DE10255650A1 - Organosilicon compounds for surface treatment, e.g. of leather or floor tiles, obtained by hydrosilylation of compounds containing 2, 3 or 4 terminal alpha-alkyl-vinyl groups with organo-hydrogen-polysiloxane compounds - Google Patents

Abstract

Organic compounds with 2, 3 or 4 terminal alpha-alkylvinyl groups are used for the production of organosilicon compounds by reaction with organo-hydrogen-polysiloxanes in presence of hydrosilylation catalysts. Organosilicon compounds obtained by reacting (1) organic compounds of formula R2(CR1=CH2)x (I) in which R1 = 1-6C alkyl; R2 = a divalent, trivalent or tetravalent 1-25 hydrocarbon residue, optionally containing oxygen, silicon and/or titanium atom(s); x = 2, 3 or 4 , with (2) organopolysiloxanes containing on average more than one hydrogen atom attached to silicon, in presence of (3) hydrosilylation catalysts. An Independent claim is also included for a method as described above for the production of organosilicon compounds.

Description

US-A 5,241,034 (Wacker-Chemie GmbH) discloses siloxane copolymers with 1-alkenyl groups, which can be linear or branched and are prepared by polyaddition of hydrogen siloxanes and olefins with at least two terminal C = C double bonds, preferably terminal CH ₂ = CH groups, so that they contain siloxane and hydrocarbon blocks alternately. The siloxane copolymers have a preferred viscosity of 10 to 10,000 mPa.s at 25 ° C.

In US-A 4,150,048 (Union Carbide Corporation) describes the preparation of linear polyether siloxanes which are obtained by reacting α, ω-dihydrogensiloxanes with organic (poly) ethers with two end groups of the formula CH ₂ = C (R) CH ₂ - under hydrosilylation reaction conditions. Only (poly) ethers are used as organic components, which in most cases are difficult to mix with the siloxanes. EP-A 896 015 (OSi Specialties, Inc., published February 10, 1999) discloses such a manufacturing process under vacuum.

US-A 6,451,909 (Wacker Chemie GmbH) describes a process for the production of multiphase preparations of organosilicon compounds, in particular of aqueous emulsions of organosilicon compounds, by reacting olefins with at least two terminal C = C double bonds, preferably terminal CH ₂ = CH groups, with hydrogen siloxanes in emulsion ,

The task was organosilicon compounds to be provided that are not networked, i.e. are soluble in toluene. Furthermore, the task was a process for the production of To provide organosilicon compounds that are simple and in which organosilicon compounds with higher molecular weights are obtained can be. The object is achieved by the invention.

The invention relates to organosilicon compounds which can be prepared by reacting organic compounds (1) which contain at least two double bonds which are reactive toward SiH groups and have the general formula R ² (CR ¹ = CH ₂ ) _x (I) where R ^{1 is} an alkyl radical having 1 to 6 carbon atoms per radical,
R ² denotes a divalent, trivalent or tetravalent hydrocarbon radical having 1 to 25 carbon atoms, which may contain one or more heteroatoms which are separate from one another and selected from the group consisting of oxygen, silicon and titanium, and
x means 2, 3 or 4,
with organopolysiloxanes (2) with an average of more than one Si-bonded hydrogen atom per molecule in the presence of catalysts that promote the attachment of Si-bonded hydrogen to an aliphatic double bond (3).

The invention further relates to a process for the preparation of organosilicon compounds by reacting organic compounds (1) which contain at least two double bonds which are reactive toward SiH groups and have the general formula R ² (CR ¹ = CH ₂ ) _x (I)
where R ^{1 is} an alkyl radical having 1 to 6 carbon atoms per radical,
R ² denotes a divalent, trivalent or tetravalent hydrocarbon radical having 1 to 25 carbon atoms, which may contain one or more heteroatoms which are separate from one another and selected from the group consisting of oxygen, silicon and titanium, and
x means 2, 3 or 4,
with organopolysiloxanes (2) with an average of more than one Si-bonded hydrogen atom per molecule in the presence of catalysts that promote the attachment of Si-bonded hydrogen to an aliphatic double bond (3).

The method according to the invention can be present of water (5), i.e. it can therefore be aqueous dispersions or watery Emulsions of organosilicon compounds can be obtained.

