DE3707908A1 - (Meth)acrylates of siloxanes containing tricyclodecane groups - Google Patents

Abstract

The novel (meth)acrylates of siloxanes containing tricyclodecane groups can be prepared by reaction of poly(hydroxymethyltricyclo-[5.2.1.0<2,6>]decanyl)siloxanes or their alkylene oxide adducts with (meth)acrylic acid or an isocyanatoalkyl (meth)acrylate. The novel compounds can be employed as monomers in dental materials.

Description

The invention relates to (meth) acrylic acid esters of Siloxanes containing tricyclodecane groups, process for their preparation and their use as monomers in dental materials.

From DE-A 29 22 932 are tooth filling materials known from hydrolysates of 3-methacryloyloxypropyl trialkoxysilanen be produced.

DE-A 30 38 153 describes a prosthesis base material described, the methyl methacrylate, a silane compound such as 3-methacryloyloxypropyl-triethoxysilane and an unsaturated carboxylic acid is obtained.

The inadequate mechanical properties of the known materials made of polysiloxanes, however, preclude their use as a matrix in dental materials in practice.

There were new (meth) acrylic acid esters of tricyclodecane groups containing siloxanes of the formula

in the

R¹ and R² are the same or different and are hydrogen, lower alkyl, halogen or trifluoromethyl, R³ is lower alkyl, cycloalkyl, cycloalkylalkyl or optionally substituted aryl or aralkyl, Z for the group stands in the

R¹² and R¹³ are the same or different and are hydrogen or methyl,
p stands for a number from 0 to 20 and
Q represents a single bond, a radical of the formula

means in the
W represents an alkylene chain,
or a residue of the formula

means in the
E is a divalent, straight-chain or branched aliphatic radical having 2 to 24 carbon atoms, an aromatic radical having 6 to 26 carbon atoms, an araliphatic radical having 7 to 26 carbon atoms or a cycloaliphatic radical having 6 to 26 carbon atoms, the aliphatic, aromatic, araliphatic and / or cycloaliphatic radicals can contain 1 or 2 oxygen bridges, and several of the aliphatic, aromatic, araliphatic and / or cycloaliphatic radicals can be connected via optionally substituted methylene groups, and
G denotes a divalent straight-chain or branched aliphatic hydrocarbon radical with 3 to 15 carbon atoms, which may optionally contain 1 to 3 oxygen bridges and may optionally be substituted by 1 to 4 additional (meth) acryloyloxy radicals,
A stands for a siloxane chain consisting of m structural elements of the formula

and the end group

consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are the same or different and are lower alkyl, cycloalkyl, cycloalkylalkyl and optionally substituted aryl or aralkyl,
the radicals R⁵, R⁷ and R⁸ also for the group

in the
R¹, R² and Z have the meaning given above,
stand,
R¹⁰ represents lower alkyl and
wherein the sum of the structural elements m independently of one another stands for a number from 0 to 600, and
B can have the same meaning as A,
where the radicals R⁴ to R¹⁰ in the chains A and B can be different,
or stands for lower alkyl,
found.

The new (meth) acrylic acid esters of tricyclodecane groups containing siloxanes result after the polymerization Plastics that meet the requirements for dental materials in practice. In particular, they show  very low polymerization shrinkage and excellent mechanical properties and high stability versus physical and chemical degradation in the oral environment. The monomers also show low siloxane content e.g. B. as a disiloxane, surprisingly a low viscosity.

In the context of the present invention, the substituents generally the following meaning:

Lower alkyl can be for a straight chain or branched Alkyl radical having 1 to about 6 carbon atoms. For example, methyl, ethyl, n-propyl, iso- Propyl, n-butyl, iso-butyl, n-pentyl, iso-pentyl, n- Called hexyl and iso-hexyl. Preferred lower alkyl radicals are methyl and ethyl.

Halogen may be fluorine, chlorine, bromine or iodine, preferred Fluorine or chlorine.

Cycloalkyl can be a cyclic, preferably monocyclic, Hydrocarbon residue with 5 to 7 carbon atoms stand. For example, cyclopentyl, Cyclohexyl and Cycloheptyl called. Are preferred Cyclopentyl and cyclohexyl.

Cycloalkyl-alkyl can represent a radical of 6 to 13 carbon atoms stand, being a straight chain or branched Alkyl radical (C₁ to C₆) by a cycloalkyl radical (C₅ to C₇) may be substituted. For example be cyclohexylmethyl, 2-cyclohexyl-1-ethyl, cycloheptylmethyl and called 2-cycloheptyl-1-ethyl. Prefers are cyclohexylmethyl, 2-cyclohexyl-1-ethyl.  

Aryl can be used for an aromatic hydrocarbon residue have 6 to 12 carbon atoms. For example phenyl, nephthyl and biphenyl may be mentioned. Prefers is phenyl.

Aralkyl can represent a residue of 7 to 18 carbon atoms stand, being a straight chain or branched Alkyl radical (C₁ to C₆) by an aromatic radical (C₆ to C₁₂) can be substituted. For example Benzyl, phenyl-ethyl and phenyl-propyl called. Prefers is benzyl.

The aryl and aralkyl radicals can optionally be substituted be. Examples include substituents Lower alkyl (C₁ to about C₆), aryl (C₆ to C₁₂) and Halogen, preferably fluorine and chlorine.

The siloxane chain (A) consists of m structural elements

and the end group

wherein the substituents R⁴ to R¹⁰ have the meaning given above to have.  

The structural elements can be distributed statistically or combined into larger structural areas (blocks) be. It is also possible that the siloxane chain is only made of one type of structural elements.

An alkylene chain (W) generally represents one double-bonded, straight-chain or branched hydrocarbon residue with 2 to 10 carbon atoms. Prefers become alkylene chains with 2 to 6 carbon atoms. For example, the following are alkylene chains called: ethylene, propylene, iso-propylene, 1-methylpropylene- (1,3), 1,2-dimethyl-propylene- (1,3).

A divalent, straight-chain or branched aliphatic radical E can be a hydrocarbon radical having 2 to 24 carbon atoms, preferably 2 to 12 carbon atoms. The following divalent aliphatic radicals may be mentioned, for example:
Ethylene, propylene, 1,4-tetramethylene, 1,6-hexamethylene or 2,2,4-trimethyl-1,6-hexamethylene and isomers.

A divalent aromatic radical E can be a hydrocarbon radical with 6 to 26, preferably 6 to 18, Mean carbon atoms. For example, the following are called aromatic residues:

A divalent araliphatic radical E can be a hydrocarbon radical with a straight chain or branched aliphatic and an aromatic part with 7 to 20 carbon atoms, the aromatic Part preferably 6 to 12 and the aliphatic preferred Contains 1 to 8 carbon atoms. For example the following araliphatic radicals are mentioned:

A divalent cycloaliphatic radical E can be one Hydrocarbon residue with 6 to 26, preferably 6 to 14 Mean carbon atoms. For example called:

It is also possible for several (preferably 1 to 3) of the aromatic, araliphatic and / or cycloaliphatic radicals via optionally substituted Methylene groups are connected.  

Optionally substituted methylene groups can for example the groups

be.

A divalent hydrocarbon residue G can be a straight chain or branched aliphatic hydrocarbon with 3 to 15 carbon atoms, preferably 3 to 10, carbon atoms. The rest G can optionally 1 to 3 oxygen bridges, preferably 1 to 2 Oxygen bridges included. It is also possible that the rest G by 1 to 4, preferably 1 to 2 (meth) - acrylate radicals is substituted. For example the following leftovers:

In general, the siloxane chain consists of a total of 0 to 600, preferably 0 to 200, particularly preferably 0 to 50, structural elements (m) . In the event that the number of structural elements (m) is 0 and B represents lower alkyl, the siloxane chain consists only of the end group (disiloxane).

A substitution of 0.5 to 100 mol%, particularly 10 to 100 mol% of all silicon atoms with tricyclo [5.2.1.0 ^2,6 ] decanyl groups is preferred for the processes according to the invention.

