WO1999007713A1

WO1999007713A1 - Organosilicon compounds containing bicyclical compounds

Info

Publication number: WO1999007713A1
Application number: PCT/EP1998/003878
Authority: WO
Inventors: Armin Fehn; Frank Achenbach
Original assignee: Wacker-Chemie Gmbh
Priority date: 1997-08-07
Filing date: 1998-06-25
Publication date: 1999-02-18
Also published as: DE19734251A1

Abstract

The invention relates to compounds corresponding to the general formula (I) R4lR5mR6nSi-(R7)o-Bi-(R8)p-SiR3kR2jR1i, where R?1, R2, R3, R4, R5, R6, R7, R8¿, i, j, k, l, m, n, o and p have the meanings given in claim 1. The invention also relates to their production and use as initial material for producing siloxanes which are bridged through at least one bicyclical compound.

Description

ORGANOSILICIUM COMPOUNDS WITH BICYCLES

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.

US Pat. No. 5,527,936 describes a process for the preparation of hydrosilylated olefins, in which mixtures which contain mono- and disilylated compounds are prepared via a radical reaction initiated by an azo compound. With radical reactions there is generally a risk that the olefins polymerize.

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 ⁴ ₁ R ⁵ _m R ⁶ _n Si- (R ⁷ ) _Q - Bi ~ (R ⁸ ) _p - SiR ³ _k R ² jR ¹ _i (I),

in which

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

Fluorine, chlorine, bromine, iodine, -OR, hydroxy, amino, -0-Si (R ¹ ) ₂ R ³ or -H,

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.

In the general formula (I), all radicals R 1 to R8 and all indices i, 1, j, k,, n, o and p are, independently of one another, the same or different.

The tetravalence of the carbon atom means that i + j + k = 3 and 1 + m + n = 3.

Straight-chain branched or cyclic hydrocarbon residues are used as 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

2, 2, 4-trimethylenepentyl; 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 - (CH ₂ ) _χ -0-C (= 0) -CH = CH ₂ , - (CH ₂ ) _χ -0-C (= 0) -C (CH ₃ ) = CH ₂ with x = 2-12 selected. Examples of substituted C _] _-C _2Q hydrocarbon radicals are the 3, 3, 3-trifluoro-n-propyl radical, the

2, 2, 2, 2 ', 2', 2 '-hexafluoroisopropyl radical, the heptafluoroisopropyl radical, and haloaryl radicals, such as the o-, m- and p-chlorophenyl radical. The methyl, ethyl, n-propyl, iso-propyl and phenyl radical are preferred.

The radicals R 1 and R4 preferably contain at most 1

Oxygen, sulfur, nitrogen or phosphorus atom on two, in particular on 4 carbon atoms.

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.

The invention also relates to a process for the preparation of compounds of the above general formula

unsubstituted or substituted by amino, mercapto, phosphino, or C ₁ -C- _j _3 substituted hydrocarbyl radicals, two Aliphatic C = C double bonds Direction bicyclic C ₇ -C ₃ g-hydrocarbon silane, which is selected from silanes of the general Formulas II or III

R ⁴ ₁ R ⁵ _m R ⁶ _n Sι-H (II),

R ¹ ₁ R ² R ³ _k Sι-H (III),

is reacted in the presence of 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

As 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. Of the 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. Depending on the desired property profile of the end product, 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.

Examples of 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 common compounds which have hitherto been used to promote the attachment of Si-bonded hydrogen to double bonds are used as the hydrosilylation catalyst. 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. Examples of such catalysts 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

Platinum-1,3-divinyl-l, 1,3,3-tetramethyldisiloxane complexes with or without content of detectable inorganic halogen, bis- (gammapicolin) -platinum dichloride, trimethylene-dipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, dimethylsul- (oxydethylene) platinum dichloride -dichloride, cyclooctadiene-platinum dichloride, norbornadiene-platinum dichloride, gammapicolin-platinum dichloride, cyclopentadiene-platinum dichloride, as well as reaction products of platinum tetrachloride with olefin and primary amine or secondary amine or primary and secondary amine dissolved in 1 as the reaction product Platinum tetrachloride with sec. -Butylamine, or ammonium-platinum complexes and palladium complexes.

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.

Depending on the reaction temperature, the amount and type of catalyst used and the structure of the starting materials used, the reaction time is preferably from a few minutes to a day.

Since the double bonds of the bicyclic diolefin tend to polymerize, especially at higher temperatures, 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.

Inert, organic solvents can be used in the process, although their use is not preferred. Examples of inert organic solvents are toluene, xylene, chlorobenzene, tetrahydrofuran, glycol dimethyl ether, diethylene glycol dimethyl ether, octane isomers and butyl acetate.

After the reaction has ended, 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. In particular, 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.

In the following examples, unless otherwise stated,

a) all quantities based on weight; b) all pressures 0.10 MPa (abs. '); c) all temperatures 20 ° C.

Examples

Example 1: Representation of

Bis (chlorodimethylsilyl) bicyclo [2.2.1.] Heptane

100 ml of 2,5-norbornadiene in 150 ml of p-xylene are placed under a nitrogen atmosphere and heated to 90 ° C.-100 ° C. 175.5 g of HSi (CH ₃ ) ₂ Cl (chlorodimethylsilane) are added, together with 20 ppm of platinum in the form of a platinum-sym-divinyltetramethylsiloxane complex (solution in cyclohexane with 1% by weight of Pt calculated as the element) . The temperature of the reaction mixture rises to approx. 100 ° C - 110 ° C. After 4 hours, the mixture is cooled and worked up. 187.5 g of the product can be isolated as a clear, colorless liquid under vacuum (approx. 2 mbar) between 110 ° C and 120 ° C. The product has the following formula:

The identity of the product was confirmed by NMR, IR, GC / MS and elemental analysis.