The process according to the invention has the advantage that the use of olefins with end groups CH ₂ = CR ¹ - (R ¹ means a C ₁ _ ₆ -alkyl radical) gives higher viscosities and molecular weights than those with end groups CH ₂ = CH organosilicon compounds ,

According to the method according to the invention are obtained as organosilicon compounds in toluene soluble are, i.e. uncrosslinked organosilicon compounds are obtained, as opposed to insoluble in toluene Organosilicon compounds that are cross-linked.

In the organosilicon compounds according to the invention, the siloxane blocks are connected to one another via hydrocarbon groups, which results in a hydrocarbon-siloxane block structure. The Or Ganosilicon compounds can be linear, branched or cyclic. They can have alkenyl groups or Si-bonded hydrogen atoms, depending on the ratio of the starting materials (1) and (2) used in their preparation. However, this does not exclude that they can contain small amounts of Si-bonded hydroxyl or alkoxy groups due to the manufacturing process.

The organosilicon compounds according to the invention preferably have a viscosity of at least 20,000 mPa.s at 25 ° C, preferably at least 500,000 mPa.s at 25 ° C, in particular at least 1 × 10 ⁶ mPa.s at 25 ° C and a viscosity of preferably to to 1 × 10 ⁹ at 25 ° C, preferably up to 1 × 10 ⁸ mPa.s at 25 ° C.

Examples of alkyl radicals R ¹ are the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo -Pentyl, tert-pentyl and hexyl, such as the n-hexyl. The methyl radical is preferred.

Examples of at least two organic compounds (1) which have aliphatic double bonds and are used in the process according to the invention are
2,3-dimethyl-1,3-butadiene,
2,5-dimethyl-1,5-hexadiene,
2,7-dimethyl-1,7-octadiene,
1.3 Diisopropenylcyclohexan,
1,3-diisopropenylbenzene,
1,3,5-triisopropenylbenzene,
Tris (methallyloxy) methylsilane, benzene tricarboxylic acid tris (methallyl ester)
Tetrakis (methallyloxy) silane,
2,5-dimethyl-1,5-hexadiene and 1,3-diisopropenylbenzene are particularly preferred.

wobei die Reste der Formel -(CH₂)₄- und -C₆H₄-bevorzugt sind.Examples of the radical R ² are therefore those of the formula

the radicals of the formula - (CH ₂ ) ₄ - and -C ₆ H ₄ - being preferred.

Preferably contain the method according to the invention Organopolysiloxanes (2) used on average at least 1.5 Si-bonded hydrogen atoms, preferably at least on average 2 Si-bonded hydrogen atoms per molecule.

The contain particularly preferably in the method according to the invention used organopolysiloxanes (2) 2 to 4 sigebonded hydrogen atoms per molecule.

In the method according to the invention can be one type of organopolysiloxane (2) or different types of organopolysiloxane (2) can be used. Also the organopolysiloxanes (2) production-related mixtures, i.e. for example included Organopolysiloxanes with 2 Si-bonded hydrogen atoms per molecule also include organopolysiloxanes with only one Si-bonded hydrogen atom per molecule.

wobei R gleiche oder verschiedene, gegebenenfalls halogenierte Kohlenwasserstoffreste mit 1 bis 18 Kohlenstoffatom(en) je Rest bedeuten,
e 0 oder 1, durchnittlich 0,002 bis 1,0,
f 0, 1, 2 oder 3, durchschnittlich 1,0 bis 2,0, und die Summe e+f nicht größer als 3 ist,
bei dem erfindungsgemäßen Verfahren eingesetzt.Preferred organopolysiloxanes (2) are those of the general formula

where R is the same or different, optionally halogenated hydrocarbon radicals having 1 to 18 carbon atoms per radical,
e 0 or 1, average 0.002 to 1.0,
f 0, 1, 2 or 3, on average 1.0 to 2.0, and the sum e + f is not greater than 3,
used in the inventive method.

Examples of radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, hexyl, like the n-hexyl residue, heptyl residues, like the n-heptyl residue, octyl residues, like the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, Decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl; Aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl; Alkaryl residues, such as o-, m-, p-tolyl residues, xylyl residues and ethylphenyl residues; and aralkyl radicals such as the benzyl radical, the α- and the β-phenylethyl radical. The methyl radical is preferred.

Examples of substituted radicals R are Haloalkyl radicals, such as 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.