Are preferred within the scope of the present invention (Meth) acrylic acid ester of tricyclodecane groups containing siloxanes of the formula

in the

R¹ and R² are the same or different and are hydrogen, lower alkyl, halogen or trifluoromethyl, R³ is lower alkyl, cycloalkyl (C₅ to C₇), cycloalkylalkyl (C₆ to C₁₃) or optionally substituted aryl (C₆ to C₁₂) or aralkyl (C₇ to C₁₈) , Z for the group stands in the

R¹² and R¹³ are the same or different and are hydrogen or methyl,
p stands for a number from 0 to 20 and
Q represents a single bond or a radical of the formula

means in the
W represents an alkylene chain with 2 to 10 carbon atoms,
or a residue of the formula

means in the
E is a divalent, straight-chain or branched aliphatic radical with 2 to 12 carbon atoms, an aromatic radical with 6 to 18 carbon atoms, or a cycloaliphatic radical with 6 to 14 carbon atoms, the aliphatic, aromatic and / or cycloaliphatic radicals containing 1 or 2 oxygen bridges can, and wherein several of the aliphatic, aromatic, and / or cycloaliphatic radicals can be connected via optionally substituted methylene groups, and
G denotes a divalent straight-chain or branched aliphatic hydrocarbon radical with 3 to 10 carbon atoms, which may optionally contain 1 to 3 oxygen bridges and may optionally be substituted by 1 to 2 additional (meth) acryloyloxy radicals,
A stands for a siloxane chain consisting of m structural elements of the formula

and the end group

consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are the same or different and are lower alkyl, cycloalkyl (C₅ to C₇), cycloalkyl-alkyl (C₆ to C₁₃) and optionally substituted aryl (C₆ to C₁₂) or aralkyl (C₇ to C₁₈) ,
the radicals R⁵, R⁷ and R⁸ also for the group

in the
R¹, R² and Z have the meaning given above,
stand,
R¹⁰ represents lower alkyl and
where the sum of the structural elements m independently of one another stands for a number from 0 to 200, and
B can have the same meaning as A,
where the radicals R⁴ to R¹⁰ in the chains A and B can be different,
or stands for lower alkyl.

(Meth) acrylic acid esters are also particularly preferred of siloxanes containing tricyclodecane groups of the formula

in the

R¹ and R² are the same or different and are hydrogen or lower alkyl, R³ lower alkyl, cycloalkyl (C₅ to C₇), cycloalkyl-alkyl (C₆ to C₁₀) or optionally substituted Aryl (C₆ to C₁₁) or aralkyl (C₇ to C₁₁) means For the group

stands in the

R¹² and R¹³ are the same or different and are hydrogen or methyl,
p represents a number from 0 to 4 and
Q represents a single bond or a radical of the formula

means in the
W represents an alkylene chain with 2 to 6 carbon atoms,
or a residue of the formula

means in the
E is a divalent, straight-chain or branched aliphatic radical having 2 to 8 carbon atoms or a cycloaliphatic radical having 6 to 14 carbon atoms, and
G denotes a divalent straight-chain or branched aliphatic hydrocarbon radical having 3 to 10 carbon atoms, which may optionally contain 1 oxygen bridge and may optionally be substituted by 1 or 2 additional (meth) -acryloyloxy radicals,
A stands for a siloxane chain consisting of m structural elements of the formula

and the end group

consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are lower alkyl, cycloalkyl (C₅ to C₇), cycloalkylalkyl (C₆ to C₁₀) and optionally substituted aryl (C₆ to C₁₁) or aralkyl (C₇ to C₁₁) ,
the radicals R⁵, R⁷ and R⁸ also for the group

in the
R¹, R² and Z have the meaning given above,
stand,
R¹⁰ represents lower alkyl and
where the sum of the structural elements m independently of one another stands for a number from 0 to 200, and
B can have the same meaning as A,
where the radicals R⁴ to R¹⁰ in the chains A and B can be different,
or stands for lower alkyl.

For example, the following are (meth) acrylic acid esters of siloxanes containing tricyclodecane groups called:  

There has also been a process for making (meth) acrylic acid esters of tricyclodecane groups Siloxanes of the formula

in the

R¹ and R² are the same or different and are hydrogen, Mean lower alkyl, halogen or trifluoromethyl, R³ lower alkyl, cycloalkyl, cycloalkyl-alkyl or optionally substituted aryl or aralkyl means For the group

stands in the
R¹² and R¹³ are the same or different and are hydrogen or methyl,
p stands for a number from 0 to 20 and
Q represents a single bond or a radical of the formula

means in the
W represents an alkylene chain,
or a residue of the formula

means in the
E is a divalent, straight-chain or branched aliphatic radical having 2 to 24 carbon atoms, an aromatic radical having 6 to 26 carbon atoms, an araliphatic radical having 7 to 26 carbon atoms or a cycloaliphatic radical having 6 to 26 carbon atoms, the aliphatic, aromatic, araliphatic and / or cycloaliphatic radicals can contain 1 or 2 oxygen bridges, and several of the aliphatic, aromatic, araliphatic and / or cycloaliphatic radicals can be connected via optionally substituted methylene groups, and
G denotes a divalent straight-chain or branched aliphatic hydrocarbon radical with 3 to 15 carbon atoms, which may optionally contain 1 to 3 oxygen bridges and may optionally be substituted by 1 to 4 additional (meth) acryloyloxy radicals,
A stands for a siloxane chain consisting of m structural elements of the formula

and the end group

consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are the same or different and are lower alkyl, cycloalkyl, cycloalkylalkyl and optionally substituted aryl or aralkyl,
the radicals R⁵, R⁷ and R⁸ also for the group

in the
R¹, R² and Z have the meaning given above,
stand,
R¹⁰ represents lower alkyl and
wherein the sum of the structural elements m independently of one another stands for a number from 0 to 600, and
B can have the same meaning as A,
where the radicals R⁴ to R¹⁰ in the chains A and B can be different,
or stands for lower alkyl,
found, which is characterized in that poly [hydroxy (alkyleneoxy) methyl-tricyclo- [5.2.1.0 ^2.6 ] - decanyl] -siloxanes of the formula

in the
R¹, R², R³, R¹³, p , A and B have the meaning given above,
for the case of the preparation of compounds in which Q represents a single bond with a (meth) acrylic acid derivative of the formula

in the
R¹² has the meaning given above, and
R¹⁴ represents hydroxy, chlorine, methoxy, ethoxy or (meth) - acryloyloxy, esterified,
or in the case of the preparation of compounds in which Q represents a radical of the formula

stands in the
W represents an alkylene chain,
with an isocyanate of the formula

in the
R¹² and W have the meaning given above,
reacted in an inert solvent,
or in the case of the preparation of compounds in which Q represents a radical of the formula

stands in the
E is a divalent, straight-chain or branched aliphatic radical with 2 to 24 carbon atoms, an aromatic radical with 6 to 26 carbon atoms, an araliphatic radical with 7 to 26 carbon atoms or a cycloaliphatic radical with 6 to 26 carbon atoms, the aliphatic, aromatic, araliphatic and / or cycloaliphatic radicals can contain 1 or 2 oxygen bridges, and a plurality of the aliphatic, aromatic, araliphatic and / or cycloaliphatic radicals can be connected via optionally substituted methylene groups, and
G is a divalent straight-chain or branched aliphatic hydrocarbon radical with 3 to 15 carbon atoms, which may optionally contain 1 to 3 oxygen bridges and may optionally be substituted by 1 to 4 additional (meth) acryloyloxy radicals,
with the addition product of 1 mol of a diisocyanate of the formula

O = C = N-E-N = C = O (V)

in the
E has the meaning given above,
and 1 mole of a hydroxyalkyl (meth) acrylic acid ester of the formula

in the
G and R¹² have the meaning given above,
where a stoichiometric equivalence between the NCO groups of the adduct from V and VI and the OH groups of II is said to exist,
reacted in an inert solvent.

