DE19602663A1 - Crosslinkable composition for production of non-stick coatings - Google Patents

Abstract

Crosslinkable compositions contain (A) organosilicon compounds with residues containing aliphatic carbon-carbon multiple bonds; (B) organosilicon compounds with silicon-bonded hydrogen atoms; (C) catalysts for addition reaction between Si-H groups and multiple C-C bonds; and optionally (D) agents which act as retarders for this reaction at room temperature. At least part of component (B) consists of organo-Si compounds (B1) with on average 8-50 Si-bonded H atoms per molecule, containing (a) terminal units of formula HaR3-aSiO1/2 (I) and optionally R3SiO1/2 (I'), at least 50 mole% of which consist of units (I); (b) carbon-based units G (II) linking together at least two Si atoms and consisting of di- to deca-valent 2-30C hydrocarbon residues which may contain one or more oxygen, boron, silicon, tin or titanium atoms; (c) units of formula RbSi(-)O(3-b)/2 (III) and/or RbSi(=)O(2-b)/2 (III') which are attached to units (G) by the Si atoms; and optionally (d) units of formula HcRdSiO(4-c-d)/2 (IV) situated between units (III)/(III') and end groups (I)/(I'). In the formulae, R is an optionally halogenated 1-8C hydrocarbyl with no aliphatic multiple bonds; a = 1, 2 or 3; b = 0, 1 or 2 (b is not 2 in formula III'); c = 0 or 1; d = 1 or 2; and c+d = 1 or 2. Also claimed are (i) compositions as above, in which compounds (B1) are obtained by a specified process; (ii) compounds (B1); and (iii) the process for production of (B1).

Description

The invention relates to crosslinkable compositions containing

• (A) Organosilicon compounds, the residues with aliphatic Have carbon-carbon multiple bonds,
• (B) Organo containing Si-bonded hydrogen atoms silicon compounds
• (C) the addition of Si-bonded hydrogen aliphatic multiple bond promoting catalysts

and if necessary

• (D) the addition of Si-bonded hydrogen aliphatic multiple bond at room temperature delaying agents

and the use of the crosslinkable compositions for Manufacture of tacky coatings. The invention further relates to Si-bonded ones Organosilicon compounds containing hydrogen atoms and a process for their production.

As a crosslinker for aliphatic unsaturated organopoly Siloxanes are used almost exclusively with organopolysiloxanes Hydrogenmethylsiloxane units used, in the simplest Case end blocked with triorganosiloxy groups Hydrogen methyl polysiloxane. To increase reactivity it has proven itself between the hydrogenmethylsiloxane units by equilibrating dimethylsiloxane units to install. However, these measures are very limited Improvements.  

In addition to those based on hydrogenmethylsiloxane units Crosslinkers are also known to be those without methyl groups. In DE-B 19 55 511 and the corresponding US-A 3,615,272 are resins made from hydrogen siloxane units trifunctional units described. For use in addition-curing organopolysiloxane compositions as However, such polymers are only very crosslinking agents limited use, since they are hardly in the networkable Dissolve diorganopolysiloxanes.

Organopolysiloxanes are known from EP-A 568 318 trifunctional siloxane units and monofunctional Siloxane units with Si-bonded hydrogen are known. According to EP-A 568 318, T units are in the form of Organosiloxane units with hydrogendimethylsiloxy groups endstoppert, with a between these groups different number of dimethylsiloxane or Hydrogenmethylsiloxane units can be installed.

According to DE-A 37 16 372 organopolysiloxanes with Si bonded hydrogen atoms and 3 to 5 silicon atoms each Molecule of [H (CH₃) ₂si] ₂0 and trialkoxysilanes in one hydrolytic process.

There was the task of Si-bonded hydrogen atoms having organosilicon compounds to provide the with organosilicon compounds, the residues with aliphatic Have carbon-carbon multiple bonds, in Presence of the attachment of Si-bonded hydrogen catalysts promoting aliphatic multiple bonds Network quickly, with higher networking speeds be achieved than before. There was also the task to provide crosslinkable compositions which are used for  Manufacture of tacky coatings are suitable. The object is achieved by the invention.

The invention relates to crosslinkable compositions containing

• (A) Organosilicon compounds, the residues with aliphatic Have carbon-carbon multiple bonds
• (B) Si-bonded hydrogen atoms Organosilicon compounds
• (C) the addition of Si-bonded hydrogen aliphatic multiple bond promoting catalysts and possibly
• (D) agents which delay the addition of Si-bonded hydrogen to aliphatic multiple bonds at room temperature, characterized in that organosilicon compounds containing Si-bonded hydrogen atoms contain such as (B)
  • (a) End units of the general formula H _a R _3-a SiO _1/2 (I) and optionally end units of the general formula R₃SiO _1/2 (I '), where
    R is the same or different and is a monovalent, optionally halogenated hydrocarbon radical free of aliphatic multiple bonds and having 1 to 8 carbon atoms per radical and
    a is 1, 2 or 3,
    with the proviso that at least 50 mol% of the end units are those of the formula (I),
  • (b) carbostructure units G (II)
    where G is the same or different and is a divalent to ten-valent hydrocarbon radical with 2 to 30 carbon atoms per radical, which may contain one or more heteroatoms selected from the group consisting of oxygen, boron, silicon, tin or titanium,
    with the proviso that at least two Si atoms are connected to one another via G,
  • (c) Units of the general formula and or in which
    R has the meaning given above,
    b is 0, 1 or 2, with the proviso that b in formula (III ') is not 2, and
    with the proviso that the units of the formula (III) or (III ′) are connected to the carbostructure units G via the Si atoms
    and if necessary
  • (d) Units of the general formula in which
    R has the meaning given above,
    c 0 or 1 and
    d 1 or 2
    and the sum c + d is 1 or 2, with the proviso that the units of the formula (IV) differ between the units of the formula (III) or (III ') and the end units of the formula (I) or (I ′) Are located, and
    with the proviso that the organosilicon compounds containing (B) Si-bonded hydrogen atoms contain on average at least 4 Si-bonded hydrogen atoms per molecule,
    be used.

The invention further relates to crosslinkable Compositions, characterized in that as (B) Si Organosilicon containing bonded hydrogen atoms Connections used can be made by in a first step aliphatic multiple bonds Hydrocarbon compounds with 2 to 30 Carbon atoms that are one or more heteroatoms selected from the group of oxygen, boron, silicon, Can contain tin and titanium with silanes (2) of the general formula

HR _b SiX _3-b

where R and b have the meaning given above and x may be the same or different, a halogen atom or is a radical of the formula -OR¹, where R¹ is an alkyl radical with 1 up to 8 carbon atoms per residue, which is represented by a Ether oxygen atom may be substituted means in the presence of the attachment of Si-bound Promoting hydrogen to aliphatic multiple bonds  Catalysts (3) are implemented and excess silanes (2) are removed by distillation, the ratio of Si-bonded used Hydrogen in silane (2) to aliphatic double bond in Hydrocarbon compound (1) 1.0 to 2.0 or too aliphatic triple bond in hydrocarbon connection (1) is 2.0 to 4.0, in a second step having the hydrolysis-capable groups thus obtained links with silanes (4) of the general formula

H _a R _3-a SiZ

or siloxanes (5) of the general formula

H _a R _3-a SiOSiR _3-a H _a

where R and a are as defined above and Z is a halogen atom or a radical of the formula -OR², where R² is a monovalent hydrocarbon radical having 1 to 8 carbon atoms per radical, which may be substituted by an ether oxygen atom,
and water are reacted in the presence of catalysts (6) which promote hydrolysis, the ratio of Si atoms used in silanes (4) or siloxanes (5) to hydrolysis-capable groups in the compounds 0.8 to 5 obtained from the first step, Is 0,
and optionally in a third step the organosilicon compounds thus obtained containing Si-bonded hydrogen atoms with organopolysiloxanes (7) optionally having Si-bonded hydrogen atoms selected from the group consisting of linear organopoly siloxanes containing terminal triorganosiloxy groups, linear organopolysiloxanes containing terminal hydroxyl groups, branched , optionally hydroxyl-containing organopolysiloxanes, cyclic organopolysiloxanes and copolymers of diorganosiloxane and monoorganosiloxane units, are equilibrated,
and with the proviso that the organosilicon compounds (B) thus obtained containing Si-bonded hydrogen atoms have on average at least 4 Si-bonded hydrogen atoms per molecule.

