WO1999007713A1 - Composes organosilicies comportant des composes bicycliques - Google Patents

Composes organosilicies comportant des composes bicycliques Download PDF

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Publication number
WO1999007713A1
WO1999007713A1 PCT/EP1998/003878 EP9803878W WO9907713A1 WO 1999007713 A1 WO1999007713 A1 WO 1999007713A1 EP 9803878 W EP9803878 W EP 9803878W WO 9907713 A1 WO9907713 A1 WO 9907713A1
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Prior art keywords
compounds
radicals
amino
platinum
unsubstituted
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PCT/EP1998/003878
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German (de)
English (en)
Inventor
Armin Fehn
Frank Achenbach
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Wacker Chemie AG
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Wacker Chemie AG
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Publication of WO1999007713A1 publication Critical patent/WO1999007713A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon 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
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0836—Compounds with one or more Si-OH or Si-O-metal linkage
    • 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
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • 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

Definitions

  • the invention relates to monomeric disilylated bicycles, their preparation and the use of these bicycles for the production of bicyclic siloxane polymers.
  • Organo (poly) siloxanes containing norbornenyl groups are known from DE-A-41 28 932, a di- rectly bonded siloxane residue being contained per norbornenyl residue.
  • the object of the present invention is to provide targeted monomeric disilylated bicycles which can be used as starting materials for the production of siloxanes which are bridged by at least one bicyclic compound.
  • the invention relates to compounds of general formula I.
  • R 1 and R4 are each monovalent unsubstituted or optionally interrupted by non-adjacent oxygen, sulfur, nitrogen or phosphorus atoms or fluorine, chlorine, bromine, iodine, cyano, hydroxyl, amino, mercapto or C 1 -C 20 hydrocarbon radicals substituted by phosphino groups, R2 and R5 each have monovalent radicals which are selected from
  • R and R are each monovalent radicals R or R, R 7 and R8 are each divalent aliphatic, unsubstituted or optionally interrupted by non-adjacent oxygen, sulfur, nitrogen or phosphorus atoms or with fluorine, chlorine, bromine or iodine -, Cyano-, Hydroxy-, Amino-, Mercapto- or Phosphino groups substituted C- j _-C 14 -hydrocarbon residues,
  • Bi a divalent bicyclic unsubstituted or substituted by fluorine, chlorine, bromine, iodine, cyano, hydroxy, amino, mercapto, phosphino groups or C 1 -C 3 hydrocarbyl radicals substituted C 1 -C2o 7-hydrocarbon radical, and i 1 the values 1, 2 or 3 *, j, k, m and n the values 0, 1 or 2 and, o and p the values 0 or 1.
  • residues R 1 and R4 e.g. Alkyl radicals such as methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert. -Butyl-, n-pentyl-, iso-pentyl-, neo-pentyl-, tert.
  • Pentyl radical Hexyl radicals, such as the n-hexyl radical; Heptyl residues, such as the n-heptyl residue; Octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the
  • Nonyl radicals such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl radicals, such as the n-dodecyl radical; Octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl residues such as cyclopentyl, cyclohexyl, cycloheptyl residues and methylcyclohexyl residues; Aryl radicals, such as the phenyl, naphthyl and anthryl and phenanthryl radical; Alkaryl residues, such as o-, m-, p-tolyl groups, xylyl groups and ethylphenyl groups and aralkyl groups, such as the benzyl group, the - and the -phenylethyl group; Acrylate or methacrylate residues such as -
  • haloaryl radicals such as the o-, m- and p-chlorophenyl radical.
  • the methyl, ethyl, n-propyl, iso-propyl and phenyl radical are preferred.
  • radicals R 1 and R4 preferably contain at most 1
  • the amino residues R 2 and R5 are, for example, for the amine residues with two identical or different residues on the amine, e.g. the radicals listed for R.
  • Preferred amine residues are dimethyl, methyl-ethyl, diethyl, ethyl-n-propyl, ethyl-isopropyl, ethyl-phenyl, diphenyl, methyl-phenylamine, with other residues on the amine e.g. cyclic and / or aromatic radicals may be preferred.
  • the divalent aliphatic radicals R 7 and R8 are preferably straight-chain or branched.
  • the radicals R 7 and R8 preferably have only carbon and hydrogen atoms.
  • the radicals R 7 and R8 preferably have 1 to 6 carbon atoms.
  • the divalent bicyclic radical Bi preferably has 7 to 12 carbon atoms, in particular the norbornenyl radical is preferred. Unsubstituted and substituted with C- j _-Cg-hydrocarbon radicals radicals Bi are preferred.
  • Preferred values for i and 1 are 2 and 3. Two radicals R and / or R on the respective Si atom are particularly preferred. Preferred values for j and are 0 and 1, particularly preferably the value 1.
  • P preferably has the value 0.
  • Two Aliphatic C C double bonds
  • hydrosilylation catalyst wwoobbeeii RR 1 ,, RR 2 ,, RR 3 ,, RR 4 ,, RR 5 ,, RR 6 ,, ii ,, jj ,, k, 1, m and n have the above meanings
  • bicyclic diolefms cheap and large amounts of available compounds such as 2 -, 5-norbornadiene, 5-C 1 -C 14 alkylene-2-norbornene and 5-Vmyl -2 -norbornene are preferably used.
  • 5-C - ⁇ - C- ] _4alkylene-2-norbornenes 5-methylene-2-norbornene and 5-ethylidene-2-norbornene are particularly preferred.
  • the divalent aliphatic radical R of the general formula I results from the bicyclic diolefin used.
  • the indices o and p result from the basic structure of the bicyclic diolefin used.