The process according to the invention can be illustrated by the following formula are explained:

1 + 2 CH₂ = CH-COOH

Poly [hydroxy (alkyleneoxy) methyl (tricyclo [5.2.1.0 ^2.6 ] decanyl] siloxanes of the formula

in the

R¹ and R² are the same or different and are hydrogen, lower alkyl, halogen or trifluoromethyl, R³ is lower alkyl, cycloalkyl, cycloalkyl-alkyl or optionally substituted aryl or aralkyl, R¹³ is hydrogen or methyl, p is an integer from 0 to 20, for a siloxane chain stands, which consists of m structural elements of the formula and the end group consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are the same or different and are lower alkyl, cycloalkyl, cycloalkylalkyl and optionally substituted aryl or aralkyl,
the radicals R⁵, R⁷ and R⁸ also for the group in the
R¹, R², R¹³ and p have the meaning given above,
stand,
R¹⁰ represents lower alkyl and
where the number of structural elements m independently of one another each represents a number from 0 to 600, and B can have the same meaning as A,
where the radicals R⁴ to R¹⁰ in the chains A and B can be different,
or stands for lower alkyl,

can be prepared by using a tricyclo [5.2.1.0 ^2,6 ] decenyl) silane of the formula

in the
R¹, R² and R³ have the meaning given above,
X represents a hydrolyzable radical,
Y stands for lower alkyl, and
n represents the numbers 0 or 1,

in the presence of water and a condensation catalyst first homocondensed or with diorganosilanes of the formulas

cocondensed
and then, if n is 0, with triorganosilanes of the formula

where X, R⁴, R⁶, R⁹ and R¹⁰ have the meaning given above, and
where R⁵, R⁷, R⁸ are the same or different and are lower alkyl, cycloalkyl, cycloalkylalkyl and optionally substituted aryl and aralkyl or for the group

in which R¹ and R² have the meaning given above,
stand, implements
wherein the molar ratio of the silanes VII to the silanes X after the homocondensation of the silanes VII or after the cocondensation of the silanes VII with the silanes VIII and / or IX is greater than or equal to 0.5 and wherein for the cocondensation m mol of the silanes VIII and / or IX, based on 1 mol of silane of the formula VII,
where m has the meaning given above,
and then reacting the poly (tricyclo [-5.2.1.0 ^2.6 ] decenyl) siloxane obtained with carbon monoxide and hydrogen (in the ratio of about 1: 1) in the presence of a hydroformylation catalyst,
the formyl derivative obtained is reduced in a further step to the hydroxymethyl derivative, and optionally (for p <0) the hydroxymethyl derivative obtained with p moles based on 1 mole of hydroxymethyl groups of an alkylene oxide of the formula

in which
R¹³ and p have the meaning given above,
in the presence of a basic catalyst.

The manufacturing process can be carried out by the following Reaction scheme are explained:  

Tricyclo- [5.2.1.0 ^2,6 ] -decenyl-silanes (VII) are known per se (Chem. Abstr. 94, 15 799 and 85, 143 184, 77, 88 573). The tricyclo- [5.2.1.0 ^2,6 ] -decenyl silanes contain a hydrolyzable residue which is split off during the condensation. Examples of hydrolyzable radicals are halogens (chlorine, bromine and iodine, preferably chlorine), alkoxy (C₁ to C₆, preferably methoxy and ethoxy), acyloxy, dialkylamino (alkyl preferably methyl and ethyl).

The tricyclo- [5.2.1.0 ^2,6 ] -decenyl-silanes can, for example, by reacting 3 (4), 8-tricyclo- [5.2.1.0 ^2,6 ] -decadiene derivatives with corresponding hydrogen silanes in the presence of hydrosilylation catalysts, e.g. . B. H₂PtCl₆, are produced.

Diorganosilanes (VIII, IX) are commercially available or, if R ^{5 ′} and R ^{7 ′ are} a tricyclo- [5.2.1.0 ^2,6 ] -decenyl radical, by reacting 3 (4), 8-tricyclo [5.2.1.0 ^2,6 ] decadiene derivatives with hydrogen silanes, e.g. B. methyldichlorosilane. For example, the following diorganosilanes are mentioned:
Dimethyldichlorosilane, dimethoxydimethylsilane, ethylmethyldichlorosilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, (2-cyclohexylethyl-1-yl) ethyl dichlorosilane, dibutyl dimethoxy silane, di-n-propyldichlorsilan, methyl-tricyclo [5.2.1.0 ^2,6] decenyl dichlorosilane , Methyl-tricyclo [5.2.1.0 ^2.6 ] decenyldimethoxysilane.

Triorganosilanes (X) are commercially available or, if R ^{8 'is} a tricyclo [5.2.1.0 ^2,6 ] decenyl radical, can be prepared analogously in the manner described for VIII and IX.

Examples include the following triorganosilanes: trimethylchlorosilane, trimethylmethoxysilane, diethylpropylethoxysilane, diphenylmethylmethoxysilane, tricyclo [5.2.1.0 ^2.6 ] decenyldimethylchlorosilane, tricyclo [5.2.1.0 ^2.6 ] decenyldimethylmethoxysilane.

Condensation catalysts (W. Noll, chemistry and technology the Silicone, Verlag Chemie [1968]) for homo / cocondensation are, for example, hydrohalic acids, Sulfuric acid, alkali metal salts, alkali and Alkaline earth metal hydroxides, carbonates and oxides, trifluoroacetic acid, Perfluorobutanesulfonic acid and acetic acid.

The homo / co-condensation is generally at normal pressure and at temperatures from -20 to + 80 ° C with a Excess water in the presence of the condensation catalyst, the z. B. with halosilanes during hydrolysis is formed in situ. The homo (co) condensation can also be in the presence of solvents, which are miscible or immiscible with water will. Examples are the following solvents called: toluene, dichloromethane, chloroform, diethyl ether, Tetrahydrofuran, methyl ethyl ketone, acetone, Hexane, ethanol, isopropanol, methanol, ethyl acetate.  

After the homocondensation of tricyclo [5.2.1.0 ^2,6 ] decenylsilanes VII, in the event that n is 0, and after the cocondensation with diorganosilanes VIII and / or IX, the aqueous phase is separated off and the reaction mixture is reacted with acidic or basic catalysts of the type mentioned above, preferably perfluorobutanesulfonic acid, equilibrated in an inert solvent. The initially formed mixtures of cyclic and linear polysiloxanes are converted into mixtures of linear polysiloxanes with higher uniformity and higher molecular weight. The course of the reaction can e.g. B. be followed by measuring the viscosity.

After the equilibration step, predominantly arise Polysiloxanes with silanol end groups. These polysiloxanes are then in the presence of triorganosilanes X. from condensation catalysts to existing ones Convert silanol end groups to triorganosiloxy end groups.

However, it is also possible to add a triorganosilane X directly the homo- / co-condensation, where it as Chain terminator acts as a triorganosiloxy end group into which polysiloxane is introduced.

In the event that n in formula VII is 1, ie the tricyclo [5.2.1.0 ^2,6 ] decenylsilane VII has only one hydrolyzable group, the reaction with triorganosilanes X is unnecessary, since from such a silane VII, in which n is 1, in the case of homocondensation the corresponding disiloxane is formed and in the case of co-condensation with diorganosilanes of the formula VI and / or IX, polysiloxanes are formed which already contain the silyl radical of silane VII as the end group.

The further reaction of the poly- (tricyclo [5.2.1.0 ^2,6 ] -decenyl) compounds to the formyl derivatives is generally carried out in the presence of a hydroformylation catalyst using carbon monoxide and hydrogen. Carbon monoxide and hydrogen are usually used in a ratio of about 1 to 1.