Preferred organopolysiloxanes (2) are those of the general formula H _d R ₃ _ _d SiO (SiR ₂ O) _o (SiRHO) _p SiR ₃ -d H _d (III), where R has the meaning given above,
d 0 or 1, in particular 1,
o 0 or an integer from 1 to 1000 and
p 0 or an integer from 1 to 6, in particular 0,
means
used in the inventive method.

The organopolysiloxanes (2) have preferably a viscosity from 0.5 to 20,000 mPa.s at 25 ° C, preferred 20 to 2,000 mPa.s at 25 ° C.

Preferred examples of organopolysiloxanes of the formula (III) are copolymers of dimethylhydrogensiloxane and dimethylsiloxane units, copolymers of dimethylhydrogensiloxane, Dimethylsiloxane and methylhydrogensiloxane units, copolymers from trimethylsiloxane and methylhydrogensiloxane units and copolymers from trimethylsiloxane, dimethylsiloxane and methylhydrogensiloxane units. Particularly preferred examples of Organopolysiloxanes of the formula (III) are copolymers of dimethylhydrogensiloxane and dimethylsiloxane units.

Particularly preferred examples of organopolysiloxanes (2) are α, ω-dihydrogenpolydimethylsiloxanes.

Process for the preparation of organopolysiloxanes with at least two Si-bonded hydrogen atoms per molecule, too of those of the preferred type are generally known.

Organic compound (1) is at the inventive method used in such amounts that aliphatic double bond in organic compound (1) to Si-bonded hydrogen in organopolysiloxane (2) in relation from preferably 0.1: 1 to 20: 1.

If it is the organopolysiloxane (2) an α, ω-dihydrogen siloxane and the organic compound (1) is an α, ω-diene, the C = C / SiH ratio in specified range can be varied freely. There will always be siloxane copolymers obtained, which are freely soluble in toluene, the one used C = C / SiH ratio the type and average chain length of the polyadduct after completion Reaction determined. If this ratio is less than 1.0, then arise SiH-functional siloxane copolymers; is it bigger than 1.0 become ω-alkenyl functional Obtained siloxane copolymers. Short polyadducts are used at low or high ratios long polyadducts are obtained if the number of used C = C and SiH groups is the same and the reaction proceeds completely.

If starting materials (1) and / or (2) are used, the one higher functionality than 2.0, will preferably be a more or less large area of the C = C / SiH ratio from 1.0 upwards and downwards excluded, therefore organosilicon compounds soluble in toluene be preserved. This range can vary depending on the type and amount of Educts (1) or (2) can be determined experimentally. The general rule, that ever higher the average functionality the starting materials (1) or (2), the more unstoichiometric they are used Need to become, to be soluble in toluene Obtain organosilicon compounds.

If the starting materials (1) and (2) are each bifunctional, ie α, ω-dihydrogensiloxane and α, ω-diene are used, the C = C / SiH ratio is preferably 0.5 to 2.0, preferably 0 , 8 to 1.2, particularly preferably 0.9 to 1.1. With a C = C / SiH ratio of 0.9 to 1.1, highly viscous organosilicon compounds are obtained. In order to obtain highly viscous organosilicon compounds, the following requirements must be met: The starting materials (1) and (2) must have clean end stoppers, ie a functionality of 2.0; During the polyaddition, side reactions, such as the conversion of Si-H into Si-OH or the isomerization of 1-alkenyl to 2-alkenyl groups, may occur to a very small extent; and the polyaddition must take place completely. The occurrence of groups which are not reactive in the sense of polyaddition, such as SiOH or 2-alkenyl groups, leads to the termination of the polyaddition on these starting materials, since they are de facto monofunctional and thus act as endstoppers in polyaddition reactions. Examples of species leading to termination of the polyaddition are 1,6-octadiene or HR ₂ SiO (R ₂ SiO) _or R ₂ SiOH.

If at least one of the starting materials (1) and (2) is more functional than 2, multiphase preparations of polymers are obtained which have branched structures. The degree of branching depends on the actual respective functionality and the stoichiometric ratio used. The higher the respective functionality of the starting materials (1) and (2), the more branched structures are obtained and the larger the excluded range of the C = C / SiH ratio from 1.0 upwards and downwards. Therefore, no generally preferred range of the C = C / SiH ratio used can be given, but only depending on the functionality of the starting materials (1) and (2), as the following table shows:

Functionality of the starting materials (1) means here the number of aliphatic double bonds (C = C) in organic Connection (1).