  • the hydrosilylation reaction on the bicyclic diolefin can give rise to various isomers which are either endo and exo to the bicyclus and which, for example in the case of norbornadiene as the bicyclus used, either 2-5- or 2-6- or 3-5- or 3-6- substituted bicycles.
  • the preferred formation of one and / or some of these isomers can be influenced by the choice of the reaction conditions, in particular by the choice of the catalyst.
  • These isomers can be separated from one another by common methods such as distillation, crystallization, sublimation and / or derivatization.
  • the isomeric purity of the compound produced can be preferred over the isomer mixture normally obtained by the preparation. In this case, the production process would be followed by a further step for the separation of the isomers.
  • silanes of the general formulas II and III are chlorodimethylsilane, chlorodiethylsilane, chlorodiphenylsilane,
  • Ethoxydimethylsilane triethylsilane, trimethylsilane, dichloromethylsilane, dichlorophenylsilane and dimethoxymethylsilane.
  • the hydrosilylation catalyst which promotes the addition of Si-bonded hydrogen to aliphatic double bonds can be added either only to the bicyclic diolefin or only to the silane of the general formulas (II) and (III) or to both reaction partners before they meet.
  • the hydrosilylation catalysts are preferably a metal from the group of platinum metals or a compound or a complex from the group of
  • Platinum metals or mixtures thereof are metallic and finely divided platinum, which can be on supports such as silicon dioxide, aluminum oxide or activated carbon, compounds or complexes of platinum, such as platinum halides, for example PtCl 4 H 2 PtClg * 6H 2 0, Na 2 PtCl 4 * 4H 2 0, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcohol complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products from H 2 PtClg * 6H 2 0 and cyclohexanone, platinum-vinylsiloxane complexes, as described in US Pat. No. 3,775,442 or
  • the hydrosilylation catalyst is preferably used in amounts of 1 to 100 ppm by weight, preferably in 5 to 40 ppm by weight, in each case calculated as elemental platinum and based on the total weight of bicyclic diolefin and silane.
  • the production process is preferably carried out at the pressure of the surrounding atmosphere, that is to say at about 1020 hPa (abs.), But it can also be carried out at higher or lower pressures. Furthermore, the process is preferably carried out at a temperature of 25 ° C. to 180 ° C., preferably at 80 ° C. to 140 ° C.
  • the reaction can be carried out in air or under inert gas, e.g. Nitrogen or argon.
  • the reaction time is preferably from a few minutes to a day.
  • radical inhibitors such as 4-methoxyphenol, 2,6-bis (tert-butyl) -4-methylphenol, phenothiazine, Hydroquinone or pyrocatechol can also be used.
  • the radical inhibitors are preferably used in amounts of 10 to 500 ppm by weight, based on the total weight of bicyclic diolefin and silane.
  • organic solvents can be used in the process, although their use is not preferred.
  • inert organic solvents are toluene, xylene, chlorobenzene, tetrahydrofuran, glycol dimethyl ether, diethylene glycol dimethyl ether, octane isomers and butyl acetate.
  • bicycles of the general formula I, starting materials, catalyst and, if appropriate, solvent can be separated by the customary workup methods, such as distillation, filtration, crystallization, column chromatography, sublimation and derivatization.
  • the disilylated bicycles of the general formula I prepared are generally liquids which can be distilled. They can therefore be obtained in high purity by distillation.
  • the disilylated bicycles of the general formula I obtained by the preparation process can subsequently be converted into other compounds of the general formula I by known substitution reactions. Examples of substitution reactions are: the conversion of chlorosilanes into hydroxysilanes, alkoxysilanes, hydridosilanes or aminosilanes and the conversion of alkoxysilanes into hydroxysilanes.
  • the invention also relates to the use of the compounds of the general formula I as starting materials for the production of siloxanes which are bridged over at least one bicyclic cycle.
  • Siloxane polymers are preferably prepared from the compounds of the general formula I.
  • the disilylated bicycles of the general formula I are preferably added by hydrolysis / condensation, condensation, addition and equilibration Polymers processed.
  • the invention encompasses all known methods by means of which the disilylated bicycles can be used for the preparation of siloxane polymers.
  • Bicyclic siloxane polymers are e.g. non-reactive polymers and reactive polymers, e.g. one or more of the following reactive groups: vinyl, acrylate, methacrylate, H -, - OH, hydroxypropyl, aminopropyl, acetoxy, alkoxy, oxomato and amino may have.
  • Example 3 144 g of 5-vinyl-2-norbornene and 35 ppm of platinum in the form of the catalyst described in US Pat. No. 3,775,442 are heated to 80.degree. 228 g of chlorodimethylsilane are added. The reaction mixture is overnight at 90 ° C.-110 ° C. After cooling, 276 g of the product can be obtained as a clear liquid by distillation in vacuo (2 mbar) between 120 ° C. and 130 ° C.
  • the following formula results from the NMR, IR, GC / MS data and the elementary analysis:
  • PNC1 2 solution is stirred at 100 ° C for one hour and then at 120 ° C for 1 hour.
  • the mixture is allowed to cool to room temperature, 0.5 ml of hexamethyldisilazane is added and the mixture is stirred another 15 min and removes volatile components in vacuo (1 mbar) at 80 ° C.
  • About 124 g of a slightly yellowish oil are obtained which, according to the 1 HN R, 29 SI NMR and IR spectra, has the following average composition:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Abstract