The invention furthermore relates to Si-bonded Organosilicon compounds containing hydrogen atoms (B) containing

• (a) end units of the general formula H _a R _3-a SiO _1/2 (I) and optionally end units of the general formula R₃SiO _1/2 (I ′), where R and a have the meaning given above,
  with the proviso that at least 50 mol% of the end units are those of the formula (I),
• (b) carbostructure units G (II) where G is the same or different and one divalent to ten-valent hydrocarbon residue with 2 to 30 carbon atoms per radical means the one or more heteroatoms selected from the group of Contain oxygen, boron, silicon, tin or titanium can, with the proviso that via G at least two Si atoms are interconnected
• (c) Units of the general formula and or where R and b have the meaning given above, with the proviso that the units of the formula (III) or (III ') are connected to the carbostructure units G via the Si atoms
  and if necessary
• (d) Units of the general formula where R, c and d have the meaning given above, with the proviso that the units of the formula (IV) are between the units of the formula (III) or (III ') and the end units of the formula (I) or (I ′) are located, and
  with the proviso that the organosilicon compounds (B) containing Si-bonded hydrogen atoms contain on average at least 4 Si-bonded hydrogen atoms per molecule.

The invention further relates to a method for Production of the Si-bonded hydrogen atoms Organosilicon compounds (B), characterized in that in a first step aliphatic multiple bonds Hydrocarbon compounds (1) with 2 to 30 Carbon atoms, each one or more heteroatoms selected from the group of oxygen, boron, silicon, Can contain tin and titanium with silanes (2) of the general formula

HR _b SiX _3-b

where R, X and b have the meaning given above, in the presence of the attachment of Si-bound Promoting hydrogen to aliphatic multiple bonds Catalysts (3) are implemented and excess silanes (2) are removed by distillation, the ratio of Si-bonded used Hydrogen in silane (2) to aliphatic double bond in Hydrocarbon compound (1) 1.0 to 2.0 or too aliphatic triple bond in hydrocarbon compound (1) is 2.0 to 4.0, in a second step having the hydrolysis-capable groups thus obtained links with silanes (4) of the general formula

H _a R _3-a SiZ

or siloxanes (5) of the general formula

H _a R _3-a SiOSiR _3-a H _a

where R, Z and a are as defined above, and water is reacted in the presence of catalysts (6) which promote hydrolysis,
wherein the ratio of Si atoms used in silanes (4) or siloxanes (5) to groups capable of hydrolysis in the compounds obtained from the first step is 0.8 to 5.0,
and optionally in a third step the organosilicon compounds thus obtained containing Si-bonded hydrogen atoms with organopolysiloxanes (7) optionally having Si-bonded hydrogen atoms selected from the group consisting of linear organopoly siloxanes containing terminal triorganosiloxy groups, linear organopolysiloxanes containing terminal hydroxyl groups, branched , optionally hydroxyl-containing organopolysiloxanes, cyclic organopolysiloxanes and copolymers of diorganosiloxane and monoorganosiloxane units, are equilibrated,
with the proviso that the organosilicon compounds (B) thus obtained containing Si-bonded hydrogen atoms have on average at least 4 Si-bonded hydrogen atoms per molecule.

An essential characteristic of the Si having bound hydrogen atoms Organosilicon compounds (B) is that per molecule Total number of terminal Si-bonded hydrogen atoms, ie the Si contained in the end units of the formula (I) bound hydrogen atoms, is greater than the total number all with each other via the carbostructure unit G per molecule connected Si atoms.  

The Si-bonded hydrogen atoms according to the invention Organosilicon compounds (B) have a good Solubility in component (A) described above crosslinkable composition.

The organosilicon compounds (B) according to the invention containing Si-bonded hydrogen atoms preferably have a viscosity of 4 to 500 mm² · _s ^-1 at 25 ° C, preferably 4 to 100 mm² · _s ^-1 at 25 ° C, and particularly preferably 4 to 40 mm² · _s ^-1 at 25 ° C.

The Si-bonded hydrogen atoms according to the invention containing organosilicon compounds (B) on average 4 to 50 Si per molecule bonded hydrogen atoms, preferably 6 to 30 Si-bonded Hydrogen atoms, particularly preferably 8 to 25 Si-bonded Hydrogen atoms.

The Si-bonded hydrogen atoms according to the invention Organosilicon compounds (B) have a Hydrogen equivalent weight of preferably 90 to 300 g per Mol Si-bonded hydrogen, preferably 90 to 120 g per Mole of Si-bonded hydrogen.

The rest R in the Si-bonded hydrogen atoms containing organosilicon compounds (B) is free of aliphatic multiple bonds so that there is none Self-networking comes, which lead to insolubility.

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, isopentyl, neopentyl, tert-pentyl; Hexyl radicals, such as the n-hexyl radical; Heptyl residues, such as the n-heptyl residue; Octyl residues like that n-octyl radical and iso-octyl radicals, such as the 2,2,4-  Trimethylpentyl; Cycloalkyl radicals, such as cyclopentyl, Cyclohexyl, cycloheptyl and methylcyclohexyl; Aryl radicals, such as the phenyl radical; Alkaryl residues, such as o-, m-, p- Tolyl, xylyl and ethylphenyl and Aralkyl radicals, such as the benzyl radical, the α- and the β- Phenylethyl radical. The methyl radical is preferred.

Examples of halogenated 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 Halogenaryl radicals, such as the o-, m- and p-chlorophenyl radical.

Examples of alkyl radicals R¹ are the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, and tert-butyl radical. Methyl and ethyl are preferred rest. Examples of alkyl radicals R¹ through an ether Substance atom are substituted, are the methoxyethyl and Ethoxyethyl radical.

Examples of hydrocarbon radicals R² are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl and tert-butyl radical, the methyl and ethyl radical is preferred, and the rest of the formula -C (= CH₂) CH₃. Examples of alkyl radicals R², the are substituted by an ether oxygen atom, are the Methoxyethyl and ethoxyethyl radical.

A preferred example of the halogen atom X is that Chlorine atom.

Examples of radicals Z are -Cl, -Br, -OCH₃, -OC₂H₅ and -OC (= CH₂) CH₃.

a is preferably 1 or 2, particularly preferably 1.  

b is preferably 0 or 1, particularly preferably 0.

c is preferably 0.

The sum of c + d is preferably 2.