Functionality of the starting materials (2) means here the average number of Si-bonded hydrogen atoms (SiH) in organopolysiloxane (2).

The catalysts used to promote the addition of Si-bonded hydrogen to an aliphatic double bond can also be used in the process according to the invention as have been used up to now to promote the addition of Si-bonded hydrogen to an aliphatic double bond binding could be used. The catalysts (3) are preferably a metal from the group of platinum metals or a compound or a complex from the group of platinum metals. 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 PtCl ₆ .6H ₂ O, Na ₂ PtCl ₄ · 4H ₂ O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products from H ₂ PtCl ₆ · 6H ₂ O and cyclohexanone, platinum-vinylsiloxane complexes, such as platinum-l, 3-divinyl-1,1,3,3-tetramethyldisiloxane complexes with or without content of detectable inorganically bound halogen, bis- (gammapicolin) -platinum dichloride, trimethylene-dipyridineplatinum dichloride, dicyclopin dichloride, dicyclopin dichloride, dicyclopin dichloride, dicyclopin dichloride, dicyclopin dichloride, dicyclopin dichloride, dicyclopin dichloride, dicyclopin dichloride, dicyclopin dichloride, dicyclopin dichloro did, - (II) dichloride, cyclooctadiene platinum dichloride, norbornadiene platinum dichloride, gamma-picolin platinum dichloride, cyclopentadiene platinum dichloride and reaction products of platinum tetrachloride with olefin in and primary amine or secondary amine or primary and secondary amine, such as the reaction product of platinum tetrachloride dissolved in 1-octene with sec-butylamine, or ammonium-platinum complexes.

The catalyst (3) is preferred in amounts of 0.5 to 1000 ppm by weight (parts by weight per million parts by weight), preferably in amounts of 2 to 50 ppm by weight, each calculated as elemental platinum and based on the total weight of organic Compound (1) and organopolysiloxane (2).

If the method according to the invention performed in water (5) is used, emulsifiers (4) are preferably used.

It can be used as an emulsifier all previously known, ionic and non-ionic emulsifiers both used individually as well as mixtures of different emulsifiers with which also previously stable aqueous dispersions, in particular aqueous Emulsions from organosilicon compounds could be produced.

Examples of non-ionic emulsifiers are: Sorbitan esters of fatty acids with 10 to 22 carbon atoms; Polyoxyethylene sorbitan esters from fatty acids with 10 to 20 carbon atoms and up to 35% ethylene oxide content; Polyoxyethylene sorbitol esters of fatty acids having 10 to 22 carbon atoms; Polyoxyethylene derivatives of phenols with 6 to 20 carbon atoms on aromatics and up to 95% ethylene oxide content; Fettamino and amido betaines with 10 to 22 carbon atoms; Polyoxyethylene condensates of fatty acids or fatty alcohols with 10 to 22 carbon atoms with up to 95% ethylene oxide content; Polyvinyl alcohols with 5 to 50% vinyl acetate units, with one Degree of polymerization from 500 to 3000; Castor oil ethoxylates with 20 to 200 ethylene oxide units.

Examples of ionic emulsifiers are:
Alkaryl sulfonates having 6 to 20 carbon atoms in the alkyl group; Fatty acid soaps with 10 to 22 carbon atoms in the alkyl group; Fatty acid soaps with 10 to 22 carbon atoms; Fatty sulfates having 10 to 22 carbon atoms;
Alkyl sulfonates containing 10 to 22 carbon atoms;
Alkali metal salts with dialkyl sulfosuccinates; Fatty amine oxides having 10 to 22 carbon atoms; Fatty imidazolines having 6 to 20 carbon atoms; Fatty amido sulfobetaines having 10 to 22 carbon atoms;
quaternary surfactants such as fatty ammonium compounds; with 10 to 22 carbon atoms; Fat morpholine oxides with 10 to 22 carbon atoms; Alkali metal salts of carboxylated ethoxylated alcohols having 10 to 22 carbon atoms and up to 95% ethylene oxide; Ethylene oxide condensates of fatty acid monoesters of glycerol with 10 to 22 carbon atoms and up to 95% ethylene oxide; Mono- or diethanolamides of fatty acids with 10 to 22 carbon atoms;
alkoxylated silicone surfactants with ethylene oxide and or propylene oxide units; Phosphatester.

