DE19525562A1 - Acryloxy gp.-contg. organo:silicon cpds. for prodn. of light-cured coatings - contain acryloxy-substd. aromatic units, formed e.g. by reacting organo:silicon cpds. contg. phenolic gps. with acryloyl chloride in presence of base - Google Patents

Abstract

(Meth)acryloxy gp.-contg. organosilicon (MASi) cpds. with units of formula AaRbSiXcO(4-(a+b-c))/2 (I), in which R = opt. halogenated 1-18 C hydrocarbyl; X = Cl or -OR1; R1 = 1-8 C alkyl, opt. with in-chain ether O; a = 0 or 1; b, c = 0, 1, 2 or 3; a + b + c = not more than 4; A = a gp. of formula (II), in which z = 1, 2, 3, 4 or 5; R2 = linear or branched 1-8 C alkylene, opt. contg. ether, amino, sulphide, ester, amide, urea or urethane gps.; R3 = H or Me; Y = X, CN, N(R4)2, SR4, OCOR4, COOR4, NR4-COR4, CON(R4)2 or NO2; R4 = as for R; with the proviso that each mol. of the cpd. contains at least one gp. A. Also claimed is (i) a process for the prodn. of MASi cpds. by reacting corresp. phenolic cpds. (1) (with B = -R2-Ar, in which Ar = a benzene ring substd. with z OH gps. and 5-z Y gps.) with (meth)acryloyl chloride (2) in presence of base (3) or with (meth)acrylic acid in presence of acid catalysts (4); (ii) compsns. which are crosslinked by irradiation with light, contg. (A) MASi cpds. as above and (B) photo-initiators and/or -sensitisers.

Description

DE-B 23 35 118 (published November 2, 1978, E. R. Martin, SWS Silicones Corp.) or the corresponding one US-A 3,878,263 relates to optionally substituted Organopolysiloxanes containing acrylate groups. The Siloxane polymers can be used as intermediates in the Production of copolymers can be used Organopolysiloxane segments contain and as Coating compounds are used. They can also acrylate-functional siloxane polymers as sizing agents and serve as protective coating compositions for paper and tissue. However, these products are more abhesive to manufacture Coating agent unsuitable. The linear diacrylate-modified polysiloxanes according to DE-B 23 35 118 also have, by definition, alkoxy groups which can be split off hydrolytically and for further Crosslinking of the polysiloxanes with deterioration for a coating compound important elastic properties to lead.

According to US-A 4,503,208 (issued March 5, 1985, Samuel Q. S. Lin et al., Loctite Corporation) become acryloxy groups having organopolysiloxanes in one Hydrosilylation reaction by reaction of Organopolysiloxane with Si-bonded hydrogen Obtain propargyl (meth) acrylate. The one for making the  Propargyl (meth) acrylates used propargyl alcohol a relatively high toxicity, and esterification of propargyl alcohol with (meth) acrylic acid gives poor results Exploit.

From EP-A 130 731 (published January 9, 1985, Samuel Q. S. Lin et al., Loctite Corporation) and from corresponding CA-A 1,242,447 is the implementation of Organopolysiloxane with Si-bonded hydrogen Beta (allyloxy) ethyl methacrylate in the presence of a Hydrosilylation catalyst known. Here are Organopolysiloxanes containing methacryloxy groups. Organopolysiloxanes containing acryloxy groups are through analog implementation not selectively available because the Hydrosilylation on both the acrylic and allyl residues occurs.

In DE-C 38 20 294 (published October 5, 1989, Christian Weitemeyer et al., Th. Goldschmidt AG) or in the corresponding US-A 4,978,726 are new polysiloxanes with (meth) acrylic acid and bonded via SiC groups Monocarboxylic acid ester groups and their use as radiation-curing abhesive coating agents described. The organopolysiloxanes according to the invention are thereby available that epoxy functional organopolysiloxanes first with (meth) acrylic acid and then with a Monocarboxylic acid, which is free from polymerization capable double bonds is implemented in such amounts, that all epoxy groups are esterified. This creates by opening the epoxy ring with (meth) acrylic acid monoester a vicinal hydroxyl group. The products are mostly prepared at 100 ° C for 30 hours, using deep green color. Because of the extreme The acrylate system must have synthesis parameters accordingly are inhibited so that no thermal crosslinking  entry. The (meth) acrylic acid is also at least fourfold excess added after the reaction must be removed by distillation. The for the production of the epoxy-functional polysiloxanes used unsaturated Epoxies vinylcyclohexene oxide and allyl glycidyl ether have one relatively high toxicity. Besides, that is Expert understandable that through the vicinal Hydroxy groups and the associated polar Interactions no stable separation forces at the Achieve use as an abhesive coating agent are.

According to U.S. 4,294,974 (issued October 13, 1981, A.R. Le Boenf, American Optical Corporation) become hydrophilic (Meth) acrylate crosslinkable polysiloxanes are described. These products are more abhesive to manufacture Coating agent unsuitable.

From EP-A 281 718 (published September 14, 1988, E. Cahivenc, M. Gay, Rhone Poulenc) and from the corresponding US-A 4,940,766 is known that Polysiloxanes with hydroxyalkyl groups by transesterification with (Meth) acrylic acid alkyl esters with tin catalysis accordingly be functionalized with (meth) acrylic acid ester groups can.