A particularly preferred example of the end unit of the Formula (I) is the hydrogendimethylsiloxane unit.

As the carbostructure unit G, residues of the general formula

R⁴ (CR³H-CH₂-) _x (II)

where R⁴ is a divalent to ten-valent hydrocarbon radical having 1 to 10 carbon atoms, which may contain one or more heteroatoms selected from the group consisting of oxygen, boron, silicon, tin and titanium, R³ is a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms per radical and
x means 2, 3, 4, 5, 6, 7, 8, 9 or 10, in particular 3, 4, 5 and 6, particularly preferably 3,
used.

Examples of alkyl radicals R³ are the methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pen tyl radical and hexyl radicals, such as the n-hexyl radical. Is preferred R³, a hydrogen atom.

Examples of divalent carbostructure units G are those of the formula

-CH₂CH₂-
-CH₂CH₂CH₂CH₂-
- (CH₂) ₆-
- (CH₂) ₁₀-
- (CH₂) ₃O (CH₂) ₃-
-CH₂CH₂-C₆H₄-CH₂CH₂- and
-CH₂CH₂Si (CH₃) ₂CH₂CH₂-.

Examples of trivalent carbostructure units G are those of the formula

(-CH₂CH₂) ₃C₆H₉
(-CH₂CH₂) ₃C₆H₃
(-CH₂CH₂CH₂OCH₂) ₃C-CH₂CH₃
(-CH₂CH₂CH₂) ₃B
(-CH₂CH₂) ₃SiCH₃ and
(-CH₂CH₂) ₃SnC₄H₉.

Examples of tetravalent carbostructure units G are those of the formula

(-CH₂CH₂) ₄C₄H₄
(-CH₂CH₂) ₄Si
(-CH₂CH₂) ₄Sn
(-CH₂CH₂) ₄Ti
(-CH₂CH₂CH₂O) ₂CH-CH (OCH₂CH₂CH₂-) ₂ and

Higher-order carbostructure units G can be those of formula

(-CH₂CH₂) ₃SiCH₂CH₂Si (CH₂CH₂-) ₃

or saturated oligomers of dienes such as butadiene or Be isoprene.

Preferred carbostructure units G are those with a Valence of 3, 4, 5 and 6, are particularly preferred trivalent carbostructural units.

Preferred as having Si-bonded hydrogen atoms Organosilicon compounds (B) are those made up of units of the formula (I), G and (III) exist.

Examples of Si-bonded hydrogen atoms Organosilicon compounds (B) are those of the formula

Me = methyl radical
n = 3 - 30
F = -CH₂CH₂-

The first in the method according to the invention Process step used hydrocarbon Connections (1) preferably contain two to ten aliphatic double bonds or an aliphatic Triple bond, preferably three to six aliphatic Double bonds, particularly preferably three aliphatic Double bonds.

Preferred hydrocarbon compounds (1) are those of the general formula

R⁴ (CR³ = CH₂) _x

where R⁴, R³ and x have the meaning given above,
used.

Examples of hydrocarbon compound (1) are
Acetylene, 1,5-hexadiene, 1,9-decadiene, diallyl ether, divinylbenzene, divinyldimethylsilane, 1,2,4-trivinylcyclohexane, 1,3,5-trivinylcyclohexane, 1,3,5-trivinylbenzene, triallylboron, trimethylolpropane triallyl ether, trivinylmethylsilane, Trivinylbutyltin, tetravinylcyclobutane, tetravinylidenecyclobutane, tetravinyltitanium, 1,1,2,2-tetraallyloxyethane, cyclooctatetraene, 1,3,5,7-tetravinylcyclooctane, 1,2-bis (trivinylsilyl) ethane, oligobutadiene, oligoisoprene.

Examples of silanes (2) used in the invention Processes are used in the first process step, are

HSiCl₃
HSiBr₃
HSi (OMe) ₃
HSi (OEt) ₃
HMeSiCl₂
HMeSi (OMe) ₂
H₂SiCl₂

Preferred silanes (2) are HSiCl₃ and H (CH₃) SiCl₂, where HSiCl₃ is particularly preferred.

In the method according to the invention, the first Process step a type of hydrocarbon compound (1) or different types of Hydrocarbon compounds (1) are used.

In the method according to the invention, the first Process step one type of silane (2) or different Types of silane (2) can be used.

In the method according to the invention, in the first Process step the ratio of Si-bound Hydrogen in silane (2) to aliphatic double bond in the hydrocarbon compound (1) is preferably 1.0 to 2.0, preferably 1.0 to 1.5, particularly preferably 1.0 to 1,2 or the ratio of Si-bonded hydrogen in Silane (2) for aliphatic triple bond in the  Hydrocarbon compound (1) preferably 2.0 to 4.0, preferably 2.0 to 3.0, particularly preferably 2.0 to 2.4.

As the addition of Si-bonded hydrogen to aliphatic double bond-promoting catalysts (3) can also be used in the process according to the invention, the same catalysts that have been used to promote the addition of Si-bonded hydrogen to aliphatic multiple bond. 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 che 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, e.g. B. PtCl₄, H₂PtCl₆ _* 6H₂O, Na₂PtCl₄ _* 4H₂O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including Lich reaction products from H₂PtCl₆ _* 6H₂O and cyclohexanone, platinum-vinylsiloxane complexes, such as platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes with or without content of detectable inorganic halogen, bis- (gamma-pico lin) -platindichlorid, trimethylenedipyridineplatinum, dicyclopentadieneplatinum, Dimethylsulfoxydethylen platinum (II) dichloride, cyclooctadiene-platinum dichloride, Nor Borna diene-platinum dichloride, gamma-picoline-platinum dichloride, cyclopentadiene-platinum dichloride, and reaction products of platinum tetrachloride with olefin and primary amine or secondary amine or primary and secondary amine according to US Pat. No. 4,292,434, such as the reaction product of platinum tetrachloride dissolved in 1-octene with sec-butylamine, or ammonium platinum complexes according to EP-B 110 370.

The catalyst (3) is in the first process step preferably in amounts of 1 to 50 ppm by weight (parts by weight each Million parts by weight), preferably in amounts of 5 to 20 Ppm by weight, calculated as elemental platinum and based on the total weight of Hydrocarbon compound (1) and silane (2) used.

The first process step is preferably when printing the surrounding atmosphere, i.e. at around 1020 hPa (abs.) led, but it can also at higher or lower Pressures are carried out. Furthermore, the first procedure step preferably at a temperature of 20 ° C to 150 ° C, preferably 40 ° C to 120 ° C, particularly preferably 60 ° C up to 120 ° C.

In the first process step, inert, organic Solvents can be used, although the use of inert, organic solvents is not preferred. Examples of inert, organic solvents are toluene, Xylene, octane isomers, butyl acetate, 1,2-dimethoxyethane, Tetrahydrofuran and cyclohexane.

The inert organic solvents which may be used after the first process step removed by distillation.

It is within the scope of the present invention that in the first Process step instead of the hydrocarbon compound (1) incomplete in combination with the silane (2) converted intermediates from the reaction of (1) with (2), i.e. H. Intermediates that are still aliphatic have unsaturated double bonds, are used and with silane (2) to the end product of the first Process step are implemented.  