As in the field of surfactants known, can the counterions in the case of anionic surfactants alkali metals, Ammonia or substituted amines, such as triethylamine or triethanolamine, his. In the case of cationic surfactants, the counter ion is a halide, Sulfate or methyl sulfate. Chlorides are mostly industrial available Links.

In the method according to the invention emulsifier (4) is preferably used in amounts of 1 to 20% by weight 3 to 15 wt .-%, based on the total weight of the ingredients (1) and (2).

Instead of water, too Polyalkylene oxide compounds in the process according to the invention be used.

In the method according to the invention optionally water (5), in amounts of preferably 10 to 90% by weight, preferably 40 to 70% by weight, based on the total weight of components (1) and (2) used.

Will the inventive method performed in water, the mixture of starting materials (1) and (2), catalyst (3), emulsifier (4) and water (5) with the usual Techniques emulsified, e.g. with rotor-stator or dissolver stirring devices, as well as with High pressure homogenizers, in aqueous, over a long period stable dispersions, preferably emulsions, transferred.

The process according to the invention can take place in the presence of water in the oil phase. This can be a continuous oil phase with water droplets or a continuous water phase with oil droplets. It is preferably an oil-in-water emulsion. This has the advantage that emulsions with high molecular weight organosilicon compounds can be produced in situ in the oil phase.

Will the inventive method performed in water, contains the aqueous dispersion according to the invention, preferably aqueous Emulsion, organosilicon compounds preferably in amounts of 20 to 70% by weight, preferably 35 to 60% by weight.

In the method according to the invention can inert organic solvents can also be used. Organic solvents are preferred used in the production of organosilicon compounds with high viscosities, examples for inert organic solvents are toluene, xylene, octane isomers, butyl acetate, 1,2-dimethoxyethane, Tetrahydrofuran and cyclohexane.

Furthermore, to regulate the viscosity profile or low molecular weight inert for handling reasons Siloxanes such as hexamethyldisiloxane, octamethyltrisiloxane or something higher Homologous and cyclic dialkylsiloxanes with 3 to 14 siloxy units be added.

In a special embodiment can also siloxanes are added, the average molecular weights from a few hundred to about 20,000 daltons, if these do not hinder the polyaddition of components (1) and (2). Examples therefor are alkyl-terminated polydimethylsiloxanes with a degree of polymerization approximately in the range of 10 to 250, also known as silicone oils. The Amount of these additives can range from a few percent to approx. 4 times the total weight of the components (1) and (2).

If from processing establish he wishes, can be the addition of Si-bonded hydrogen to aliphatic Multiple binding retardant at room temperature - for example the mixture of organic compound (1) and organopolysiloxane (2) - added become.

As inhibitors which retard the addition of Si-bonded hydrogen to aliphatic multiple bonds at room temperature, all inhibitors which could previously also be used for the same purpose can also be used in the compositions according to the invention. Examples of inhibitors are 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, benzotriazole, dialkylformamides, alkylthioureas, methylethylketoxime, organic or organosilicon compounds with a boiling point of at least 25 ° C. at 1012 mbar (abs.) And at least one aliphatic triple bond according to US-A 3,445,420 such as 1-ethynylcyclohexan-1-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentin-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol and 3,5-Dimethyl-1-hexin-3-ol, 3,7-dimethyl-oct-1-in-6-en-3-ol inhibitors according to US-A 2,476,166 , such as a mixture of diallyl maleate and vinyl acetate, and inhibitors according to US 4,504,645 like maleic acid monoesters.

The inhibitor is preferably used in Quantities from 0.001 to 10 wt .-%, based on the total weight of the Components (1) and (2) used, the amount of 0.005 up to 0.01% by weight is preferred.

The method according to the invention is preferred at the pressure of the surrounding atmosphere, i.e. around 1020 hPa (abs.), carried out, but it can also be used at higher ones or lower pressures be performed. It is preferably in a temperature range from 0 ° C to 160 ° C, preferred from 0 ° C up to 120 ° C. The inventive method for the production of an aqueous Dispersion, preferably aqueous Emulsion, is carried out in a temperature range from 0 ° C to 80 ° C.

The process according to the invention can be carried out in batches, be carried out semi-continuously or fully continuously.

The organosilicon compounds according to the invention or their aqueous Dispersions, preferably aqueous Emulsions are used for the surface treatment of flexible Materials such as leather or synthetic leather, e.g. made of polyurethane, as well rigid surfaces, like floors Stone, artificial stone, plastics, ceramic tiles, earthenware or Stoneware.