In U.S. 4,348,454 (published March 2, 1981, R. F. Eckberg, General Electric Company) are (meth) acrylic acid esters modified polysiloxanes by reacting polysiloxanes with alkyl chloride groups and (meth) acrylic acid with addition obtained from bases neutralizing hydrogen chloride.

The object was to have (meth) acryloxy groups To provide organosilicon compounds in one simple process with high selectivity, using  easily accessible raw materials and avoiding the thermal polymerization of (meth) acrylic ester groups and discoloration of the organosilicon compounds can be. There was also the task Organopolysiloxanes containing (meth) acryloxy groups to be provided, which with exposure to light Network radical initiators quickly. The continued to exist Task to have (meth) acryloxy groups To provide organopolysiloxanes that are used for the production of Covers can be used. The task is through solved the invention.

The invention relates to (meth) acryloxy groups having organosilicon compounds with units of formula

where R is identical or different, denotes a monovalent, optionally halogenated hydrocarbon radical having 1 to 18 carbon atoms per radical,
X is the same or different, is a chlorine atom or a radical of the formula -OR¹,
where R¹ is an alkyl radical having 1 to 8 carbon atoms per radical, which can be substituted by an ether oxygen atom,
a 0 or 1,
b 0, 1, 2 or 3,
c 0, 1, 2 or 3
and the sum a + b + c is 4 and
A is a residue of the formula

where z is 1, 2, 3, 4 or 5,
R² is a linear or branched alkylene radical having 1 to 8 carbon atoms, which may optionally contain ether, amine, sulfide, ester, amide, urea and urethane groups,
R³ is a hydrogen atom or a methyl radical and
Y is the same or different, a linear or branched alkyl radical having 1 to 6 carbon atoms per radical,

or -NO₂, where X is the above Has meaning and R⁴ has the meaning of R, with the proviso that at least one radical A per molecule is included.

The invention is also a Process for the preparation of (meth) acryloxy groups having organosilicon compounds characterized in that organosilicon compounds (1) with Units of the formula

where R, X, a, b and c have the meaning given above and
B is a radical of the formula

where R², Y and z have the meaning given above,
with the proviso that at least one radical B is contained per molecule,
with (meth) acrylic acid chloride (2) of the formula

wherein R³ is a hydrogen atom or a methyl radical, are reacted in the presence of bases (3).

The invention relates to a further method for Production of (meth) acryloxy groups Organosilicon compounds characterized in that Organosilicon compounds (1) with units of the formula

where X, a, b and c have the meaning given above and
B is a radical of the formula

where R², Y and z have the meaning given above,
with the proviso that at least one radical B is contained per molecule,
are esterified with (meth) acrylic acids in the presence of acidic catalysts (4).

The organosilicon compounds according to the invention preferably have an average molecular weight of 500 to 1,000,000 g / mol, preferably 5000 to 150,000 g / mol and preferably a viscosity of 10 to 1,000,000 mm² · s ^-1 at 25 ° C, preferably 20 to 100 000 mm² · s ^-1 at 25 ° C.

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 radical; Hexyl residues like that n-hexyl; Heptyl residues, such as the n-heptyl residue; Octyl residues, like the n-octyl residue and iso-octyl residues like the 2,2,4-trimethylpentyl; Nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl residues like that n-dodecyl residue; Octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals, such as the cyclopentyl, cyclohexyl, Cycloheptyl and methylcyclohexyl; Aryl residues, like the phenyl, naphthyl, anthryl and phenanthryl radical;  Alkaryl radicals, such as o-, m-, p-tolyl radicals; 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 halogenated radicals R are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2 ', 2', 2'-hexa fluorisopropyl radical, the heptafluoroisopropyl radical and Halogenaryl radicals, such as the o-, m- and p-chlorophenyl radicals.

Examples of alkyl radicals R¹ are methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert-butyl residues. The methyl and ethyl radicals are preferred. Examples of alkyl radicals R¹, which by a Ether oxygen atom are substituted Methoxyethyl and ethoxyethyl radical.

Examples of radicals R² are alkyl radicals of the formula

and substituted alkyl radicals of the formula

The radical R³ is preferably a hydrogen atom.

Examples of radicals A are those of the formula

In formulas (I) and (II), c is preferably 0.
In formula (I) and (II) is preferred
a on average 0.01 to 1.0,
0.0 to 3.0 on average,
c 0.0 to 3.0 on average and
preferably the sum a + b + c on average 0.1 to 4.0.

The organosilicon ver bonds organopolysiloxanes.

Preferred as having (meth) acryloxy groups Organopolysiloxanes are those of the formula

A _g R _3-g SiO (SiR₂O) _n (SiRAO) _m SiR _3-g A _g (III)

where A and R have the meaning given above, g 0, 1 or 2, n 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 A per molecule is included.  

These are preferred in the methods according to the invention Organosilicon compounds used (1) Organopolysilo xane. Those of the formula are preferred

B _g R _3-g SiO (SiR₂O) _n (SiRBO) _m SiR _3-g B _g (IV)

where B, R, g, n and m have the meaning given above have used in the inventive method.

Examples of radicals B are those of the formula

Examples of bases (3) used in the invention Processes used are amines, such as triethylamine, Triisooctylamine, pyridine, diethylamine, and piperazine and inorganic bases, such as potassium hydroxide, sodium hydroxide, Cesium hydroxide, calcium hydroxide, sodium carbonate, Sodium bicarbonate and sodium methylate.