An example of this is the conversion of acetylene with HSiCl₃ to Cl₃SiCH₂tH₂SiCl₃ in the first step. As an intermediate product CH2 = CHSiCl₃, which as Starting material can be used instead of acetylene and implemented with HSiCl₃ to the same end product of the first Process step, Cl₃SiCH₂CH₂SiCl₃, leads.

Another example of this is the implementation of 1,5-hexadiene with HSi (OEt) ₃ (Et = ethyl radical) (OEt) ₃Si (CH₂) ₆Si (OEt) 3 in the first process step. As Intermediate product CH2 = CH (CH₂) ₄Si (OEt) 3, which as Starting material can be used instead of 1,5-hexadiene can and implemented with HSi (OEt) ₃ (Et = ethyl radical) to the same End product of the first process step, (OEt) ₃Si (CH₂) ₆Si (OEt) ₃, leads.

Another example of this is the implementation of 1,2,4-trivinylcyclohexane with HSiCl₃ too

in the first step.

As an intermediate product

which as a starting material instead of 1,2,4-trivinylcyclohexane can be used and implemented with HSiCl₃ to the same end product of the first mentioned above Process step leads.

Examples of silanes (4) used in the invention Process used in the second step are dimethylchlorosilane, methylchlorosilane, chlorosilane, Methyl bromosilane, dimethyl methoxysilane, methyl methoxysilane, Dimethylethoxysilane, diethylchlorosilane, Dimethylisopropenoxysilane, methyldiisopropenoxysilane.

Examples of siloxanes (5) used in the invention Process used in the second step are 1,1,3,3-tetramethyldisiloxane, 1,3-dimethyldisiloxane, 1,1,1,3,3-pentamethyldisiloxane, 1,1-dimethyldisiloxane.

In the method according to the invention, the second Process step one type of silane (4) or different Types of silane (4) and one type of siloxane (5) or different types of siloxane (5) can be used.

The second in the method according to the invention Process step used the hydrolysis promoting Catalysts (6) can be the same as those previously the hydrolysis of groups capable of hydrolysis having organosilicon compounds are promoted could. Acids or bases can be used as catalysts (6) are used, the acids being preferred. Examples of acids are hydrochloric acid, hydrobromic acid, Sulfuric acid, perchloric acid, with hydrochloric acid being preferred. Hydrochloric acid is particularly preferred in a concentration of 1 to 20%.  

Water is preferably in in the second process step Amounts of 20 to 200 g, based on mole of Si-bonded hydrolysis-capable group X used.

In the method according to the invention, the second Process step the ratio of Si atoms in silanes (4) or siloxanes (5) to groups capable of hydrolysis in the hydrolysis-capable obtained from the first process step Group-containing compounds, preferably 0.8 to 5.0, preferably 0.8 to 2.5, particularly preferably 1.0 to 2.5.

Preferred procedures in the second process step are either-premixing from the first process step obtained compounds with silanes (4) and the common Cohydrolysis by metering this mixture into the initial charge Acid or the mixture of siloxanes (5) with acid and Dosing in from the first process step Links.

The second process step is preferably during printing the surrounding atmosphere, i.e. around 1020 hPa (abs.), performed, but it can also be done at higher or lower Pressures are carried out. Furthermore, the second procedure step preferably at a temperature of 0 ° C to 40 ° C, preferably 10 ° C to 25 ° C.

The second process step is worked up preferably by separating the aqueous phase and washing with water and bicarbonate solution.

Excess silane (4) and siloxane (5) are after the second process step preferably separated, preferred removed by distillation.  

In the second process step, inert, organic Solvents can also be used. Examples of inert, organic solvents are cyclohexane, toluene, xylenes, lower ketones, such as acetone or butanone.

The inert organic solvents which may be used The second step of the process is the means of funds separated, preferably removed by distillation.

The Si obtained after the second process step having bound hydrogen atoms Organosilicon compounds can be used in a third Process step with optionally Si-bonded Organosiloxanes containing hydrogen atoms (7) be equilibrated. The equilibration is carried out contain the Si-bound ones according to the invention Organosilicon compounds containing hydrogen atoms preferably at most ten units of the formula (IV), preferably at most five units of the formula (IV).

As optionally having Si-bonded hydrogen atoms Organopolysiloxanes (7) are preferably selected from the group consisting of linear, terminal Organopolysiloxanes containing triorganosiloxy groups of formula

R₃′SiO (SiR₂′O) _r siR₃ ′,

where R ′ has the same meaning as R or represents a hydrogen atom,
r is 0 or an integer from 1 to 500, preferably 10 to 200,
linear organopo lysiloxanes having hydroxyl groups of the formula

HO (SiR₂′O) ₅H,

where R 'has the meaning given above and s is an integer from 1 to 1000, preferably 10 to 500,
branched, optionally hydroxyl-containing organopolysiloxanes from units of the formula

R₃′SiO _1/2 , R₂′SiO and R′SiO _3/2 ,

where R ′ has the meaning given above, cyclic organopolysiloxanes of the formula

(R₂′SiO) _t ,

where R 'has the meaning given above and t is an integer from 3 to 12, and copolymers of units of the formula

R₂′SiO and R′SiO _3/2 ,

where R ′ has the meaning given above, used.

Preferred organopolysiloxanes (7) are those of the formulas R₃′SiO (SiR₂′O) _r SiR₃ ′ and HO (SiR₂′O) _s H.

The quantitative ratio of which may have been carried out performed equilibration of used organopolysiloxanes (7) and having Si-bonded hydrogen atoms Organosilicon compounds is only by the desired proportion of the Si-bonded hydrogen atoms in the in the event of any equilibration carried out generated organosilicon compounds and by the desired average chain length determined.  

In the eventual 'equilibration will be carried out acidic catalysts that promote equilibration, used.

Examples of acidic catalysts are sulfuric acid, Phos phosphoric acid, trifluoromethanoic acid, phosphorus nitride chlorides and acid catalysts which are solid under the reaction conditions, such as acid-activated bleaching earth, acidic zeolites, sulfonated Coal and sulfonated styrene-divinylbenzene copolymers sat. Phosphorus nitride chlorides are preferred. Phosphorni Tridchloride are preferably used in amounts of 5 to 1000 Ppm by weight (= parts per million), in particular 50 to 200 parts by weight ppm, each based on the total weight of the used Organosilicon compounds and used Organopolysiloxanes (7) used.

If necessary, the equilibration is carried out preferably at 100 ° C to 150 ° C and when printing the surrounding Atmosphere, i.e. at about 1020 hPa (abs.). If desired, however, higher or lower ones can also be used Pressures are applied. The equilibration is preferably two se in 5 to 20 wt .-%, based on the total weight of each Weil used organosilicon compounds and used organopolysiloxanes (7), in with water immiscible solvent such as toluene. In front the processing of that obtained during the equilibration Mixtures can render the catalyst ineffective.

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

The Si-bonded hydrogen atoms according to the invention containing organosilicon compounds (B) crosslinkable compositions are preferably used for  Production of coatings which repel sticky substances, e.g. B. used for the production of release papers.

The making of the self associated with the release paper adhesive materials are made using the off-line process or the in-line process. In the off-line process, the Si Licon composition applied to the paper and ver network, then, in a subsequent stage, usually after after winding the release paper on a roll and after the Storage of the roll is an adhesive film, for example lies on a label face paper, on the coated Paper is applied and the composite is then joined together presses. In the in-line process, the silicone is assembled applied to the paper and cross-linked, the silicone Plating is coated with the adhesive that labels face paper is then applied to the adhesive and the Composite finally pressed together.