Example 1:

724 g of a linear, α, ω-dihydrogenpolydimethylsiloxane are mixed with 0.054 wt .-% Si-bonded hydrogen with 17.5 g of 2,5-dimethyl-1,5-hexadiene at 25 ° C with good stirring (C = C / Si-H = 0.81).

The homogeneous mixture is then catalyzed with 4 mg of platinum in the form of a 1% by weight (based on elemental platinum) solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in an α, ω-divinyldimethylpolysiloxane with a viscosity of 1000 mPa.s at 25 ° C, a solution of the so-called Karstedt catalyst (its production in US 3,775,452 is described).

After 10 minutes, the same amount is added again. An exothermic reaction leads to a sharp increase in viscosity and finally to a clear oil with a viscosity of 3,034 mm ² / s at 25 ° C.

Example 2:

134.5 g of a linear, α, ω-dihydrogenpolydimethylsiloxane with 0.0106% by weight of Si-bonded Hydrogen is mixed homogeneously with 0.84 g of 2,5-dimethyl-1,5-hexadiene (C = C / Si-H = 1.07) and at 25 ° C. with 1.4 mg of platinum in the form of that in Example 1 Karstedt catalyst solution described activated. There is a sharp increase in viscosity within a few minutes. After 4 hours, a sample of the high polymer obtained is dissolved in 3.2 times the amount of toluene. The solution has a viscosity of 4 150 mm ² / s at 25 ° C.

In comparison, a polydimethylsiloxane with a viscosity of 10 ⁷ mPa.s at 25 ° C at the same dilution has a viscosity of 3 560 mm ² / s at 25 ° C after dilution.

Comparative Example 1:

Example 2 is repeated with identical amounts of hydrogen siloxane and diene, with 2,5-dimethyl-1,5-hexadiene being exchanged for 1,7-octadiene with the same molecular weight (C = C / Si-H = 1.07). The viscosity of the solution diluted with 3.2 times the amount of toluene after 4 hours is this time only 560 mm ² / s at 25 ° C., ie the polymer obtained has a lower molecular weight.

Comparative Example 2:

Example 2 is repeated with identical amounts of hydrogen siloxane, but only 0.63 g of 1,5-hexadiene instead of 0.84 g of 2,5-dimethyl-1,5-hexadiene, the amount of CH ₂ = C groups remaining the same (C = C / Si-H = 1.07). The viscosity of the solution diluted with 3.2 times the amount of toluene after 4 hours is determined at 585 mm ² / s at 25 ° C., ie the polymer obtained has a lower molecular weight.

Example 3:

Example 2 is now carried out with 141.5 g of the hydrogen siloxane instead of only 134.5 g (C = C / Si-H = 1.02). This increases the viscosity increase even more. After 4 hours, the high polymer is diluted with 3.2 times the amount of toluene. The solution has a viscosity of 10,900 mm ² / s at 25 ° C.

Example 4:

A siloxane high polymer can also be prepared in an inert diluent. For this purpose, 43 g of α, ω-dihydrogenpolydimethylsiloxane (0.0106% by weight of active hydrogen) and 0.25 g of 2,5-dimethyl-1 are added in succession to 173 g of silicone oil with a viscosity of 10 mm ² / s (25 ° C.) , 5-hexadiene dissolved (C = C / Si-H = 1.00) and activated after good homogenization with 2.2 mg of platinum in the form of the Karstedt catalyst solution described in Example 1.

In the course of several hours, the viscosity at 25 ° C rises to 29,000 mm ² / s and thus almost 1000 times the original value.

Example 5:

1,570 g of an α, ω-dihydrogenpolydimethylsiloxane with 0.051% by weight of Si-bonded hydrogen are mixed homogeneously with 69.5 g of 1,3-diisopropenylbenzene (C = C / Si-H = 1.10) and at 25 ° C. activated with 0.08 g of the Karstedt catalyst described in Example 1 (21% platinum). The exothermic reaction reaches approx. 50 ° C in approx. 10 minutes. At this temperature, the mixture is left to react for a further 4 hours until the detection of sigebound hydrogen is negative. The highly viscous product has a viscosity of 12 400 mm ² / s at 25 ° C.