Stabilizer additives can be advantageous; use radical stoppers such as phenothiazine, methoxyphenol, butylated hydroxytoluene, copper or copper compounds Find.

In the process according to the invention, per mole Hydroxy group in residue B of the organosilicon compound (1) preferably 0.5-12 mol (meth) acrylic acid chloride (2), preferably 0.5-6 mol (meth) acrylic acid chloride (2) and particularly preferably 1-2 mol (meth) acrylic acid chloride (2) used. The in the method according to the invention amine hydrochlorides or salts are formed by Filtration removed.

The bases 3 are preferably used in such amounts used that 0.5 to 6 moles, preferably 1 to 2 moles per mole Hydroxy group in residue B of the organosilicon compound available.  

In the further process according to the invention, per mole Hydroxy group in residue B of the organosilicon compound (1) preferably 0.5-12 mol (meth) acrylic acid, preferably 0.5-6 mol (Meth) acrylic acid and particularly preferably 1-3 moles (Meth) acrylic acid used.

Catalysts (4) which promote esterification can also the same in the method according to the invention Catalysts are used, which have also been used for Promotion of esterification could be used. Both Catalysts (4) are preferably Protonic acids, such as sulfuric acid, hydrogen chloride, Phosphoric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, and so-called acidic soils such as Tonsil and KSF / O.

The catalysts (4) are preferably used in amounts of 0.01 up to 5% by weight, preferably in amounts of 0.1 to 2% by weight, based on the total weight of (meth) acrylic acid and Organosilicon compound (1) used.

The methods of the invention are preferably used in Pressure of the surrounding atmosphere, i.e. around 1020 hPa (abs.) carried out. But you can also at higher or lower pressures. Furthermore, the inventive method preferably in a Temperature from 25 ° C to 150 ° C, preferably 25 ° C to 120 ° C, particularly preferably 25 ° C to 60 ° C, carried out.

In the processes according to the invention, inert organic solvents can also be used. examples for inert organic solvents are toluene, xylene, Octane isomers, butyl acetate and THF.  

Furthermore, can not in the inventive method esterified hydroxy groups of the organosilicon compound (1) by vinyl ether under acid catalysis or by Carboxylating agents, such as acetic anhydride, diketene, Dihydropyran be implemented further.

Of those produced by the processes according to the invention (Meth) acryloxy groups Organosilicon compounds preferably become excess (Meth) acrylic acid chloride (2) or excess (Meth) acrylic acid, excess carboxylating agent and optionally used inert organic Solvent preferably removed by distillation.

Process for the preparation of the inventive Organosilicon compounds (1) used in the process in DE-A 15 95 789 (published February 12, 1970, K.W. Krautz, General Electric Company) or in the corresponding GB-A 1 175 266.

The unsaturated hydroxyphenyl components for the Preparation of the organosilicon compound (1) with the rest B of formula II in a hydrosilylation reaction Hydrosilylation catalysts are present for example under the name eugenol (4-allyl-2-methoxyphenol) can be purchased from Haarmann & Reimer workable and have compared to volatile unsaturated alcohols, such as allyl alcohol or Propargyl alcohol a much lower toxicity. Eugenol in particular is even for the food sector authorized.

The additional functionalized hydroxyphenyl components for the preparation of the organosilicon compound (1) with the B radical of formula II by a nucleophile Substitution reactions are, for example, under the  Name phloroglucin or 3,5-dihydroxybenzoic acid commercially available and also have a low Toxicity.

For the representation of the organosilicon compound (1) with the B radical of formula II by a hydrosilylation reaction are preferably organosilicon compounds with at least one Si-bonded hydrogen each Molecule of the formula

where R has the meaning given above,
e 0 or 1, on average 0.01 to 1.0,
f 0, 1, 2 or 3 on average 0.0 to 3.0 and the sum e + f is not greater than 3.

The organopolysiloxanes with at least one Si-bonded hydrogen atom preferably contain at least 0.04% by weight, preferably 0.1 to 1.6% by weight of Si-bonded hydrogen, and their average viscosity is preferably 5 to 20,000 mm² · s ^-1 at 25 ° C, preferably 10 to 2000 mm² · s ^-1 at 25 ° C, particularly preferably 10 to 500 mm² · s ^-1 at 25 ° C.

Preferred as organopolysiloxanes are at least one Si-bonded hydrogen atom per molecule of the formula

H _h R _3-h SiO (SiR₂O) _o (SiRHO) _p SiR _3-h H _h (VI)

where R has the meaning given above, h 0, 1 or 2, o 0 or an integer from 1 to 1500 and p is 0 or an integer from 1 to 200 is used.  

Unsaturated hydroxyphenyl compounds are used in the Hydrosilylation reaction preferably in such amounts used that 1 to 2 mol, preferably 1.05 to 1.20 mol, unsaturated hydroxyphenyl compound per gram atom Si-bonded hydrogen in the organosilicon compound (V) is present.