L'invention concerne des composés de formule générale (I) R<4>lR<5>mR<6>nSi-(R<7>)o-Bi-(R<8>)p-SiR<3>kR<2>jR<1>i, formule dans laquelle R<1>, R<2>, R<3>, R<4>, R<5>, R<6>, R<7>, R<8>, i, j, k, l, m, n, o et p ont les significations indiquées dans la revendication 1. L'invention concerne également la production de ces composés et leur utilisation comme produits de départ pour la production de siloxanes pontés par l'intermédiaire d'au moins un composé bicyclique.
PCT/EP1998/003878 1997-08-07 1998-06-25 Composes organosilicies comportant des composes bicycliques Ceased WO1999007713A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19734251.5 1997-08-07
DE19734251A DE19734251A1 (de) 1997-08-07 1997-08-07 Bicyclen aufweisende Organosiliciumverbindungen

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Publication Number Publication Date
WO1999007713A1 true WO1999007713A1 (fr) 1999-02-18

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PCT/EP1998/003878 Ceased WO1999007713A1 (fr) 1997-08-07 1998-06-25 Composes organosilicies comportant des composes bicycliques

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10287400B2 (en) 2016-04-14 2019-05-14 Momentive Performance Materials Inc. Curable silicone composition and applications and uses thereof
US10385210B2 (en) 2017-06-20 2019-08-20 Momentive Performance Materials Inc. Curable silicone composition and applications and uses thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5527936A (en) * 1995-02-17 1996-06-18 E. I. Du Pont De Nemours And Company Hydrosilylation of unsaturated compounds
WO1996027599A1 (fr) * 1995-03-08 1996-09-12 E.I. Du Pont De Nemours And Company Composes d'organosilicium reactifs

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5527936A (en) * 1995-02-17 1996-06-18 E. I. Du Pont De Nemours And Company Hydrosilylation of unsaturated compounds
WO1996027599A1 (fr) * 1995-03-08 1996-09-12 E.I. Du Pont De Nemours And Company Composes d'organosilicium reactifs

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 117, no. 5, 3 August 1992, Columbus, Ohio, US; abstract no. 48671, ZICHE, WOLFGANG ET AL: "Silaheterocycles. 15. Cycloaddition behavior of 1,1-dichloro-2-neopentyl-2-(trimethylsilyl)silene" XP002083735 *
CHEMICAL ABSTRACTS, vol. 55, no. 26, 25 December 1961, Columbus, Ohio, US; abstract no. 27131e, PETROV, A.D. ET AL.: "preparation of organosilicon derivatives of bicyclo(2.2.1)heptane" XP002083745 *
ORGANOMETALLICS (1992), 11(7), 2494-9 CODEN: ORGND7;ISSN: 0276-7333, 1992 *
ZHUR. OBSHCHEI KHIM, vol. 31, 1961, pages 1199 - 1208 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10287400B2 (en) 2016-04-14 2019-05-14 Momentive Performance Materials Inc. Curable silicone composition and applications and uses thereof
US10385210B2 (en) 2017-06-20 2019-08-20 Momentive Performance Materials Inc. Curable silicone composition and applications and uses thereof

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Publication number Publication date
DE19734251A1 (de) 1999-02-11

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