Comparative Example 3:

Example 5 is repeated with 57.2 g of 1,3-divinylbenzene instead of the 69.5 g of 1,3-diisopropenylbenzene. Under otherwise identical conditions, a clear polymer with a viscosity of only 2,350 mm ² / s at 25 ° C. is obtained. Although siloxane and diene are used in the same molar ratio (C = C / Si-H = 1.10), only a much thinner siloxane polymer is produced.

Example 6:

17.0 g of distilled water and 50.0 g of an 80% aqueous solution of an isotridecyl alcohol ethoxylate of the average formula C ₁₃ H ₂₇ O (C ₂ H ₄ O) ₁₀ H are mixed in a container.

In a dissolver, this mixture at 1000 rpm. a total of 349.5 g of an α, ω-dihydrogenpolydimethylsiloxane (corresponding to 56 mg of Si-bonded hydrogen) are metered in, whereupon a highly viscous phase forms. 90 g of distilled water are added over a period of 4 minutes, where by obtaining a mixture with a creamy consistency.

2.33 g of 2,5-dimethyl-1,5-hexadiene (C = C / Si-H = 1.00) and 0.64 g of the Karstedt catalyst solution described in Example 1 are then added in succession with 1.1% by weight. -% platinum content fed in and distributed in the creamy mass. When the speed drops, a total of 300 ml of distilled water are metered in slowly, then more quickly within 10 minutes. The filtered emulsion has an average particle size of 190 nm. The polymer precipitated with acetone and washed with water is soluble in toluene and has a viscosity of 3 × 10 ⁷ mPa.s at 25 ° C.

Comparative example 4:

Example 6 is carried out analogously with 2.33 g of 1,7-octadiene instead of 2,5-dimethyl-1,5-hexadiene (C = C / Si-H = 1.00). The polymer has a viscosity of only 1.4 x 10 ⁶ mPa.s at 25 ° C.

Claims (10)

Organosilicon compounds can be prepared by reacting organic compounds (1) which contain at least two double bonds which are reactive toward SiH groups and have the general formula R ² (CR ¹ = CH ₂ ) _x (I) where R ^{1 is} an alkyl radical with 1 to 6 carbon atoms per radical, R ^{2 is} a divalent, trivalent or tetravalent hydrocarbon radical with 1 to 25 carbon atoms, which may contain one or more heteroatoms selected from the group consisting of oxygen, silicon and titanium , and x denotes 2, 3 or 4, with organopolysiloxanes (2) with an average of more than one Si-bonded hydrogen atom per molecule in the presence of catalysts (3) which promote the attachment of Si-bonded hydrogen to an aliphatic double bond. Organosilicon compounds according to claim 1, characterized characterized that the process is carried out in water and watery Dispersions or aqueous Emulsions of organosilicon compounds can be obtained. Organosilicon compounds according to claim 1 or 2, characterized in that they are soluble in toluene. Organosilicon compounds according to claim 1, 2 or 3, characterized in that it has a viscosity of 20 up to 1,000,000 Pa · s at 25 ° C exhibit. Organosilicon compounds according to one of claims 1 to 4, characterized in that the organic compound (1) 2,5-dimethyl-1,5-hexadiene or 1,3-diisopropenylbenzene. Process for the preparation of organosilicon compounds by reacting organic compounds (1) which contain at least two double bonds reactive towards SiH groups, of the general formula R ² (CR ¹ = CH ₂ ) _x (I) where R ^{1 is} an alkyl radical with 1 to 6 carbon atoms per radical, R ^{2 is} a divalent, trivalent or tetravalent hydrocarbon radical with 1 to 25 carbon atoms, which may contain one or more heteroatoms selected from the group consisting of oxygen, silicon and titanium , and x denotes 2, 3 or 4, with organopolysiloxanes (2) with an average of more than one Si-bonded hydrogen atom per molecule in the presence of catalysts (3) which promote the attachment of Si-bonded hydrogen to an aliphatic double bond. A method according to claim 6, characterized in that R ^{1 is} a methyl radical. A method according to claim 6 or 7, characterized in that that as organic compound (1) 2,5-dimethyl-l, 5-hexadiene or 1,3-diisopropenylbenzene be used. Method according to claim 6, 7 or 8, characterized in that that as organopolysiloxanes (2) α, ω-dihydrogenpolydimethylsiloxanes be used. Method according to one of claims 6 to 9, characterized in that that the process is carried out in the presence of water.