As component (A) can also in the invention Compositions the same aliphatic carbon Having multiple carbon bonds Organosilicon compounds are used in all previously known crosslinkable compositions aliphatic carbon-carbon multiple bonds containing organosilicon compounds, Si-bonded Organosilicon compounds containing hydrogen atoms, the addition of Si-bonded hydrogen to aliphatic Multi-bond promoting catalysts are used could.

In the compositions according to the invention, one species of component (A) or different types of Component (A) can be used.  

As organosilicon compounds (A), the residues with alipha tables have carbon-carbon multiple bonds, are preferably linear or branched organopoly siloxanes from units of the general formula

where R⁵ is a monovalent hydrocarbon radical with 1 to 18 carbon atoms per radical and free from aliphatic carbon-carbon multiple bonds
R⁶ denotes a monovalent hydrocarbon radical with at least one terminal aliphatic carbon-carbon multiple bond with 2 to 12 carbon atoms per radical,
e 0, 1, 2 or 3,
f 0, 1 or 2
and the sum e + f is 0, 1, 2 or 3,
with the proviso that an average of at least 1 radical R⁶ per molecule, preferably at least 2 radicals R⁶ per molecule, is used.

Preferred organosilicon compounds (A) are organo polysiloxanes of the general formula

where R⁵ and R⁶ have the meaning given above,
g 0, 1 or 2,
n is 0 or an integer from 1 to 1500 and
m is 0 or an integer from 1 to 200,
with the proviso that at least one radical R⁶ per molecule, in particular at least 2 radicals R⁶ per molecule, are contained.

For the purposes of this invention, formula (VI) is to be understood in this way be that n units - (SiR₂⁵O) - and m units - (SiR⁵R⁶O) - in any way in the organopolysiloxane molecule can be distributed.

As organosilicon compounds (A) can also Siloxane copolymers containing alkenyl groups, as described in US-A 5,241,034 and that are made of siloxane blocks and hydrocarbon blocks are used. The alkenyl groups described in US-A 5,241,034 having siloxane copolymers are therefore part of the content of Disclosure of the application.

The organosilicon compounds (A) preferably have an average viscosity of 100 to 100,000 mPa · s at 25 ° C, preferably 100 to 10,000 mPa · s at 25 ° C, particularly preferably 100 to 500 mPa · s at 25 ° C.

Examples of hydrocarbon radicals R⁵ are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- Butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl; 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-trimethylpentyl radical; No nyl radicals, such as the n-nonyl radical; Decyl residues, such as the n-decyl residue, dodecyl residues, such as the n-dodecyl residue; Octadecyl residues, like the n-octadecyl radical; Cycloalkyl radicals, such as cyclopentyl, Cyclohexyl, cycloheptyl and methylcyclohexyl; Aryl radicals such as the phenyl, naphthyl, anthryl and phenane thryl residue; Alkaryl residues, such as o-, m-, p-tolyl residues, xylyl residues and ethylphenyl residues; and aralkyl residues, such as the Ben zylrest, the α- and the β-phenylethylrest.  

Examples of R⁶ radicals are alkenyl radicals, such as the vinyl, 5-hexenyl, 2,4-divinylcyclohexylethyl, 3,4-divinylcyclo hexylethyl, 2-propenyl, 3-butenyl and 4-pentenyl; and Alkynyl radicals, such as the ethynyl, propargyl and 2-propynyl.

The Si-bonded hydrogen atoms according to the invention having organosilicon compounds in the known crosslinkable compositions Organosilicon compounds, the residues with aliphatic Have carbon-carbon multiple bonds, Si-bonded hydrogen atoms Organosilicon compounds and the attachment of Si-bonded hydrogen to aliphatic Multi-bond promoting catalysts the Si-bonded hydrogen atoms Replace all or part of the organosilicon compounds. The crosslinkable compositions according to the invention can therefore, although not preferred as component (B) besides the organosilicon compounds according to the invention also others known Si-bonded hydrogen atoms Contain organosilicon compounds.

As Si-bonded hydrogen atoms Organosilicon compound can therefore preferably Organopolysiloxanes from units of the formula

where R has the meaning given above,
k 0 or 1,
l 0, 1, 2 or 3 and
the sum k + l is not greater than 3,
preferably those of the formula

H _y R _3-y SiO (SiR₂O) _o (SiRHO) _p SiR _3-y H _y

where R has the meaning given above,
y 0 or 1
o 0 or an integer from 1 to 100 and
p is 0 or an integer from 1 to 100 can also be used.

Examples of such organopolysiloxanes are in particular Copolymers on dimethylhydrogensiloxane, Methylhydrosiloxane, dimethylsiloxane and Trimethylsiloxane units, copolymers of Trimethylsiloxane, dimethylhydrogensiloxane and Methylhydrosiloxane units, copolymers from Trimethylsiloxane, dimethylsiloxane and Me thylhydrosiloxane units, copolymers of methyl hydrogensiloxane and trimethylsiloxane units, mixed poly merisate from methylhydrogensiloxane, diphenylsiloxane and Trimethylsiloxane units, copolymers made from methylhy drug siloxane, dimethylhydrogensiloxane and diphenyl silo xane units, copolymers of methylhydrogen siloxane, Phenylmethylsiloxane, trimethylsiloxane and / or dimethylhy drug siloxane units, copolymers of methylhydro gensiloxane, dimethylsiloxane, diphenylsiloxane, trimethyl siloxane and / or dimethylhydrogensiloxane units and Copolymers of dimethylhydrogensiloxane, trimethylsi loxane, phenylhydrosiloxane, dimethylsiloxane and / or Phenylmethylsiloxane units.

Component (B) is preferably used in amounts of 0.8 to 5.0, preferably 0.8 to 2.5, particularly preferably 1.0 to 2.0 Gram atom of Si-bonded hydrogen per mole of Si-bonded  Rest with aliphatic carbon-carbon Multiple bond used in component (A).

As the attachment of Si-bonded hydrogen to alipha Table double catalyst promoting catalyst (C) can also the same Ka in the compositions according to the invention Talyzers are used, which are also used with the previously known compositions for crosslinking aliphatic Organosilicon compounds containing multiple bonds with compounds containing Si-bonded hydrogen, could be used to promote networking. As Constituent (C) are preferably those mentioned above Catalysts (3) used.

Catalyst (C) is preferably used in amounts of 5 to 500 Ppm by weight (parts by weight per million parts by weight), in particular 10 to 200 ppm by weight, each calculated as elementary platinum metal and based on the total weight the organosilicon compounds (A) and (B) used.

Examples of other ingredients in the Invention according to the compositions can also be used the addition of Si-bonded hydrogen to aliphatic Multiple binding agents delaying room temperature, so-called called inhibitors (D), means for adjusting the separation strength, solvents, adhesion promoters and pigments.

As inhibitors (D) can also in the invention Compositions used are all inhibitors could previously also be used for the same purpose. Examples of inhibitors are 1,3-divinyl-1,1,3,3-tetrame thyldisiloxane, benzotriazole, dialkylformamides, alkylthio ureas, methyl ethyl ketoxime, organic or silicon or ganic 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-ethynylcyclohe xan-1-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentin-3-ol, 2,5-dimethyl-3-hexin-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 Vi nyl acetate, and inhibitors according to US 4,504,645, such as malein acid monoesters, and inhibitors according to the German Registration of the applicant with the file number 19541451.9, like the compound of the formula HC≡C-C (CH₃) (OH) -CH₂-CH₂-CH = C (CH₃) ₂, commercially available under the trade name "Dehydrolinalool" from BASF.