Hydroformylation catalysts (Houben-Weyl, Methods of Organic Chemistry, Vol. E3, p. 180 ff. [1983]) generally used rhodium catalysts. For example, the so-called Wilkinson's Complex or the bis (dicarbonylchlororhodium). In particular preference is given to a heterogeneous catalyst which contains, for example, 5% rhodium on aluminum oxide.

In general, 10 ^-3 to 10 ^-7 mol, preferably 10 ^-3 to 10 ^-5 mol of rhodium, based on one mol of tricyclo- [5.2.1.0 ^2,6 ] decenyl groups, is used.

The hydroformylation is generally in the pressure range from 30 to 250 bar carbon monoxide / hydrogen and in the temperature range from 50 to 180 ° C, preferably 70 to 150 ° C carried out.

The hydroformylation can preferably in the presence of a Solvent are carried out. As a solvent Examples include methylcyclohexane, toluene and xylene called.  

The formyl compound according to the invention obtained can be in in a manner known per se, for example by removal the solvent and cleaning with an adsorbent, be isolated.

The hydrogenation of the formyl compounds to the alcohol is in the presence of a hydrogenation catalyst a hydrogen pressure of 5 to 250 bar, preferably from 50 to 200 bar and in the temperature range from 20 to 180 ° C, preferably from 60-150 ° C in inert solvents, e.g. B. saturated hydrocarbons or aliphatic Alcohols. As saturated hydrocarbons Examples include: cyclohexane, n-hexane, n-heptane, methylcyclohexane. Suitable alcohols are lower alcohols, e.g. B. methanol, ethanol, isopropanol, n-propanol, n-butanol.

Aliphatic alcohols are preferred as solvents.

The hydrogenation catalyst is, for example Transition metal, which is in the form of its salts, complexes or is used in the form of a supported catalyst. Examples are the following hydrogenation catalysts called: Tris (triphenylphosphine) chloro-rhodium, Raney- Nickel, bis (dicarbonylchlororhodium), 5% rhodium Alumina.

Optionally, activators can be added to accelerate the hydrogenation. Suitable activators are, for example: sodium hydroxide, triethylamine, tri-n-butylamine, pyridine, hexachloroplatinic acid. The catalyst is used in an amount of 1 to 10 ^-6 mol, preferably 10 ^-1 to 10 ^-4 mol of metal, based on 1 mol of formyl groups. The activator is used in an amount of 10 ^-1 to 10 ^-6 mol, based on 1 mol of metal.

The hydrogenation is monitored by IR spectroscopy and continued until a quantitative reduction all formyl groups is reached.

The resulting poly (hydroxymethyl-tricyclo [5.2.1.0 ^2,6 ] decanyl) siloxane can be freed of catalyst and impurities after the hydrogenation has ended by filtration and / or using adsorbents such as Celite®, silica gel or aluminum oxide and by removing the solvent in vacuo be isolated. The siloxane derivatives are obtained as colorless, highly viscous to waxy substances. If necessary, cleaning can also be carried out by vacuum distillation, provided that the products e.g. B. are disiloxanes.

This poly (hydroxymethyl-tricyclo [5.2.1.0 ^2.6 ] decanyl) siloxane can optionally in the presence of basic catalysts with 1-20 moles (based on 1 mole of hydroxymethyl groups) of an alkylene oxide, for. B. oxirane or methyloxirane, at temperatures of 70 to 150 ° C, preferably 90 to 120 ° C, to compounds of formula II, the alkylene oxide is advantageously metered in according to its consumption.

The basic catalysts used are preferably alkali or alkaline earth alcoholates, which are also used in situ can be produced.  

Another process for the preparation of α , ω- bis [hydroxy (alkyleneoxy) methyl-tricyclo [5.2.1.0 ^2,6 ] -decanyl] siloxanes of the formula

in the

R¹ and R² are the same or different and are hydrogen, lower alkyl, halogen or trifluoromethyl, R³ is lower alkyl, cycloalkyl, cycloalkyl-alkyl or optionally substituted aryl or aralkyl, R¹³ is hydrogen or methyl, p is an integer from 0 to 20, for a siloxane chain stands, which consists of m structural elements of the formula and the end group consists of
R⁴, R⁵, R⁶, R⁷ and R⁹ are identical or different and are lower alkyl, cycloalkyl (C₅ to C₇), cycloalkylalkyl (C₆ to C₁₀) and optionally substituted aryl (C₆ to C₁₁) or aralkyl (C₇ to C₁₁),
R⁸ for the group in the
R¹, R², R¹³ and p have the meaning given above,
R¹⁰ represents lower alkyl and
where the sum of the structural elements m independently of one another stands for a number from 0 to 600, and B stands for lower alkyl,

is characterized in that in a first stage an α , l - bishydrogen siloxane of the formula

in the

A 'represents a siloxane chain consisting of m structural elements of the formula and the end group consists of
R⁴, R⁵, R⁶, R⁷, R⁹ and R¹⁰ have the meaning given above and
R⁸ '' stands for hydrogen, the sum of the structural elements m independently being a number from 0 to 600 and
B and R³ have the meaning given above,

with a tricyclo [5.2.1.0 ^2,6 ] decadiene derivative of the formula

in the
R¹ and R² have the meaning given above,
in the presence of noble metal catalysts, or that bis (tricyclo [5.2.1.0 ^2,6 ] decenyl) disiloxanes of the formula

in the
R¹, R², R³, R⁹, R¹⁰ and B have the meaning given above
in the presence of acids or bases with a cyclosiloxane of the formula

in the
R⁴ and R⁵ have the meaning given above,
and / or with a cyclosiloxane of the formula

in the
R⁶ and R⁷ have the meaning given above,
equilibrated,
and then reacting the a , ω - bis (tricyclo- [5.2.1.0 ^2,6 ] decenyl) siloxane obtained according to the variants in a subsequent step in the presence of a hydroformylation catalyst with carbon monoxide and hydrogen in a ratio of about 1: 1,
the formyl derivative obtained is reduced in a further step to the corresponding hydroxymethyl derivative and optionally (for p <0) the hydroxymethyl derivative obtained with p mol (based on 1 mol hydroxymethyl groups) of an alkylene oxide of the formula

in which
R¹³ and p have the meaning given above,
in the presence of a basic catalyst.

The manufacturing process can be carried out by the following Reaction scheme will be explained.  

The first stage of this procedure can come in two variations be performed:

According to the first variant, α , l - bishydrogen siloxanes (XII) are reacted with a tricyclo- [5.2.1.0 ^2,6 ] decadiene derivative (XIII).

α , ω - Bishydrogen siloxanes (XII) are commercially available and can be prepared, for example, by equilibration of dihydrogen tetraorganodisiloxanes with cyclotrisiloxanes.

The following α , l - bishydrogen siloxanes (XII) may be mentioned, for example:

H-Si (CH₃) ₂-O-Si (CH₃) ₂-H

H-Si (CH₃) ₂-OSi (CH₃) ₂-OSi (CH₃) ₂-H

H- (CH₃) ₂Si [-O-Si (CH₃) ₂] ₁₀-OSi (CH₃) ₂-H

H-Si (CH₃) ₂ [-OSi [CH₃) ₂] ₁₅₀-O-Si (CH₃) ₂H

Tricyclo- [5.2.1.0 ^2,6 ] decadiene derivatives (XIII) are commercially available and can be prepared, for example, by the Diels-Alder reaction of the corresponding cyclopentadiene derivatives (Houben-Weyl, Methods of Organic Chemistry, Volume V / 1b, Pp. 438-447 [1972]).

For example, the following tricyclo [5.2.1.0 ^2,6 ] decadiene derivatives may be mentioned:

The reaction of the α , ω - bishydrogen siloxanes with the tricyclo- [5.2.1.0 ^2,6 ] decadiene derivatives (hydrosilylation) is carried out in the presence of hydrosilylation catalysts. Platinum compounds are preferably used, such as hexachloroplatinic acid in isopropanol, the Lamoreaux catalyst (US 32 20 972) or the Karstedt catalyst (US 37 75 452). It is also possible to carry out the hydrosilylation using a platinum-supported catalyst, for example using platinum on activated carbon.