In the hydrosilylation reaction, the catalysts which promote the attachment of Si-bonded hydrogen to aliphatic multiple bonds, so-called hydrosilylation catalysts, can be the same catalysts which have hitherto been used to promote the attachment of Si-bonded hydrogen to aliphatic multiple bonds. The catalysts 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, e.g. B. PtCl₄, H₂PtCl₆ _* 6H₂O, Na₂PtCl₄ _* 4 H₂O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including Reaction products from H₂PtCl₆ _* 6H₂O and cyclohexanone, platinum-vinylsiloxane complexes, such as platinum-1,3-divinyl-1,1,3,3-tetramethyldi siloxane complexes with or without content of detectable inorganic halogen, bis- (gamma-picolin) platinum dichloride , Trimethylene dipyridine platinum dichloride, dicyclopentadiene platinum dichloride, dimethyl sulfoxide ethylene platinum (II) dichloride, cyclooctadiene platinum dichloride, norbornadiene platinum dichloride, gammapicolin platinum dichloride, cyclopentadiene platinum dichloride and primary amine or secondary amine products with amine or primary amine dichloride and primary amine aminochemicals with amine or secondary amine products from amine or secondary amine with secondary amine products from 92 434, such as the reaction product of platinum tetrachloride dissolved in 1-octene with sec-butylamine, or ammonium-platinum complexes g according to EP-B 1 10 370.

In the hydrosilylation reaction, the catalyst preferably in amounts of 2 to 200 ppm by weight (Parts by weight per million parts by weight), preferably in Amounts from 5 to 50 ppm by weight, each calculated as elemental platinum and based on the total weight of unsaturated hydroxyphenyl compound and Organosilicon compound with at least one Si-bonded Hydrogen atom used.

The hydrosilylation reaction is preferably carried out under pressure the surrounding atmosphere, i.e. at around 1020 hPa (abs.) performed, but it can also at higher or lower pressures. Furthermore, the Hydrosilylation reaction preferably at one temperature from 25 ° C to 150 ° C, preferably 40 ° C to 100 ° C, carried out.

In the hydrosilylation reaction, inert, organic Solvents can be used, although the use of inert, organic solvents is not preferred. Examples of inert, organic solvents are toluene, Xylene, isophorone, octane isomers, butyl acetate and Isopropanol.

Of those made after the hydrosilylation reaction Organosilicon compounds containing hydroxyphenyl groups (1) is preferably excess unsaturated Hydroxyphenyl compound and optionally used inert organic solvent removed by distillation.  

For the representation of the organosilicon compound (1) with B radical of formula II by a nucleophile Substitution reactions are preferred Organosilicon compounds with at least one Si-linked chloroalkyl group per molecule of the formula

where R² has the meaning given above,
e 0 or 1, average 0.01 to 1.0,
f 0, 1, 2 or 3 on average 0.0 to 3.0 and the sum e + f is not greater than 3.

The organopolysiloxanes with at least one Si-bonded chloroalkyl group preferably contain at least 0.1% by weight, preferably 0.5 to 7.0% by weight of chlorine as Si-bonded chloroalkyl groups and their average viscosity is preferably 5 to 20,000 mm² · s ^-1 at 25 ° C., particularly preferably 10 to 500 mm² · s ^-1 at 25 ° C.

Preferred organopolysiloxanes are at least one Si-linked chloroalkyl group per molecule of the formula

Cl-R² _h R _3-h SiO (SiR₂O) _o (SiRR²-ClO) _p SiR _3-h R²-Cl (VIII),

where R and R² have the meaning given above,
h 0, 1 or 2,
o 0 or an integer from 1 to 1,500 and
p is 0 or an integer from 1 to 200 is used.

Process for producing the organosilicon compounds with at least one Si-bonded chloroalkyl group per molecule, also those of the preferred type are generally known  and for example in US 3,346,405 (issued October 1967, R.V. Viventi, General Electric Company).

Substituted hydroxyphenyl compounds are used in the nucleophilic substitution reaction preferably in such Amounts used that 1 to 2 mol, preferably 1.05 to 1.2 Mol, substituted hydroxyphenyl compound per gram atom Si-alkyl-bonded chlorine in the organosilicon compound (VII) or (VIII) is present.

As more common in nucleophilic substitution Hydrogen chloride neutralizing bases are amines, such as Triethylamine, triisooctylamine, pyridine, diethylamine, Piperazine and inorganic bases such as potassium hydroxide, Sodium hydroxide, cesium hydroxide, calcium hydroxide, Sodium carbonate, sodium hydrogen carbonate and Sodium methylate.

The bases are preferably used in amounts such that 1 to 2 moles, preferably 1.0 to 1.3 moles, per gram atom Si-alkyl-bonded chlorine in the organosilicon compound (VII) or (VIII) are present. Excess base can optionally neutralized with acids after the reaction will.

The nucleophilic substitution reaction is preferably carried out at Pressure of the surrounding atmosphere, i.e. around 1020 h Pa (abs.) performed, but can also at higher or lower pressures. Furthermore, the nucleophilic substitution reaction preferably in a Temperature from 70 ° C to 150 ° C, preferably 80 ° C to 125 ° C, carried out.

In the nucleophilic substitution reaction, inert, organic solvents can also be used. examples for inert organic solvents are toluene, xylene,  Isophorone, butyl acetate, 1,4-dioxane, isopropanol, Glycol monomethyl ether, diethoxyethane and acetonitrile.

After the nucleophilic substitution reaction prepared containing hydroxyphenyl groups Organosilicon compounds (1) are preferred excess substituted hydroxyphenyl compound as well optionally used inert organic Solvent by distillation or by known methods away.