The inhibitor (D) is preferably used in amounts of from 0.01 to 10 wt .-%, based on the total weight of the Organosilicon compounds (A) and (B) used.

Examples of means for adjusting the release force of the the compositions produced according to the invention Coatings that repel other substances are silicone resins made of one units of the formula

R⁷ (CH₃) ₂SiO _1/2 and SiO₂,

So-called MQ resins, where R⁷ is a hydrogen atom, a methyl radical, a vinyl radical or a radical A, which is described in the above-cited US-A 5,241,034 and therefore belongs to the content of the disclosure of the application, and the units of Formula R⁷ (CH₃) ₂SiO _{1/2 may be the} same or different. The ratio of units of the formula R⁷ (CH₃) ₂SiO _1/2 to units of the formula SiO₂ is preferably from 0.6 to 2. The silicone resins are preferably used in amounts of 5 to 80% by weight, based on the total weight of the organosilicon compounds ( A) and (B) used.

The given in the compositions of the invention if solvents used, the same Lö be means that with the previously known composition tongues made of Si-bonded vinyl groups Organopo lysiloxanes, Si-bonded hydrogen containing organo polysiloxanes and the addition of Si-bound water Catalyst promoting aliphatic double bond could be used. Examples of such solvents are petrol, e.g. B. alkane mixtures with a boiling range of 80 ° C to 110 ° C at 1012 mbar (abs.), N-heptane, benzene, Toluene and xylenes, halogenated alkanes with 1 to 6 Carbon atoms such as methylene chloride, trichlorethylene and Perchlorethylene, ethers such as di-n-butyl ether, esters such as Ethyl acetate, and ketones such as methyl ethyl ketone and Cyclohexanone.

If organic solvents are used, they will appropriately in amounts of 10 to 95 wt .-%, based on the Weight of organosilicon compounds (A) used.

The sequence when mixing the components (A), (B), While (C) and optionally (D) is not critical to in practice, however, it has proven effective to use component (C), the catalyst, the mixture of the other components add last.

The crosslinking of the compositions according to the invention follows preferably at 50 ° C to 150 ° C, preferably 70 ° C to 120 ° C. An advantage with the invention Compositions is that rapid cross-linking already low temperatures is achieved. As energy sources for the crosslinking by heating is preferably ovens, e.g. B. Circulating air drying cabinets, heating ducts, heated rollers, heated Plates or heat rays of the infrared range are used.  

The compositions according to the invention can, in addition to Heating also by exposure to ultraviolet light or can be crosslinked by irradiation with UV and IR light. As Ultraviolet light usually becomes one with a wel len length of 253.7 nm used. There is one in the trade Variety of lamps that emit ultraviolet light with a wave emit lengths of 200 to 400 nm, and the ultraviolet light with a wavelength of 253.7 nm preferably emits ren.

The application of the compositions according to the invention surfaces to be made repellent to the sticky substances can be made in any, for the production of coatings liquid substances in a suitable and widely known manner take place, for example by dipping, painting, pouring, Spraying, rolling, printing, e.g. B. by means of an offset graph vur coating device, knife or knife coating or with an air brush.

In the case of the surfaces to be made repellent, that can be treated in the context of the invention, it can any surfaces at room temperature and 1012 Trade mbar (abs.) solid substances. Examples of such Surfaces are those of paper, wood, cork and Plastic films, e.g. B. polyethylene films or polypropylene foils, woven and non-woven cloth made of natural or synthetic fibers or glass fibers, ceramic counter stands, glass, metals, Pa coated with polyethylene pier and cardboard, including asbestos. At the above-mentioned polyethylene can each be Trade high, medium or low pressure polyethylene. At Pa pier can be inferior types of paper, such as absorbent paper current papers, including raw, d. H. not with chemicals lien and / or polymeric natural substances pretreated Kraftpa pier with a weight of 60 to 150 g / m², unsized Pa  piere, papers with low freeness, wood-containing papers, non-calendered or non-calendered papers, papers, which by using a dry smoothing cylinder at ih Manufacturing without further complex measures on one Side are smooth and therefore as "machine smooth on one side Papers ", uncoated papers or made of Papers produced from paper waste, i.e. by so-called Ab fall papers, act. To treat according to the invention paper can of course also be high-quality paper types, such as low-suction papers, glued Pa piere, papers with a high degree of grinding, woodfree papers, kalan third or satin papers, glassine papers, parchment coated papers or pre-coated papers. Also the cardboards can be high or low quality.

The compositions according to the invention are suitable for for example, for the production of separating, covering, and mitlau fer papers, including follower papers, which at the Production of e.g. B. cast or decorative films or Foams, including those made of polyurethane be set. The compositions according to the invention continue to be used, for example, to manufacture Separating, masking and idler cardboards, foils and towels, for finishing the backs of self-adhesive Tapes or self-adhesive foils or the labeled Pages of self-adhesive labels. The invention Compositions are also suitable for the finishing of Packaging material, such as paper, cardboard boxes, Metal foils and barrels, e.g. B. cardboard, plastic, wood or Iron for storage and / or transportation of sticky goods, such as adhesives, sticky foods, e.g. B. cakes, honey, sweets and meat, bitumen, asphalt, greased materials and raw rubber, is or are determined. Another example of the application of the ß compositions is the equipment of vehicles for  Transfer of pressure sensitive adhesive layers in the so-called "Trans fer process ".

The compositions according to the invention are suitable for the manufacture position of the self-adhesive template connected to the release paper materials according to both the off-line process and the in-line process.

example 1 a) Preparation of 1,2,4 tris [2-trichlorosilylethyl-] cyclo hexane

162 g of 1,2,4-trichlorovinylcyclohexane are mixed with 4 mg of Pt in Form of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane Complex, the so-called Karstedt catalyst, which in the following the catalyst corresponds to that according to US-A 3,775,452 (issued November 27, 1973, Bruce D. Karstedt, General Electric Company) is manufactured, offset and on heated to approx. 80 ° C. Over a period of approx. 2 A total of 450 g of trichlorosilane was added dropwise, where under reflux the bottom temperature slowly rises against End of the reaction drops again. You still cook the mixture about 1 hour at reflux and then distilled volatile Components from 3 mPa · s to 100 ° C. You get that Title substance in almost quantitative yield (564 g).

b) Preparation of the Carbosiloxane Crosslinker 1

167 g 1,1,3,3-tetramethyldisiloxane together with 100 g Water and 20 g conc. HCI submitted at room temperature and stirred turbulently. A solution drips out with cooling 71 g 1,2,4-tris [2-trichlorosilylethyl] cyclohexane, the Preparation described above under a) in 24 g Cyclohexane too, the internal temperature not 30 ° C  should exceed. After the stirring of about 1 hour, the aqueous phase is separated off, washed twice with 100 ml water and then once with approx. 10% Sodium carbonate solution. The reaction mixture is at 110 ° C. and 3 mPa.s concentrated. You get 90g of a clear one Silicone oil with a viscosity of 31 mm / s. The²⁹Si NMR Spectrum shows a narrow peak group at -62 ppm for Alkylsiloxy units and at -6 ppm for Hydrogen dimethylsiloxy units with an integral ratio of 1: 2.87. The product has the structure of the formula

the product contains higher molecular weight components, and is free of Cl-Si compounds and 1,1,3,3- Tetramethylsiloxane. It contains exactly 1.0 g atom per 104 g Si-bound hydrogen.