The hydrosilylation catalyst is generally used in an amount of 10 ^-7 to 10 ^-3 mol of platinum, preferably 10 ^-6 to 10 ^-3 mol of platinum, based on one mol of SiH groups of the α , ω - bishydrogen siloxane.

The hydrosilylation is generally in the temperature range from 20 to 180 ° C, preferably in the range of 50 up to 150 ° C.

In general, the hydrosilylation is carried out at normal pressure carried out. However, implementation is also possible at increased pressure (for example in the pressure range from 1.5 to 10 bar).

In general, the hydrosilylation is carried out Exclusion of moisture through.

It is possible to hydrosilylate with or without Solvent.  

Solvents are those that are among the Reaction conditions are inert. For example Toluene, chlorobenzene, xylene, octahydronaphthalene and Called ethylene glycol dimethyl ether.

In general, 1.0 to 2.2 mol of the tricyclo [5.2.1.0 ^2.6 ] decadiene derivative are used per 1 mol of SiH groups in the α , ω - bishydrogen siloxane.

The reaction in the hydrosilylation can be followed by IR spectroscopy. The end of the reaction can be determined, for example, by the fact that no more absorption of the SiH group is observed at about 2100 cm ^-1 .

Hydrosilylation gives α , ω - bis (tricyclo [5.2.1.0 ^2,6 ] decenyl) siloxanes. Before the further reaction, it may be appropriate to purify the reaction product of this reaction step. Low-boiling siloxanes, preferably disiloxanes, with tricyclo [5.2.1.0 ^2,6 ] decenyl) substituents can be purified by vacuum distillation. It may be expedient to add a polymerization inhibitor in an amount of 100 to 1000 ppm, based on the reactants, before the distillation. Examples of polymerization inhibitors are 2,6-di-tert-butyl-4-methylphenol and hydroquinone monomethyl ether. The polymerization inhibitor is generally added in an amount of 0.01 to 1% by weight, based on the reactants. α , ω - bis (tricyclo [5.2.1.0 ^2.6 ] decenyl) siloxanes with z. B. more than two siloxane diyl groups are freed from the catalyst by adsorbents such as activated carbon, aluminum oxide or silica gel, Celite etc. and then from volatile components by vacuum treatment.

Under the hydrosilylation conditions specified in the process according to the invention, the addition of the SiH group preferably takes place in the 8- or 9-position of the 3 (4), 8-tricyclo [5.2.1.0 ^2,6 ] decadiene derivatives.

According to the second variant, bis (tricyclo- [5.2.1.0] ^2,6 -decenyl) disiloxanes (XIV) are reacted with cyclosiloxanes (XV) and / or (XVI).

Bis- (tricyclo- [5.2.1.0 ^2,6 ] -decenyl) disiloxanes are known per se (Chem. Abst. 85, 143 184) and can be obtained, for example, by reacting tricyclo [5.2.1.0 ^2,6 ] - decadiene- Derivatives are prepared with dihydrogen tetraorganodisiloxanes.

The following bis- (tricyclo- [5.2.1.0 ^2,6 ] -decenyl) disiloxanes may be mentioned for example:

Cyclosiloxanes (XV) and (XVI) are commercially available and can, for example, by condensation of Diorganodihalosilanes can be obtained (Preparative Methods in Polymer Chemistry, Wiley [1969], p. 384, or W. Noll, Chemistry and technology of silicones, Verlag Chemie [1968]).

For example, the following cyclosiloxanes called: hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, tetramethyltetraethylcyclotetrasiloxane and tetramethyltetraphenylcyclotetrasiloxane.

The equilibration is generally carried out in the presence of an acid or base. Strong acids with a p _k value of less than 2 are preferably used as acids. Examples include the following acids: sulfuric acid, trifluoroacetic acid, trifluoromethanesulfonic acid and perfluorobutanesulfonic acid.

The acid is generally used in an amount of 10 ^-3 to 5 mol%, preferably 10 ^-2 to 1.0 mol%, of the reactants.

The bases used are (earth) alkali hydroxides, tetraalkylammonium hydroxides, (earth) alkali oxides or (earth) alkali carbonates in an amount of 10 ^-3 to 2 mol% of the reactants.

The equilibration is generally in the temperature range from 20 to 120 ° C, preferably from 20 to 80 ° C, carried out.  

In general, the equilibration is carried out at normal pressure. However, it is also possible to carry out the equilibration at an overpressure or underpressure (for example in the pressure range from 10 ^-2 to 100 bar).

Equilibration can be done with or without solvent be performed. Solvents for this stage of the process are inert solvents, which are among the Do not change reaction conditions. For example be chloroform, toluene, chlorobenzene and hexane called.

The course of the reaction can be measured by measuring the viscosity be followed. The balance is reached when no change in viscosity is observed.

The number m of different structural elements in the polysiloxane can be determined by the molar ratio of the cyclosiloxanes of the formula (XV) and / or (XVI), based on the bis (tricyclo [5.2.1.0 ^2.6 ] decenyl) disiloxane (XIV), be determined.

After the reaction has ended, the equilibration catalyst neutralized and / or extracted; fleeting Components of the reaction mixture can in vacuo be distilled off to about 200 ° C.

The α , l - bis-tricyclo- [5.2.1.0 ^2,6 ] -decenyl) -siloxane obtained according to both variants can generally be used in the further reaction stages by the purification processes mentioned above.

Hydroformylation to formyl derivatives, their hydrogenation to the corresponding hydroxymethyl derivatives and the reaction with alkylene oxides can be found in the above described manner.

Another process for the preparation of poly [hydroxy (alkyleneoxy) methyltricyclo- [5.2.1.0 ^2,6 ] -decanyl] siloxanes of the formula

in the

R¹ and R² are the same or different and are hydrogen, lower alkyl, halogen or trifluoromethyl, R³ is lower alkyl, cycloalkyl, cycloalkyl-alkyl or optionally substituted aryl or aralkyl, R¹³ is hydrogen or methyl, p is an integer from 0 to 20, for a siloxane chain stands, which consists of m structural elements of the formula and the end group consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are the same or different and are lower alkyl, cycloalkyl, cycloalkylalkyl and optionally substituted aryl or aralkyl,
the radicals R⁵ and / or R⁷ also for the group in the
R¹, R², R¹³ and p have the meaning given above,
R¹⁰ represents lower alkyl, and,
where the sum of the structural elements m independently of one another stands for a number from 0 to 600, and B can have the same meaning as A,
where the radicals R⁴ to R¹⁰ in the chains A and B can be different,

is characterized in that in a first Stage a polyhydrogensiloxane of the formula

in the

A 'represents a siloxane chain consisting of m structural elements of the formula and the end group consists of
R ^{5 ″} and R ^{7 ″ are} identical or different and are hydrogen, lower alkyl, cycloalkyl, cycloalkylalkyl and optionally substituted aryl or aralkyl, at least one of the radicals being hydrogen,
m, R ⁴ , R ⁶ , R ⁸ , R ⁹ and R ^{10 have} the meaning given above and
B ′ can have the scope of A ′,
where the radicals R ⁴ , R ^{5 ″} , R ⁶ , R ^{7 ″} , R ⁸ , R ⁹ and R ¹⁰ in the chains A ′ and B ′ can be different,

with a tricyclo [5.2.1.0 ^2,6 ] decadiene derivative of the formula

in the
R ¹ and R ^{2 have} the meaning given above,
implemented in the presence of precious metal catalysts,
and then reacting the poly (tricyclo- [5.2.1.0 ^2,6 ] decenyl) siloxane obtained in the presence of a hydroformylation catalyst with carbon monoxide and water in a ratio of about 1: 1,
the formyl derivative obtained is reduced to the hydroxymethyl derivative in a further stage,
and optionally (for p <0) the hydroxymethyl derivative obtained with p mol (based on 1 mol hydroxymethyl groups) of an alkylene oxide of the formula

where R¹³ and p have the meaning given above,
in the presence of a basic catalyst.