Those obtained by the processes according to the invention Organopolysiloxanes containing (meth) acryloxy groups can with organopolysiloxanes (5) selected from the group consisting of linear, terminal triorganosiloxy groups having organopolysiloxanes, linear, terminal Organopolysiloxanes containing hydroxyl groups, cyclic Organopolysiloxanes and copolymers Diorganosiloxane and monoorganosiloxane units equilibrated will.

Preferably used as a linear, terminal triorganosilo Organopolysiloxanes containing xy groups have those of the formula

R₃SiO (SiR₂O) _r SiR₃

where R has the meaning given above and r is 0 or an integer from 1 to 1500, as a linear organo with terminal hydroxyl groups polysiloxanes of the formula

HO (SiR₂O) _s H

where R has the meaning given above and s is an integer from 1 to 1500, as cyclic organopolysiloxanes those of the formula

(R₂SiO) _t

where R has the meaning given above and t is an integer from 3 to 12,
and as copolymers from units of the formula

R₂SiO and RSiO _3/2

where R has the meaning given above for it puts.

The quantitative ratios of the possibly carried out performed equilibration of organopolysiloxanes (5) and (meth) acryloxy group-containing organopolysiloxanes are only determined by the desired proportion of (Meth) -acryloxy groups in the optionally carried out Equilibration generated by organopolysiloxanes and desired average chain length determined.

When performing an equilibration, if necessary preferably acidic catalysts, which are the equilibration promote, deployed. Examples of such catalysts are Sulfuric acid, phosphoric acid, trifluoromethanoic acid, phosphorus nitride chlorides and solid under the reaction conditions, acidic catalysts, such as acid-activated bleaching earth, acidic Zeolites, sulfonated coal and sulfonated styrene divinyl benzene copolymer. Phosphorus nitride chloros are preferred ride. Phosphorus nitride chlorides are preferably used in quantities from 5 to 1000 ppm by weight (= parts per million), in particular 50 to 200 ppm by weight, based in each case on the total weight of the organosilicon compounds used. The  Use of basic equilibration catalysts is true possible, but not preferred.

If necessary, the equilibration is carried out preferably at 80 ° 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 because used organosilicon compounds in with water immiscible solvent such as toluene.

Before working up the Ge obtained during the equilibration mixed, the catalyst can be rendered ineffective.

The methods of the invention can be batch, semi-con be carried out continuously or continuously.

The (meth) acryloxy groups according to the invention Organosilicon compounds are characterized by their low SiOC content, their fine aromatic smell, their Transparency and their low discoloration. By the Methods according to the invention can contain hydroxyphenyl groups having organosilicon compounds (1) with (Meth) acrylic acid chloride (2) at low temperatures without Risk of thermal polymerization of the (Meth) acrylate groups with short reaction times without Discoloration are implemented. The gentle conditions allow a low content of stabilizer additives, what is known to the person skilled in the art in photochemical Cross-linking often gives rise to inhibition phenomena.

The invention furthermore relates to radiation containing light crosslinkable compositions

• (A) Organopolysiloxanes containing (meth) acryloxy groups and
• (B) Photoinitiators and / or photosensitizers.

The composition that can be crosslinked by irradiation with light gene are used for the production of coatings.

The (meth) acryloxy according to the invention are preferably used group-containing organopolysiloxanes by ultraviolet light cross-linked, such with wavelengths in the range from 200 to 400 nm is preferred. The ultraviolet light can, e.g. B. in xenon, low mercury, mercury high pressure or high pressure mercury lamps. For Networking through light is also one with a wavelength ge from 400 to 600 nm, so-called "halogen light", ge is suitable.

In the crosslinking of the organopolysilo according to the invention Suitable energy sources can also be X-ray, gamma or electron beams or at the same time permanent use of at least two different types act rays. In addition to the high energy Radiation can include heat input, including heat input infrared light. Such warmth drove is in no way necessary and preferably un it remains to reduce the expenditure for energy.

Suitable photoinitiators and / or photosensitizers are optionally substituted acetophenones, Propiophenones, benzophenones, anthraquinones, benziles, Carbazole, xanthones, thioxanthones, fluorenes, fluorenones, Benzoins, naphthalenesulfonic acids, benzaldehydes and Cinnamic acids.

Examples include fluorenone, fluorene, carbazole; Aceto phenone; substituted acetophenones, such as 3-methylacetophenone,  2,2′-dimethoxy-2-phenylacetophenone, 4-methylacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, p-tert-butyltrichloroacetophenone; Propiophenone; substituted Propiophenones, such as 1- [4- (methylthio) phenyl] -2-morpholinepro panon-1, benzophenone; substituted benzophenones, such as Mich lers ketone, 3-methoxybenzophenone, 4,4'-dimethylaminobenzo phenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-di methoxybenzophenone, 4-chloro-4'-benzylbenzophenone; Xanthone; substituted xanthones such as 3-chlorxanthone, 3,9-dichlorxane thon, 3-chloro-8-nonylxanthone; Thioxanthone; substituted Thioxanthones such as isopropylthioxanthone; Anthraquinone; substituted anthraquinones such as chloroanthraquinone and Anthrachino-1,5-disulfonic acid disodium salt; Benzoin; substituted benzoins such as benzoin methyl ether; Benzil; 2-naphthalenesulfonyl chloride; Benzaldehyde; Cinnamic acid. Especially 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino is preferred propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino phenyl) butan-1-one, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, benzene alkyl ether, 2,2-dialk oxy-1-phenylethanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy 2-methyl-1-phenyl-propan-1-one.

