° C, per minute to 150 to 250 ° C, preferably 180 to 200 ° C, heated.
  • the transesterification is carried out in such a way that, based on the amount of methanol or ethanol distilled off, a degree of transesterification of 50 to 99%, preferably 85 to 95%, is achieved.
  • the degree of transesterification is understood to mean a percentage which results from the quotient of the amount of alcohol actually distilled off and the amount of alcohol which can theoretically be achieved with quantitative conversion.
  • the transesterification of tetramethoxy or tetraethoxysilane with the corresponding alcohol is carried out in a molar ratio of 1: 4 to 1:10, preferably 1: 4.5 to 1: 6.
  • a slight excess of alcohol is therefore preferred, which is either removed together with the methanol or ethanol in the course of the distillative separation or is separated off in a separate distillation step.
  • straight and / or branched-chain, saturated and / or unsaturated, aliphatic alcohols having 3 to 32 carbon atoms can be used for the transesterification according to the invention.
  • propanol, butanol, fatty alcohols having 6 to 32 carbon atoms and mixtures of these compounds are to be mentioned here.
  • Guerbet alcohols with 6 to 20 carbon atoms, such as 2-methylpentanol, 2-ethylhexanol, 2-hexyldecanol, 2-0ctyldecanol, 2-Hexyldodecanol and / or 2-octyldodecanol, preferably used.
  • aromatic alcohols such as benzyl alcohol, cinnamon alcohol, phenol, dihydroxy- or trihydroxy-benzene derivatives, and cycloaliphatic alcohols having 3 to 20 carbon atoms, such as cyclopropanol, cyclobutanol or cyclodecanol, can also be used according to the invention for the transesterification.
  • the double-layer hydroxide compounds of the general formula I are used in an amount of 1 to 20% by weight, preferably 5 to 15% by weight, based on the respective amount of tetramethoxy or tetraethoxysilane.
  • smaller amounts of double-layer hydroxide compounds can also be added, although longer reaction times must be expected.
  • the double-layer hydroxide compounds can be used several times for further transesterification even without special work-up.
  • the present invention furthermore relates to tetraalkoxysilanes of the general formula Si (0R) 4, in which R represents the rest of Guerbet alcohols having 12 to 38 C atoms, preferably R each represents the same radical of a Guerbet alcohol.
  • Suitable examples of Guerbet alcohols are 2-butyloctanol, 2-hexyldecanol, 2-nonyltridecanol, 2-0ctyldodecanol and n-dodecylhexadecanol.
  • Technical Guerbet alcohols are preferred, the technical Guerbet alcohols due to it Manufacturing process can contain up to 20 wt .-% tri- and tetramer Guerbet alcohols.
  • tetraalkoxysilanes according to the invention can either be prepared by the process according to the invention or by one of the processes known from the prior art.
  • the decisive factor here is whether particularly light-colored tetraalkoxy lanes are desired for the application or not. If the color is not important, the preparation is carried out by the processes known from the prior art, preferably by transesterification of tetramethoxy or tetraethoxysilane in the presence of bases, preferably sodium methoxide, as a catalyst, for example in accordance with the American patents US Pat. No. 2,643,263 or 26 73870.
  • tetramethoxy or tetraethoxysilane to be used and the respective Guerbet alcohols correspond to the details of the process according to the invention.
  • the tetraalkoxysilanes are expediently the
  • Guerbet alcohols with 12 to 38 carbon atoms are then neutralized in a conventional manner, for example with an acid such as the dilute phosphoric acid.
  • the resulting sodium phosphate is then separated off via the aqueous phase. If light-colored tetraalkoxysilanes according to the invention of Guerbet alcohols are desired, they must be prepared by the process according to the invention.
  • the invention furthermore relates to the use of the light-colored tetraalkoxysilanes prepared by the process according to the invention as cosmetic ingredients, cooling lubricants, hydraulic fluids, heat transfer fluids or defoamers.
  • reaction mixture was then heated to 80-90 ° C. in the course of 15-20 minutes and, after the reaction had started, the methanol formed as the reaction temperature rose (heating rate approx. 0.5 ° C. per minute, up to 200 ° C. ) separated by distillation. At a degree of transesterification of approximately 85 to 95% (determined by indirectly determining the amount of methanol), the reaction was stopped. After cooling, the crude product was mixed with water in a volume ratio of 1: 1 and dilute phosphoric acid was added until neutralization. The organic phase was separated off and then fractionally distilled (bp at 1 torr: 194 ° C., tetra-2-ethylhexylsilane).
  • reaction mixture was then heated to 90-100 ° C. in the course of 15-20 minutes and, after the reaction had started, the resulting ethanol or methanol at an increasing reaction temperature (heating rate approx. 0.5 ° C. per minute, up to 200 ° C) separatively separated.
  • heating rate approx. 0.5 ° C. per minute, up to 200 ° C
  • the reaction was stopped, after cooling the crude product was mixed with 1: 1 by volume with H2O and dilute phosphoric acid was added until neutralization.
  • the organic phase was separated and fractionally distilled.
  • Table 3 Reaction of tetraethoxysilane with 2-ethylhexanol
  • Example 2 Analogously to Example 1, 114 g (0.75 mol) of tetramethoxysilane were reacted with 1399 g (3.4 mol) of 2-0ctyldodecanol in the presence of 11.4 g of a hydrophobicized hydrotalcite (1 kg lauric acid to 2 kg hydrotalcite). After the hydrotalcite had been separated off, the excess 2-0ctyldodecanol was distilled off in vacuo. A colorless tetraalkoxysilane was obtained.