The manufacturing process can be carried out by the following Reaction scheme are explained:  

Polyhydrogensiloxanes (XVII) are commercially available and can for example by equilibration of Hexaorganodisiloxanes with tetrahydrogen tetraorgano- cyclosiloxanes and optionally octaorganocyclotetra- siloxanes can be produced. For example called the following polyhydrogen siloxanes:

The hydrosilylation and all subsequent reaction stages to give the derivatives according to the invention can be carried out analogously to the process which gives α , ω - bis [hydroxy (alkyleneoxy) methyl [tricyclo [5.2.1.0 ^2,6 ] decenyl] siloxanes.

For example, the following poly [hydroxy (alkyleneoxy) methyltricyclo- [5.2.1.0 ^2,6 ] decanyl] siloxane derivatives may be mentioned:

The (meth) acrylic acid esters (I) according to the invention from the hydroxyl compounds of the formula (II) Esterification with (meth) acrylic acid or its reactive Derivatives (III) or by reaction with isocyanatoalkyl (meth) acrylates (IV) or by reaction with 1: 1- Addition products from diisocyanates (V) and hydroxyalkyl Obtained (meth) acrylic acid esters (VI).

For the esterification, (meth) acrylic acid, (meth) acrylic acid chloride, (Meth) acrylic anhydride or for example Esters such as (meth) acrylic acid methyl ester or ethyl ester be used. The esterification takes place preferably with (meth) acrylic acid in the presence of a acid catalyst, e.g. B. p-toluenesulfonic acid, Sulfuric acid or ion exchangers in the H⊕ form in one Solvent that is immiscible with water, e.g. B. Toluene, chloroform, xylene, etc.

The esterification can be carried out as follows, for example will:

The hydroxyl compound (II) and an excess of (Meth) acrylic acid are dissolved in the solvent and with the acid catalyst and a polymerization Inhibitor added. That during the esterification Water formed is removed by azeotropic distillation removed the balance. The reaction is general in the temperature range from 50 ° C to about 120 ° C carried out.

Suitable polymerization inhibitors are, for example 2,6-di-tert-butyl-4-methylphenol, methylene blue and hydroquinone in an amount of 0.01 to 1% by weight.  

After the esterification has ended, unreacted (meth) - Acrylic acid by extraction with a basic aqueous Solution removed. The inhibitor is, for example, by Addition of adsorbents separated. The invention Reaction products are by distilling off the Solvent isolated.

It is also possible to esterify the hydroxyl compound (II) with (meth) acrylic acid chloride in the presence of tertiary amines, such as pyridine, triethylamine, Dicyclohexylmethylamine, p-dimethylaminopyridine, tri-n- butylamine, N-methylpiperidine, cyclohexyldimethylamine etc. in inert solvents.

1.0 to 1.5 mol of (meth) acrylic acid chloride are preferred, based on each mole of hydroxyl groups, used. The tertiary amine is in the OH groups of (II) equivalent amount added. The reaction is preferably in the presence of 0.01 to 1 wt .-% of one of the above polymerization inhibitor performed in anhydrous conditions. As a solvent are suitable those with the (meth) acrylic acid chloride not react. Examples include: Dichloromethane, chloroform, toluene, n-hexane, methylcyclohexane, Xylene, acetone, etc.

The reaction is generally in the temperature range from 0 to 80 ° C, preferably from 10 to 50 ° C.  

When the reaction has ended, the precipitated hydrochloride filtered off the tertiary amine and the filtrate with aqueous mineral acids, with aqueous alkali hydrogen carbonate or carbonate solution and water washed. The compounds of the invention are, for example after cleaning the dried solution with activated carbon, Celite, bleaching earth or other adsorbents Distill off the solvent in vacuo.

It is also possible to use the esterification of (II) (Meth) acrylic acid esters in the presence of transesterification catalysts such as tetrabutoxytitanium, tetra (isopropoxy) - titanium, etc. to carry out the (meth) acrylic acid ester underlying alcohol is out of balance is removed by distillation.

For the implementation of the hydroxyl compounds (II) to Urethane isocyanates (IV) (meth) acrylic acid isocyanatoalkyl ester) used.

Isocyanates (IV) are commercially available or can for example by reacting 5,6-dihydrooxazines with Phosgene (DE-OS 33 38 077) or by phosgenation of the corresponding amino compounds (US Pat. No. 2,821,544) getting produced.

The following isocyanates may be mentioned, for example: 2-isocyanatoethyl methacrylate, 3-isocyanato-1,2-dimethyl propyl methacrylate, 3-isocyanatopropyl methacrylate, 3- Isocyanatopropyl acrylate.  

The process according to the invention is generally described in Exclusion of water carried out in an inert solvent. For example, chloroform, tetrahydrofuran, Acetone, dioxane, dichloromethane, toluene and acetonitrile called. Preferred solvents are chloroform and toluene and dichloromethane.

The process according to the invention is generally carried out in Temperature range from 20 to 100 ° C, preferably from 30 up to 70 ° C.

The process according to the invention is generally described in Normal pressure carried out. However, it is also possible the process in the pressure range from 1 to 15 bar perform.

In the implementation of the invention to urethane preferably worked under exclusion of water (preferably under 0.1% water).

To speed up the implementation are preferred tin-containing catalysts such as dibutyltin dilaurate, Tin (II) octoate or dibutyltin dimethoxide is used.

It is also possible to use compounds as catalysts tertiary amino groups or titanium compounds to use. For example, the following catalysts called: diazabicyclo [2.2.2] octane, triethylamine, N- Methylpiperidine, tetrabutoxy-titanium (Ullmann, Encyclopedia of Technical Chemistry, Vol. 19, p. 306 [1981]).  

Generally the catalyst is used in an amount of 0.01 to 2.5% by weight, preferably 0.1 to 1.5% by weight, based on the total amount of reactants used.

The conversion to urethane is generally in the presence from 0.01 to 0.2% by weight of a polymerization inhibitor, for example 2,6-di-tert-butyl-4-methylphenol carried out.

The method according to the invention can, for example, how be carried out as follows:

The reactants are dissolved in the solvent and mixed with the catalyst. The temporal The course of the implementation can be, for example, by measurement of the IR spectra are tracked. After more complete Implementation of the isocyanate groups become the reaction products isolated by removing the solvent. A prior cleaning with the aid of absorbents, for example activated carbon, bleaching earth, silica gel or Aluminum oxide is of course also possible.

The reaction with acrylic acid derivatives can be carried out in a similar manner Way.

For the implementation of the hydroxyl compounds (II) to Urethane methacrylate can also be made from addition products 1 mol of a diisocyanate (V) and 1 mol of a hydroxyalkyl (meth) acrylic acid ester (VI) can be used.  

Diisocyanates of the formula (V) are known per se and can be prepared, for example, by reacting the diamines with phosgene. Examples include the following diisocyanates: hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, 1,4-diisocyanato-cyclohexane, 1-isocyanato-4-methyl-4-isocyanato-cyclohexane, 3 (4), 8-bis (isocyanatomethyl) - tricyclo [5.2.1.0 ^2,6 ] decane, 2,4-diisocyanatotoluene, 1,5-diisocyanatonaphthalene.

Hydroxyalkyl (meth) acrylic acid esters of the formula (VI) known per se and can for example by partial Esterification of the corresponding polyols can be obtained. For example, the following hydroxyalkyl (meth) called acrylic acid ester: 2-hydroxyethyl acrylate, 2- Hydroxypropyl methacrylate, glycerol dimethacrylate, 1- Methacryloyloxy-3-acryloyloxy-propanol-2, trimethylolpropane dimethacrylate, dipentaerythritol pentaacrylate.