Photoinitiators and / or photosensitizers are in the Compositions according to the invention preferably in amounts from 0.01 to 10% by weight, in particular from 0.5 to 5 Weight percent, based in each case on the total weight of the to be used to crosslink organopolysiloxanes.

Examples of surfaces on which the invention Coatings can be applied are those of Pa pier, wood, cork, plastic sheeting, e.g. B. polyethylene films or polypropylene films, ceramic objects, glass, including glass fibers, metals, cardboards, including those made of asbestos, and made of woven and non-woven cloth natural or synthetic organic fibers. application  find the coatings of the invention for example in the Release paper coating.

The application of the invention by irradiation with Light cross-linkable compositions on which to coat the surfaces can be in any, for the production of Coatings made of liquid substances more suitable and often be known manner, for example by diving, streak Chen, pouring, spraying, rolling, printing, z. B. by means of egg ner offset engraving coating device, knife or squeegee layering.

example 1

• a) A solution of 47.2 g eugenol (0.288 mol) in 104.7 g Isopropanol was mixed with 2.1 g (0.020 mol) sodium carbonate added and under nitrogen inerting to 80 ° C. heated up. At this temperature, 3,490 ml (10 ppm Platinum) of a hexachloroplatinic acid catalyst in Isopropanol added. Subsequently, in the course of 30 Minutes 1000 g (0.250 mol SiH) of a polydimethylsiloxane with pendant Si-bonded hydrogen atoms and a viscosity of 282 mm² / s at 25 ° C and that Reaction mixture for 2 hours at a temperature of 90 ° C stirred. Then volatiles were at 120 ° C and a vacuum of 5 mbar. After cooling and subsequent filtration gave a brownish, clear oil with a viscosity of 430 mm² / s and one Hydroxyl number of 14.97 mg KOH / g. Yield: 89.6% (th.) (VS I).
• b) 40.0 g (0.01069 mol of hydroxyl groups) VS I, whose Preparation described above under a), 50.0 g (0.6934 mol) tetrahydrofuran and 1.993 g (0.01069 mol)  Potassium hydroxide (30 wt .-% in methanol) are added Submitted room temperature under protective gas and at 10 minutes 30 ° C stirred. Then it is heated to 40 ° C and becomes 1.258 g (0.01399 mol) acrylic acid chloride slowly added dropwise so that a temperature of 43 ° C is not exceeded. After that is stirred at 40 ° C for 30 minutes and after cooling filtered. In vacuo at 80 ° C to constant weight constricted. 38.65 g (95.25% of theory) of one are obtained clear pale yellow oil (AS I). Example 2
• a) A solution of 292.3 g eugenol (1,780 mol) in 149.2 g Isopropanol was mixed with 3.0 g (0.028 mol) sodium carbonate added and under nitrogen inerting to 80 ° C. heated up. At this temperature, 4,973 ml (10 ppm Platinum) of a hexachloroplatinic acid catalyst in Isopropanol added. Subsequently, in the course of 30 Minutes 1200 g (1,548 mol SiH) of a polydimethylsiloxane with pendant Si-bonded hydrogen atoms and a viscosity of 67 mm² / s at 25 ° C and that Reaction mixture for 2 hours at a temperature of 90 ° C stirred. After that, volatile components were added 120 ° C and a vacuum of 5 mbar away. After cooling and subsequent filtration, a brownish, clear oil with a viscosity of 760 mm² / s and one Hydroxyl number of 58.25 mg KOH / g. Yield: 67.9% (th.) (VS II).
• b) 60.0 g (0.06389 mol of hydroxyl groups) VS II, whose Preparation described above under a), 300.0 g (4.16 mol) tetrahydrofuran and 11.91 g (0.06389 mol) Potassium hydroxide (30 wt .-% in methanol) are added Submitted room temperature under protective gas. 8.67 g (0.0958 mol) acrylic acid chloride are slowly added dropwise and the  Solution was stirred under reflux at 66 ° C for 10 minutes. After this Cooling and subsequent filtration is carried out in vacuo Concentrated 80 ° C to constant weight. 60.55 g are obtained (95.43% of theory) of a light yellow oil (AS II). Example 3
• a) A solution of 64.0 g eugenol (0.390 mol) in 75.5 g Isopropanol was treated with 1.5 g (0.014 mol) sodium carbonate added and under nitrogen inerting to 80 ° C. heated up. At this temperature, 2,516 ml (10 ppm Platinum) of a hexachloroplatinic acid catalyst in Isopropanol added. Subsequently, in the course of 30 Minutes 691.2 g (0.339 mol SiH) of a polydimethylsiloxane with pendant Si-bonded hydrogen atoms and a viscosity of 68.3 mm² / s at 25 ° C and that Reaction mixture for 2 hours at a temperature of 90 ° C stirred. After that, volatile components were added 120 ° C and a vacuum of 5 mbar away. After cooling and subsequent filtration, a brownish, clear oil with a viscosity of 205 mm² / g and one Hydroxyl number of 27.29 mg KOH / g. Yield: 78.8% (th.) (VS III).