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Abstract

L'invention concerne des silanes tétraalcoxyliques d'alcools de Guerbet, un procédé de production de silanes tétraalcoxyliques de couleur claire répondant à la formule générale Si(OR)4 par transestérification de silane tétraméthoxylique ou tétraéthoxylique avec un alcool en présence de quantités catalytiques d'au moins un composé hydroxyde à couche double répondant à la formule générale (I), alors que le méthanol ou l'éthanol sont éliminés en continu, ainsi que l'utilisation des silanes tétraalcoxyliques de couleur claire comme ingrédients de produits cosmétiques, comme réfrigérants lubrifiants, comme fluides hydrauliques, comme fluides caloporteurs ou comme agents antimousse.
PCT/EP1991/002426 1990-12-19 1991-12-17 Silanes tetraalcoxiliques, leur procede de production et leur utilisation WO1992011266A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4040679A DE4040679A1 (de) 1990-12-19 1990-12-19 Verfahren zur herstellung von hellfarbigen tetraalkoxysilanen und deren verwendung
DEP4040679.2 1990-12-19

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WO1992011266A1 true WO1992011266A1 (fr) 1992-07-09

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8591605B2 (en) 2007-07-26 2013-11-26 Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno Methods, systems, and apparatus for obtaining biofuel from coffee and fuels produced therefrom

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19629760A1 (de) * 1996-07-23 1998-01-29 Wacker Chemie Gmbh Verfahren zur Herstellung von Alkoxysilanen
KR100574249B1 (ko) * 2004-08-26 2006-04-26 주식회사 두본 인(p)이 염착된 하이드로탈사이트의 제조방법
US8481776B2 (en) 2008-03-14 2013-07-09 Kao Corporation Functional substance-releasing agent

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD251353A1 (de) * 1986-07-23 1987-11-11 Akad Wissenschaften Ddr Verfahren zur umesterung von kieselsaeureestern

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD251353A1 (de) * 1986-07-23 1987-11-11 Akad Wissenschaften Ddr Verfahren zur umesterung von kieselsaeureestern

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, (Online STN), American Chemical Society 1992, Accession-No. CA104(2):7778j; & SU,A,1 155 602. *
CHEMICAL ABSTRACTS, (Online STN), American Chemical Society 1992, Accession-No. CA113(19):171486u; & JP,A,02 160 792. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8591605B2 (en) 2007-07-26 2013-11-26 Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno Methods, systems, and apparatus for obtaining biofuel from coffee and fuels produced therefrom

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