The preparation of the addition compounds from 1 mol a diisocyanate (V) and 1 mole of a hydroxyalkyl (Meth) acrylic acid ester (VI) is carried out in a manner known per se Way by reacting the two reactants in a molar ratio 1: 1 to 10: 1 and when using excess Diisocyanate by subsequent cleaning of the resulting isocyanatourethane.

The adduct of (V) and (VI) is purified preferably by extraction with aliphatic solvents with boiling points below 120 ° C at normal pressure, e.g. B. with pentane, n-hexane, isopentane.  

The preparation of the addition compounds is general performed in an inert solvent. Examples include acetone, chloroform, tetrahydrofuran, Dioxane, methylene chloride, toluene, acetonitrile called. Chloroform, toluene, Acetonitrile and acetone.

The method according to the invention can, for example, how be carried out as follows:

The (meth) acrylic acid ester of formula (VI) and optionally the polymerization inhibitor are inert Solvent and with stirring to the optionally dissolved diisocyanate (V) added dropwise. The catalyst is added to one of the two reactants. The reactants are in the molar ratio V: VI of about 1: 1 up to 10: 1 implemented and until complete Turnover of the OH groups or to the corresponding Sales of the isocyanate groups led. Implementation of the Isocyanate groups can be known in a known manner by IR Spectroscopy and / or controlled by titration will.

An excess of diisocyanate can then be mixed with n-hexane, n-pentane or other aliphatic solvents a boiling point below 120 ° C (at normal pressure) extracted will.

In the second stage of the method according to the invention the isocyanatourethane obtained in the first stage if applicable after extraction excess diisocyanate, with the hydroxyl compound  (II) implemented so that the number of hydroxyl equivalents the number of remaining NCO equivalents corresponds.

The reaction is generally completed Sales led so that neither free isocyanate nor free II remain in the reaction mixture. After finished The reaction product is implemented by removing the Solvent isolated. A previous filtration or Cleaning with the help of adsorbents or activated carbon, Bleaching earth, silica gel or aluminum oxide is possible.

According to the inventive method in the Usually a mixture of urethane groups (Meth) acrylic acid derivatives separated on adsorbents can be.

It is also possible to take the first and second stages of the to swap the above procedure in their order. In this case, the first stage is diisocyanate V and hydroxy compound II in a molar ratio NCO: OH = 2 to 4, preferably in the molar ratio NCO: OH = 2.0 to 2.3 until all the hydroxyl groups have reacted reacted in urethane groups.

Then any excess is present of diisocyanate (if used in excess was) in the manner described above with the above Extracted solvents. The remaining NCO groups are then in the second stage with a hydroxyalkyl (meth) acrylate VI to the (meth) acrylic acid ester according to the invention I implemented a stoichiometric equivalence of NCO and OH groups.  

With the help of diisocyanates with different reactivities However, the NCO group is quite able to the (meth) - containing the urethane groups according to the invention to selectively produce acrylic acid derivatives of the formula I. Suitable diisocyanates for this are, above all, which in addition to a sterically unhindered, aliphatic bound, a sterically hindered, cycloaliphatic bound Have isocyanate group. For example 1-isocyanato-1-methyl-4-isocyanatomethyl-cyclohexane, preferably called isophorone diisocyanate, etc.

When these diisocyanates are used, they naturally result different reaction speeds for the first and second synthesis stages, so that in the first A stoichiometry of NCO: OH = 20 to 2.05 is preferred is.

For the use of the new urethane according to the invention (meth) acrylates in the dental field is a separation of the reaction mixtures obtained is not necessary.

The (meth) acrylic acid esters of tricyclodecane groups according to the invention containing siloxanes can as Monomers for the production of polymer materials be used. The polymerization can in itself known manner carried out by radical initiation are and results in polymers that have a high Have cross-linking density.

The (meth) acrylic acid esters of tricyclodecane groups according to the invention containing siloxanes can in particular are used as monomers for dental materials, from which dental moldings through the polymerization  getting produced. As dental materials are for example filling materials for teeth, coating agents for teeth and components for manufacturing called from dentures. Depending on the area of application Dental materials can contain other auxiliary materials.

The dental materials according to the invention contain generally as polymerizable compounds (monomers) 30 to 100% by weight, preferably 60 to 100% by weight (Meth) acrylic acid esters of tricyclodecane groups Siloxanes.

For use as monomers for dental fillings or Coating agents (tooth varnishes) in the dental field can the (meth) acrylic acid esters of tricyclodecane groups according to the invention containing siloxanes with themselves known comonomers can be mixed. For example the viscosity adapted to the intended use will. These monomer mixtures have in general a viscosity in the range of 60 to 10,000 mPas.

For example, the following comonomers are mentioned:
Triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,12-dodecanediol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, 2,2-bis (p- (2'-hydroxy-3'-methacryloyloxypropoxy) phenyl) propane, 2,2-bis (p- ( 2'-methacryloyloxyethoxy) phenyl) propane, trimethylolpropane tri (meth) acrylate, bis (meth) acrylic oyloxyethoxymethyl) tricyclo (5.2.1.0 ^2.6 ) decane (according to DE-OS 29 31 925 and 29 31 926) , 1,3-Di ((meth) acryloyl oxypropyl) -1,1,3,3-tetra-methyldisiloxane, 1,3-bis (3- (meth) acryloyloxyethylcarbamoyloxypropyl) -1,1,3,3- Tetramethyl disiloxane. In particular, comonomers are preferred which have a boiling point above 100 ° C. at 13 mbar.

It is also within the scope of the present invention preferred, mixtures of different inventive Use (meth) acrylic acid ester.

It is also possible to use monomer mixtures that contain several comonomers.

The (meth) acrylic acid esters according to the invention can be cured, if appropriate as a mixture with the monomers mentioned, to form crosslinked polymers using methods known per se (GM Brauer, H. Argentar, Am. Chem. Soc., Symp. Ser. 212, p. 359-371 [1983]). A system consisting of a peroxidic compound and a reducing agent, for example based on tertiary aromatic amines, is suitable for the so-called redox polymerization. Examples of peroxides are:
Dibenzoyl peroxide, dilauroyl peroxide and di-4-chlorobenzoyl peroxide.

Examples of tertiary aromatic amines are N, N- Dimethyl-p-toluidine, bis- (2-hydroxyethyl) -p-toluidine, Bis (2-hydroxyethyl) -3,5-dimethylaniline and that in the DE-PS 27 59 239 described N-methyl-N- (2-methyl- carbamoyloxypropyl) -3,5-dimethylaniline called.

The concentration of the peroxide or the amine advantageously chosen so that they 0.1 to 5 wt .-%, preferably 0.5 to 3% by weight, based on the monomer mixture  be. The peroxide or amine-containing monomer mixtures are stored separately until use.

The monomers of the invention can also by Irradiation with UV light or visible light (for example in the wavelength range from 230 to 650 nm) be brought to polymerization. As initiators for photo-initiated polymerization is suitable, for example Benzil, benzil dimethyl ketal, benzoin monoalkyl ether, Benzophenone, p-methoxybenzophenone, fluorenone, Thioxanthone, phenanthrenequinone and 2,3-bornanedione (Camphorquinone), optionally in the presence of synergistic acting photoactivators, such as N, N- Dimethylaminoethyl methacrylate, triethanolamine, 4-N, N- Dimethylaminobenzenesulfonic acid bisallylamide.

The implementation of the photopolymerization process is described for example in DE-A 31 35 115.

In addition to the initiators described above, the (Meth) acrylic acid esters according to the invention per se this purpose known light stabilizers and Polymerization inhibitors are added.

The light stabilizer and the polymerization inhibitor are each generally in an amount of 0.01 up to 0.50 parts by weight, based on 100 parts by weight of Monomer mixture used. The monomer mixtures can without the addition of fillers as a coating agent (Tooth enamel) are used.