• b) 40.0 g (0.01710 mol of hydroxy groups) VS III, whose Preparation described above under a), 20.0 g (0.2774 mol) tetrahydrofuran and 3.84 g (0.01710 mol) Potassium hydroxide (25 wt .-% in methanol) are added Submitted room temperature under protective gas and at 10 minutes 30 ° C stirred. Then the mixture is heated to 40 ° C. and 2.012 g (0.02233 mol) acrylic acid chloride slowly added dropwise so that the temperature of 43 ° C is not exceeded. The mixture is then stirred at 40 ° C for one hour and after  Cooling filtered. In a vacuum at 80 ° C to Constant weight restricted. 38.06 g (93.01% of the Theory) of a clear yellow oil. 35.61 g of the obtained Product with 0.256 g (0.003045 mol) dihydropyran, 100.76 µl (0.52 10-5 mol) of p-toluenesulfonic acid (1% by weight in Tetrahydrofuran) and 5.0 g (0.06934 mol) of tetrahydrofuran added and stirred at room temperature for 12 hours. Then 524.05 ul (0.52 10-5 mol) of dimethylethanolamine (0.1 % By weight in tetrahydrofuran) and 20 minutes Stirred at room temperature, filtered and then in vacuo concentrated at 80 ° C to constant weight. You get 34.44 g (96.71% of theory) of a clear, slightly yellow Oil (AS III). Example 4
• a) A solution of 96.3 g eugenol (0.587 mol) in 109.6 g Isopropanol was mixed with 2.2 g (0.021 mol) sodium carbonate added and under nitrogen inerting to 80 ° C. heated up. At this temperature, 3,653 ml (10 ppm Platinum) of a hexachloroplatinic acid catalyst in Isopropanol added. Subsequently, in the course of 30 Minutes 1000 g (0.510 mol SiH) of one α, ω-Dihydrogenpolydimethylsiloxans with a viscosity of 58 mm² / s metered in at 25 ° C. and the reaction mixture 2 Stirred at a temperature of 90 ° C for hours. After that volatiles at 120 ° C and a vacuum of 5 mbar away. After cooling and then Filtration gave a brownish, clear oil with a Viscosity of 105 mm² / g and a hydroxyl number of 30.14 mg KOH / g. Yield: 86.4% (th.) (VS IV).  
• b) 20.0 g (0.01079 mol of hydroxy groups) VS IV, whose Preparation described above under a), 40.0 g (0.5547 mol) tetrahydrofuran and 2.011 g (0.01079 mol) Potassium hydroxide (30 wt .-% in methanol) are under Shielding gas and 15 minutes at room temperature touched. 1.27 g (0.01403 mol) of acrylic acid chloride slowly added dropwise so that the temperature of 43 ° C does not is exceeded. Then the temperature of approx. 35 ° C held for 30 minutes and after cooling and Filter in a vacuum at 50 ° C to constant weight constricted. 18.95 g (92.08% of theory) of one are obtained almost colorless oil (AS IV). Example 5
• a) A solution of 283.2 g eugenol (1,725 mol) in 103.3 g Isopropanol was mixed with 2.1 g (0.020 mol) sodium carbonate added and under nitrogen inerting to 80 ° C. heated up. At this temperature, 3,282 ml (10 ppm Platinum) of a hexachloroplatinic acid catalyst in Isopropanol added. Subsequently, in the course of 30 Minutes 750 g (1,500 mol SiH) of one α, ω-Dihydrogenpolydimethylsiloxans with a viscosity of 7.8 mm² / s metered in at 25 ° C. and the reaction mixture 2 Stirred at a temperature of 90 ° C for hours. After that volatiles at 120 ° C and a vacuum of 5 mbar away. After cooling and then Filtration gave a brownish, clear oil with a Viscosity of 61 mm² / g and a hydroxyl number of 88.45 mg KOH / g. Yield: 86.4% (th.) (VS V).
• b) 886.0 g (1.4072 mol of hydroxyl groups) VS V, whose Preparation is described above under a) and 886.0 g (12.29 mol) tetrahydrofuran with stirring and protective gas  266.08 g (1.4776 mol) of sodium methylate (30% by weight in Methanol) and then 1 hour at room temperature touched. 165.58 g (1.8294 mol) of acrylic acid chloride slowly added dropwise so that the temperature of 43 ° C does not is exceeded. Then two hours at 30 ° C. stirred and after cooling and filtering in vacuo Concentrated 80 ° C to constant weight. 783.9 g are obtained (81.48% of theory) of a faint orange-yellow clear Oil (AS V).

Example 6

2 g of AS IV, the preparation of which is described in Example 4b, is mixed with 0.06 g (3.65 × 10 ^-4 mol) of the photosensitizer with the trade name Darocure 1173 and applied to a polyethylene film in a layer thickness of 2 μm. The polymer is crosslinked in 2 seconds by irradiation with a medium pressure mercury lamp with an output of 80 mW / cm at a distance of 10 cm under a nitrogen atmosphere. The surface of the coating is non-sticky.

Example 7

2 g of AS V, the preparation of which is described in Example 5b, is mixed with 0.06 g (3.65 × 10 ^-4 mol) of the photosensitizer with the trade name Darocure 1173 (commercially available from Ciba-Geigy) and with applied with a doctor blade in a thickness of 20 µm on a polyethylene film. The polymer is crosslinked in 2 seconds by irradiation with a medium pressure mercury lamp with an output of 80 mW / cm at a distance of 10 cm under a nitrogen atmosphere. The surface of the coating is non-sticky.