Example 2 a) Preparation of 1,2-bis (trichlorosilyl) ethane

162 vinyl trichlorosilane (where vinyl trichlorosilane from Reaction of acetylene with trichlorosilane in the presence of the Karstedt catalyst is obtained) together with 4 mg Pt in the form of the Karstedt catalyst described in Example 1 is described under a), heated to about 60 ° C. To do this  metered in a total of 150 g of trichlorosilane so that the Reaction mixture remains permanently at reflux temperature. Towards the end of the reaction, the mixture is held by heating another hour at boiling temperature and distilled volatile components in a vacuum at approx. 50.C. It stays approx. 286 g of the title compound in combination with the 1,1- Isomer back. This crystallizes over the course of hours Product and then has a melting point of about 40 ° C.

b) Preparation of the carbosiloxane crosslinker 2

The procedure of Example 1 under b) is repeated with the change that instead of 1,2,4-tris [2- trichlorosilylethyl) cyclohexane a solution of 56 g 1,2- Bis [trichlorosilyl] ethane, the preparation of which under a) is described, is added dropwise in 20 g of cyclohexane. Also the reaction temperature should be kept below 30 ° C. After an hour of additional reaction time at Room temperature and concentration in a vacuum are obtained low viscosity silicone oil with a viscosity of 4 mm² / s 25 ° C in approx. 85% of the theoretical yield. The Integral ratio in the ²⁹Si-NMR spectrum of alkylsiloxy to Hydrogen dimethylsiloxy units is 1: 2.9. The so obtained Carbosiloxane crosslinker has the structure of the formula

and contains exactly 1.0 g atom of Si-bound per 90 g Hydrogen.  

c) Preparation of the carbosiloxane crosslinker 3

The procedure of Example 2 b is repeated with the Modification that instead of only 0.45 val chlorine per presented val Si-bound hydrogen exactly 1.0 val Chlorine in the form of a solution of 123 g 1,2- Bis [trichlorosilyl] ethane in about 40 g of cyclohexane becomes. With the same implementation and refurbishment you get 180 g of a silicone oil with a viscosity of 4.5 mm² / s 25 ° C. The integral ratio in the ²⁹Si-NMR spectrum of Alkylsiloxy to hydrogendimethylsiloxy units is exactly 1  : 2.67. The carbosiloxane crosslinker thus obtained contains pro 92 g exactly 1.0 g atom of Si-bonded hydrogen.

Example 3

100 g of an α, ω-divinyldimethylpolysiloxane with 100 Siloxane units (corresponding to 27 meq c = c) are 0.30 g of the compound of the formula HC≡C-C (CH₃) (OH) -CH₂-CH₂-CH = C (CH₃) ₂, which under the Trade names Dehydrolinalool commercially available from the company Is BASF, and 5.4 g of the carbosiloxane crosslinker 1 are mixed. Add 10.5 mg Pt in the form of a solution from the Karstedt Catalyst, which is described in Example 1 under a), in α, ω-divinyldimethylpolysiloxane with a viscosity of 1000 mm² / s at 25 ° C. The ratio H-Si / C = C is 1.9. At constant temperatures, heat flow / time Curves (DSC) of this mixture were recorded. The results are summarized in Table 1.  

Table 1

Comparative Experiment 1 (VI):

The procedure of Example 3 is repeated with the Modification that 1 3.3 g instead of the carbosiloxane crosslinker a common H-siloxane crosslinker from approx. 40 Hydrogenmethyl and 2 trimethylsily units used becomes. As in Example 3, the ratio is H-Si / C = C 1.9. The results of the DSC curves are in Table 1 summarized.

The comparison shows that although the final sales of the active C = C double bonds is almost the same, the formulation with the carbosiloxane crosslinker the end of the reaction much faster reached. At 80 ° C the peak sharpness is 300 times! Even at 50 ° C the reactivity is considerably higher than at conventional wording.  

Example 4

The formulation of Example 3 is made with a reduced amount Crosslinker repeated so that only exactly 1.0 mol of SiH used per mole of C = C double bonds of the vinyl polymer becomes. The DSC curves were again constant Temperatures recorded. The evaluations are shown in Table 2.

Table 2

Comparative test 2 (V2):

The formula of comparative experiment 1 is reduced Amount of crosslinker repeated, so that only exactly 1.0 mol SiH used per mole of C = C double bond of the vinyl polymer becomes. The results of the DSC curves are in Table 2 summarized.

Because of the lack of SiH excess, everyone reacts Recipes slower than in example 3. The comparison at 80 ° C clearly shows the superiority of the Carbosiloxane-related in terms of speed and Completeness of the reaction.  

Example 5

100 g of the vinylsiloxane polymer from Example 3 are added 0.30 g of dehydrolinalool mixed homogeneously, then 2.9 g of the Carbosiloxane crosslinker 3 stirred. Finally mix 5.2 mg Pt in the form of the Karstedt catalyst from Example 3. The formulation contains 50 ppm Pt and a ratio of HSi / C = C of 1.2.

The freshly prepared mixes are made using a glass stick on satin-absorbent glassine paper (67 g / m²) applied and exactly 3 seconds or 5 seconds in Fan oven exposed to a temperature of 120 ° C. The The substrate reaches approx. 90 ° C. the results are in Table 3 summarized.

Table 3

Comparative experiment 3 (V3):

The procedure of Example 5 is repeated with the Modification that instead of the carbosiloxane crosslinker 3 2.1 g a common H-siloxane crosslinker from approx. 40 Hydrogenmethyl and 2 trimethylsily units (65 g contain 1.0 g atom of Si-bonded hydrogen) used will. As in Example 5, the ratio is H-Si / C = C 1.2. The results are summarized in Table 3.

Claims (8)

1. Containing crosslinkable compositions

• (A) Organosilicon compounds that have residues with aliphatic carbon-carbon multiple bonds
• (B) Si-bonded organosilicon compounds containing hydrogen atoms
• (C) the addition of Si-bonded hydrogen to aliphatic multiple bond-promoting catalysts and optionally
• (D) agents which retard the addition of Si-bonded hydrogen to aliphatic multiple bonds at room temperature,
  characterized in that as (B) Si-bonded hydrogen atoms containing organosilicon compounds containing them
• (a) End units of the general formula H _a R _3-a SiO _1/2 (I) and optionally end units of the general formula R₃SiO _1/2 (I '), where
  R is the same or different and is a monovalent, optionally halogenated hydrocarbon radical free of aliphatic multiple bonds and having 1 to 8 carbon atoms per radical and
  a is 1, 2 or 3,
  with the proviso that at least 50 mol% of the end units are those of the formula (I),
• (b) carbostructure units G (II)
  in which
  G is the same or different, means a divalent to ten-valent hydrocarbon radical with 2 to 30 carbon atoms per radical, which may contain one or more heteroatoms selected from the group consisting of oxygen, boron, silicon, tin or titanium,
  with the proviso that at least two Si atoms are connected to one another via G,
• (c) Units of the general formula and or in which
  R has the meaning given above, b is 0, 1 or 2, with the proviso that b in the formula (III ') is not 2, and
  with the proviso that the units of the formula (III) or (III ′) are connected to the carbostructure units G via the Si atoms
  and if necessary
• (d) Units of the general formula in which
  R has the meaning given above,
  c 0 or 1 and
  d 1 or 2
  and the sum c + d is 1 or 2,
  with the proviso that the units of the formula (IV) are between the units of the formula (III) or (III ') and the end units of the formula (I) or (I'), and
  with the proviso that the organosilicon compounds containing (B) Si-bonded hydrogen atoms contain on average at least 4 Si-bonded hydrogen atoms per molecule.