Example 2:

Under a nitrogen atmosphere, 100 g of 5-methylene-2-norbornene are heated to 80 ° C.-90 ° C. with 20 ppm platinum in the form of the catalyst described in US Pat. No. 3,775,442. For this purpose, 180 g of chlorodimethylsilane, together with 20 ppm of platinum in the form of the catalyst described in US Pat. No. 3,775,442, are metered in. The resulting reaction mixture is stirred for 4 hours, the temperature rising to 100 ° C - 120 ° C. It is then cooled and worked up. 235 g of the product can be isolated as a clear, slightly yellowish liquid under vacuum (approx. 1 mbar) between 100 ° C and 110 ° C. Due to the reaction, the product has the formula:

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:

Example 4

100 g of 5-ethylidene-2-norbornene and 20 ppm of platinum in the form of a platinum-sym-divinyltetramethylsiloxane complex (solution in cyclohexane with 1% by weight of Pt calculated as the element) are heated to 80-100 ° C. 152 g of chlorodimethylhydrogensilane are then slowly added dropwise. After the dropwise addition, the mixture is stirred at 100-120 ° C. overnight. The crude product is distilled in vacuo at about 2 mbar. Between 120 and 130 ° C, 183 g of product with the following composition are obtained:

Mixture of

Example 5:

A solution of 16.4 g NaOH, 25.8 g water and 5.2 ml triethylamine are cooled to 0-5 ° C. A mixture of 58.2 g of the product from Example 2 and 300 ml of diethyl ether is added dropwise to this solution. After dropping, the mixture is stirred at RT for 3 hours. The mixture is shaken out with water and the ether phase is dried over sodium sulfate. After removing the sodium sulfate and diethyl ether, 43 g of product are obtained with the following formula:

Example of use 1:

28 g of product from Example 3, 12.5 g of dimethyldichlorosilane and 0.12 g of a 10% by weight toluene PNC1 ₂ solution are heated to 80-100 ° C. After the addition of 24 g of water, the mixture is stirred at 80-100 ° C. for 2 hours and volatile constituents are removed in vacuum (2 mbar) at 80 ° C. About 32 g of a slightly yellowish cloudy oil with the following composition (statistical distribution of the bicycles) are obtained:

Example of use 2:

12.5 g of dichlorodimethylsilane are slowly added dropwise to a mixture of 26.5 g of product from Example 5, 15 g of pyridine and 20 ml of toluene. A white precipitate is formed and the mixture is stirred at 40 ° C overnight. After filtering, volatile components are removed in vacuo (2 mbar) at 80 ° C. About 28 g of a slightly yellow alternating copolymer with the following composition are obtained:

n

Example of use 3:

50.0 g of product from use example 1 and 91 g of polymethylhydrogensiloxane are heated to 80 ° C. under protective gas. After the addition of 0.2 ml of a 10 wt .-% toluene

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:

Example of use 4:

100 g of product from Example 3, 4.0 g of ViSi ₂ , 24 g of an a, w-dihydroxypolydimethylsiloxane with a viscosity at 25 ° C. of 1000 mPa * s, 30 g of toluene and 0.2 ml of a 10% by weight toluene PNC1 ₂ solution are stirred at 100 ° C. for 1 hour. 30 g of water are then added dropwise at 80.degree. After stirring for 1 hour, the excess water is distilled off, a further 0.1 ml of a 10% by weight toluene PNC1 ₂ solution is added to the reaction mixture and the mixture is stirred at 100-125 ° C. for 12 hours. Finally, volatile components are removed in vacuo (1 mbar) at 100 ° C. and about 100 g of a viscous oil with the following composition are obtained:

Claims

claims

1. Compounds of the general formula I

R ⁴ ₁ R ⁵ _m R ⁶ _n Si- (R ⁷ ) ₀ - Bi - (R ⁸ ) _p - SiR ³ _k R ² _j R ¹ _i (I),

in which

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 phosphino groups substituted C_-C ₂₀ -

Hydrocarbon residues,

R 2 and R5 are each monovalent radicals which are selected from fluorine, chlorine, bromine, iodine, -O-R, hydroxy, amino,

-0-Si (R ¹ ) ₂ R ³ or -H, c 1 9

R and R each have 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 fluorine, chlorine, bromine, iodine, cyano, hyroxy, amino or , Mercapto or phosphino groups substituted C- _j _-C ₁₄ hydrocarbon residues, Bi a divalent bicyclic unsubstituted or with fluorine, chlorine, bromine, iodine, cyano, hydroxy, amino, mercapto, phosphino groups or - _] _-C-L3 -hydrocarbon residues substituted Cη-C _{2 Q} -hydrocarbon residue, i and 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 mean.

2. Compounds according to claim 1, in which R 1 and R4 each

Methyl, ethyl, n-propyl, iso-propyl or phenyl radicals mean.

3. Compounds according to claim 1 or 2, in which Bi represents a norbornenyl radical. A process for the preparation of compounds of the general formula I as claimed in claim 1, in which bicyclic C ₇ -C ₃ g which has two aliphatic C = C double bonds and is unsubstituted or substituted with amino, mercapto, phosphino groups or C ₁ -C ₁ 3 -hydrocarbon radicals -Carbon with silane, which is selected from silanes of the general formulas II or III

R ⁴ ₁ R ⁵ _m R ⁶ _n Si-H (II),

in the presence of hydrosilylation catalyst, where R 1, R2, R3, R'4, R5, R6, x, j, k, 1, m and n have the meanings given in claim 1.

5. Use of the compounds of the general formula I according to claim 1 as starting materials for the preparation of siloxanes which are bridged over at least one bicyclus.