Example 8

2 g of AS I, the preparation of which is described in Example 1b, is mixed with 0.06 g (2.0 × 10 ^-4 mol) of the photosensitizer with the trade name Irgacure 369 (commercially available from Ciba Geigy) in 0.5 g of toluene mixed and applied to a paper with the tradename Bosso Buxil using a doctor blade in a thickness of 20 µm. The polymer is crosslinked in one second by irradiation with a medium pressure mercury lamp with an output of 80 mW / cm at a distance of 10 cm under a nitrogen atmosphere. The surface of the coating is non-sticky.

Claims (8)

1. (Meth) acryloxy group-containing organosilicon compounds with units of the formula where R is identical or different, denotes a monovalent, optionally halogenated hydrocarbon radical having 1 to 18 carbon atoms per radical,
X is the same or different, is a chlorine atom or a radical of the formula -OR¹,
where R¹ is an alkyl radical having 1 to 8 carbon atoms per radical, which can be substituted by an ether oxygen atom,
a 0 or 1,
b 0, 1, 2 or 3,
c 0, 1, 2 or 3
and the sum a + b + c is 4 and
A is a residue of the formula where z is 1, 2, 3, 4 or 5,
R² is a linear or branched alkylene radical having 1 to 8 carbon atoms, which may optionally contain ether, amine, sulfide, ester, amide, urea and urethane groups,
R³ is a hydrogen atom or a methyl radical and
Y is the same or different, a linear or branched alkyl radical having 1 to 6 carbon atoms per radical, or -NO₂, where X has the meaning given above and R⁴ has the meaning of R, with the proviso that at least one radical A is contained per molecule. 2. (meth) acryloxy groups Organosiliciumverbin compounds according to claim 1, characterized in that they are organopolysiloxanes of the formula A _g R _3-g SiO (SiR₂O) _n (SiRAO) _m SiR _3-g A _g (III) wherein R is or is different, is a monovalent, optionally halogenated hydrocarbon radical having 1 to 18 carbon atoms per radical,
A is a residue of the formula where z is 1, 2, 3, 4 or 5,
R² is a linear or branched alkylene radical having 1 to 8 carbon atoms, which may optionally contain ether, amine, sulfide, ester, amide, urea and urethane groups,
R³ is a hydrogen atom or a methyl radical and
Y is the same or different, a linear or branched alkyl radical having 1 to 6 carbon atoms per radical, or -NO₂, where X has the meaning given above and R⁴ has the meaning of R, with the proviso that at least one radical A is contained per molecule. 3. (Meth) acryloxy group-containing organosilicon compounds according to claim 1 or 2, characterized in that A is a radical of the formula is. 4. A process for the preparation of (meth) acryloxy groups on pointing organosilicon compounds according to claim 1, 2 or 3, characterized in that organosilicon compounds (1) with units of the formula where R is identical or different, denotes a monovalent, optionally halogenated hydrocarbon radical having 1 to 18 carbon atoms per radical,
X is the same or different, is a chlorine atom or a radical of the formula -OR¹,
where R¹ is an alkyl radical having 1 to 8 carbon atoms per radical, which can be substituted by an ether oxygen atom,
a 0 or 1,
b 0, 1, 2 or 3,
c 0, 1, 2 or 3
and the sum a + b + c is 4 and
B is a radical of the formula where z is 1, 2, 3, 4 or 5,
Y is the same or different, a linear or branched alkyl radical having 1 to 6 carbon atoms per radical, or -NO₂, where X has the meaning given above and R⁴ has the meaning of R,
with the proviso that at least one radical B is contained per molecule,
with (meth) acrylic acid chloride (2) of the formula wherein R³ is a hydrogen atom or a methyl radical, are reacted in the presence of bases (3). 5. A process for the preparation of (meth) acryloxy groups on pointing organosilicon compounds according to claim 1, 2 or 3, characterized in that organosilicon compounds (1) with units of the formula where R is identical or different, denotes a monovalent, optionally halogenated hydrocarbon radical having 1 to 18 carbon atoms per radical,
X is the same or different, is a chlorine atom or a radical of the formula -OR¹,
where R¹ is an alkyl radical having 1 to 8 carbon atoms per radical, which can be substituted by an ether oxygen atom,
a 0 or 1,
b 0, 1, 2 or 3,
c 0, 1, 2 or 3
and the sum a + b + c is 4 and
B is a radical of the formula where z is 1, 2, 3, 4 or 5,
Y is the same or different, a linear or branched alkyl radical having 1 to 6 carbon atoms per radical, or -NO₂, where X has the meaning given above and R⁴ has the meaning of R,
with the proviso that at least one radical B is contained per molecule,
are esterified with (meth) acrylic acid in the presence of acidic catalysts (4). 6. The method according to claim 4 or 5, characterized in net that the (meth) acryloxy groups thus obtained have send organopolysiloxanes with vinyl ethers Acid catalysis or implemented with carboxylating agents will. 7. Containing crosslinkable compositions by irradiation with light

• (A) (Meth) acryloxy group-containing organopolysiloxanes according to Claim 1, 2 or 3 and
• (B) Photoinitiators and / or photosensitizers.

8. Use of the compositions according to claim 7 for Manufacture of coatings.