2. Crosslinkable compositions according to claim 1, characterized in that such (B) Si-bonded hydrogen atoms containing organosilicon compounds are used, which can be produced in a first step by aliphatic multiple bonds containing hydrocarbon compounds having 2 to 30 carbon atoms and one or more heteroatoms selected from the group May contain a group of oxygen, boron, silicon, tin and titanium, with silanes (2) of the general formula HR _b SiX _3-b where R is the same or different and a monovalent, optionally halogenated hydrocarbon radical with 1 to 8, free of aliphatic multiple bonds Carbon atoms means
X may be the same or different, is a halogen atom or a radical of the formula -OR¹, where R¹ is an alkyl radical having 1 to 8 carbon atoms per radical, which may be substituted by an ether oxygen atom, and
b is 0, 1 or 2,
in the presence of catalysts (3) which promote the attachment of Si-bonded hydrogen to aliphatic multiple bonds and excess silanes (2) are removed by distillation,
wherein the ratio of Si-bonded hydrogen in silane (2) to aliphatic double bond in hydrocarbon compound (1) is 1.0 to 2.0 or to aliphatic triple bond in hydrocarbon compound (1) is 2.0 to 4.0 in one second step
the compounds thus obtained which have hydrolysis-capable groups and have silanes (4) of the general formula H _a R _3-a SiZ or siloxanes (5) of the general formula H _a R _3-a SiOSiR _3-a H _a where R has the meaning given above,
Z is a halogen atom or a radical of the formula -OR², where R² is a monovalent hydrocarbon radical having 1 to 8 carbon atoms per radical, which may be substituted by an ether oxygen atom, and
a is 1, 2 or 3,
and water are reacted in the presence of catalysts (6) which promote hydrolysis,
wherein the ratio of Si atoms used in silanes (4) or siloxanes (5) to groups capable of hydrolysis in the compounds obtained from the first step is 0.8 to 5.0,
and optionally in a third step the organosilicon compounds thus obtained containing Si-bonded hydrogen atoms with organopolysiloxanes (7) optionally containing Si-bonded hydrogen atoms
selected from the group consisting of linear organopolysiloxanes containing terminal triorganosiloxy groups, linear organopolysiloxanes containing terminal hydroxyl groups, branched organopolysiloxanes optionally having hydroxyl groups, cyclic organopolysiloxanes and copolymers of diorganosiloxane and monoorganosiloxane units,
with the proviso that the organosilicon compounds (B) thus obtained containing Si-bonded hydrogen atoms have on average at least 4 Si-bonded hydrogen atoms per molecule. 3. Use of the crosslinkable compositions after Claim 1 or 2 for the production of sticky substances repellent coatings. 4. Si-bonded hydrogen atoms
Containing organosilicon compounds

• (a) End units of the general formula H _a R _3-a SiO _1/2 (I) and optionally end units of the general formula R₃SiO _1/2 (I '), where
  R is identical or different and represents a monovalent, optionally halogenated hydrocarbon radical with 1 to 8 carbon atoms per radical and free from aliphatic multiple bonds,
  a is 1, 2 or 3,
• (b) carbostructure units G (II)
  where G is the same or different and is a divalent to ten-valent hydrocarbon radical with 2 to 30 carbon atoms per radical, which may contain one or more heteroatoms selected from the group consisting of oxygen, boron, silicon, tin or titanium,
  with the proviso that at least two Si atoms are connected to one another via G,
• (c) Units of the general formula and or in which
  R has the meaning given above, b is 0, 1 or 2, with the proviso that b in the formula (III ') is not 2, and
  with the proviso that the units of the formula (III) or (III ′) are connected to the carbostructure units G via the Si atoms and, if appropriate
• (d) Units of the general formula in which
  R has the meaning given above,
  c 0 or 1 and
  d 1 or 2
  and the sum c + d is 1 or 2,
  with the proviso that the units of the formula (IV) are between the units of the formula (III) or (III ') and the end units of the formula (I) or (I'), and

with the proviso that the Si-bonded hydrogen atoms having organosilicon compounds on average at least 4 Si-bonded hydrogen atoms per molecule contain. 5. Si-bonded hydrogen atoms Organosilicon compounds according to claim 4, characterized characterized in that b is 0 or 1. 6. A process for the preparation of the Si-bonded hydrogen atoms containing organosilicon compounds according to claim 4, characterized in that in a first step
aliphatic multiple bonds hydrocarbon compounds having 2 to 30 carbon atoms, which may contain one or more heteroatoms selected from the group of oxygen, boron, silicon, tin and titanium, with silanes (2) of the general formula HR _b SiX _3-b where R is equal to or is different and denotes a monovalent, optionally halogenated hydrocarbon radical having 1 to 8 carbon atoms and free of aliphatic multiple bonds,
X may be the same or different, is a halogen atom or a radical of the formula -OR¹, where R¹ is an alkyl radical having 1 to 8 carbon atoms per radical, which may be substituted by an ether oxygen atom, and
b is 0, 1 or 2,
in the presence of catalysts (3) which promote the attachment of Si-bonded hydrogen to aliphatic multiple bonds and excess silanes (2) are removed by distillation,
wherein the ratio of Si-bonded hydrogen in silane (2) to aliphatic double bond in hydrocarbon compound (1) is 1.0 to 2.0 or to aliphatic triple bond in hydrocarbon compound (1) is 2.0 to 4.0 in one second step
the compounds thus obtained which have hydrolysis-capable groups and have silanes (4) of the general formula H _a R _3-a SiZ or siloxanes (5) of the general formula H _a R _3-a SiOSiR _3-a H _a where R has the meaning given above,
Z is a halogen atom or a radical of the formula -OR², where R² is a monovalent hydrocarbon radical having 1 to 8 carbon atoms per radical, which may be substituted by an ether oxygen atom, and
a is 1, 2 or 3,
and water are reacted in the presence of catalysts (6) which promote hydrolysis,
wherein the ratio of Si atoms used in silanes (4) or siloxanes (5) to groups capable of hydrolysis in the compounds obtained from the first step is 0.8 to 5.0,
and optionally in a third step the organosilicon compounds thus obtained containing Si-bonded hydrogen atoms with organopolysiloxanes (7) optionally having Si-bonded hydrogen atoms selected from the group consisting of linear organopoly siloxanes containing terminal triorganosiloxy groups, linear organopolysiloxanes containing terminal hydroxyl groups, branched , optionally hydroxyl-containing organopolysiloxanes, cyclic organopolysiloxanes and copolymers of diorganosiloxane and monoorganosiloxane units, are equilibrated,
with the proviso that the organosilicon compounds thus obtained containing Si-bonded hydrogen atoms have an average of at least 4 Si-bonded hydrogen atoms per molecule 7. The method according to claim 6, characterized in that as hydrocarbon compound (1) 1,2,4-trivinylcyclohexane is used.