When used as a dental filling compound, you set the obtained monomer mixtures in general fillers  to. In order to achieve a high degree of filling, are Monomer mixtures that have a viscosity in the range of Have 60 to 10,000 mPas, particularly advantageous. The containing the compounds of formula I according to the invention Monomer mixtures can preferably be inorganic Fillers are added. For example be rock crystal, quartzite, crystallobalite, quartz glass, finely divided silica, aluminum oxide and glass ceramics, for example containing lanthanum and zircon Glass ceramics (DE-A 23 47 591) called.

The inorganic fillers are used to improve the Compound to the polymer matrix of the dental molded body preferably pretreated with an adhesion promoter. The Mediation can take place, for example, through treatment can be achieved with organosilicon compounds (E. P. Plueddemann, Progress in Organic coatings, 11, 297 to 308 [1983]). 3-Methacryloyloxypropyltrimethoxysilane is preferred used.

The fillers for the dental filling materials according to the invention generally have an average particle diameter from 0.01 to 100 µm, preferably from 0.05 to 50 µm on, particularly preferably 0.05 to 5 microns. It can also be advantageous, several fillers side by side use a different particle diameter and different degrees of silanization have.

The filler content in the tooth filling materials is in generally 5 to 85% by weight, preferably 50 to 80% by weight.  

For the production of the dental filling materials Components using commercially available Kneaders processed.

The proportion of the (meth) acrylic acid esters according to the invention in the fillings is generally 10 to 90% by weight, preferably 45 to 85% by weight, based on the filling mass.

The (meth) acrylic acid esters of Siloxanes containing tricyclodecane groups can also be used as Components used in the manufacture of dentures will.

The monomers of the invention Usually used, known components combined. The monomers are preferably mixed with alkyl methacrylates such as methyl methacrylate used. It can also be known in addition Bead polymers are added. For setting the tooth shade can known inorganic and organic Color pigments and opacifiers are added. Auc 15193 00070 552 001000280000000200012000285911508200040 0002003707908 00004 15074h die Use of stabilizers and light stabilizers is possible.

The plastic teeth are made by radical polymerization of the dental materials produced under shaping. Processing is both according to injection procedures Embossing processes are also possible and generally take place according to the usual manufacturing methods for teeth Base of poly (methyl methacrylate), e.g. B. by thermal Polymerization using known per se Polymerization initiators, for example based on  Peroxides and azo compounds such as dibenzoyl peroxide, Dilauroyl peroxide, cyclophexyl percarbonate, azoisobutyronitrile. Mixtures of Polymerization initiators with different Decay temperatures.

The plastics produced using the (meth) acrylic esters of tricyclo [5.2.1.0 ^2,6 ) decanylsiloxane derivatives according to the invention have a very low polymerization shrinkage, a low water absorption, very good mechanical properties and one compared to known (meth) acrylic acid esters that are used in dental materials, significantly improved abrasion resistance. In addition to these advantages, the very low viscosity of the pure monomers is surprising.

Examples Example 1 1,3-bis (tricyclo [5.2.1.0 ^2,6 ] dec-3-en-8 (9) -yl) -1,1,3,3-tetramethyldisiloxane Synthetic route A

A solution of 924 g of distilled diclopentadiene in 2 l of chlorobenzene is added with 10 ^-4 mol of platinum, in the form of the Lamoreaux catalyst according to US 32 20 972. 469 g of 1,1,3,3-tetramethyldisiloxane are slowly added dropwise to the reaction solution, which has been heated to 80.degree. C., and the temperature of the mixture should not exceed 100.degree. When the addition is complete, the decrease in the SiH band is monitored by IR spectroscopy. After the reaction has ended (about 24 h at 100 to 120 ° C.), the mixture is cooled and the solvent is removed in a water jet vacuum. The residue is fractionated in a high vacuum after adding 500 ppm of hydroquinone monomethyl ether. In addition to a small amount of unreacted dicyclopentadiene and an intermediate fraction which contains the monoadduct of the disiloxane as the main component, 1091 g of the bis-adduct are obtained. The product is a colorless, low-viscosity liquid and is a mixture of the endo and exo isomers.
Yield: 78%.
Boiling point (0.07 mm Hg); 155 to 160 ° C.

Synthetic route B

1) 68.9 g of dicyclopentadiene and 5 × 10 ^-5 mol of platinum in the form of the Lamoreaux catalyst are dissolved in 780 ml of chlorobenzene and heated to 80 ° C. 59.5 g of chlorodimethylsilane are added dropwise at this temperature. When the addition is complete, the mixture is stirred at 120 ° C. for 24 hours and then distilled.

38 g of 8 (9) - (chlorodimethylsilyl) tricyclo [5.2.1.0 ^2,6 ] dec-3-ene are obtained.
Boiling point (0.12 mm Hg): 80 to 85 ° C.

2) 8.9 g of 8 (9) - (chlorodimethylsilyl) tricyclo [5.2.1.0 ^2,6 ] dec-3-ene are dissolved in 50 ml of toluene. 1.2 g of methanol and 3.7 g of triethylamine are simultaneously added dropwise at room temperature. The mixture is subsequently stirred at 40 ° C. for 1 hour and, after the solvent has been removed and the triethylamine hydrochloride has been separated off, the residue is fractionated in vacuo.
Yield: 8.5 g of 8 (9) - (methoxydimethylsilyl) tricyclo [5.2.1.0 ^2.6 ] dec-3-ene.
Boiling point (0.12 mm Hg): 88 to 91 ° C.

3) hydrolysis

10 mmol of 8 (9) - (methoxydimethylsilyl) tricyclo [5.2.1.0 ^2.6 ] dec-3-ene and 10 mmol of 8 (9) - (chlorodimethylsilyl) - tricyclo [5.2.1.0 ^2.6 ] dec-3 -en are dissolved in 50 ml of ether and added dropwise in 100 ml of 0.01N hydrochloric acid or in 100 ml of saturated sodium bicarbonate solution. The mixture is left to stir at room temperature for 2 hours and the organic phase is separated off. The disiloxane solution is washed neutral, dried and freed from the solvent. Based on the analytical data, the product is identical to the 1,3-bis (tricyclo [5.2.1.0 ^2,6 ] dec-3-en-8 (9) -yl) -1,1,3,3 obtained according to synthesis route A. tetramethyldisiloxane.

Example 2 1,3-bis [3 (4) - (hydroxymethyl) tricyclo [5.2.1.0 ^2.6 ] decan-8 (9) -yl] -1,1,3,3-tetramethyl-disiloxane

244 g of the disiloxane from Example 1 are in 700 ml Toluene dissolved. It becomes 1 g of a hydroformylation catalyst (5% Rh on alumina) was added. The Suspension is placed in a stirred autoclave and at 140 ° C and 180 to 200 bar with a (1: 1) H₂ / CO mixture brought to reaction. After 2.5 hours the implementation is complete completed. The catalyst is filtered off and that Filtrate optionally treated with activated carbon and filtered. The solvent is removed in vacuo. The 1 H-NMR spectrum of the residue shows none olefinic protons. The product contains after gas chromatographic analysis of the dialdehyde with a Share <98%.  

For reduction, 200 g of the crude product in 500 ml Dissolved ethanol and mixed with 2 ml of triethylamine. Then 10 g of Raney nickel and then 0.5 ml of one 0.1% solution of hexachloroplatinic acid in isopropanol admitted. In a stirred autoclave at 120 ° C. and hydrogenated 100 bar hydrogen pressure for 3 hours. The Hydrogenation is checked by IR spectroscopy. If necessary, hydrogenation is continued until the carbonyl band is no longer present in the IR spectrum.

The product is after filtration over activated carbon and Removing the solvent as a viscous, colorless Obtained residue with almost quantitative yield.

The diol is readily soluble in toluene and polar solvents such as alcohols, acetone, chlorinated hydrocarbons and ethyl acetate.
Boiling point (0.05 mm Hg): 220-230 ° C.

Molar mass (osmometric):

found. 475 about 462

Elemental analysis:

calc. C (%) 67.53 H (%) 9.96 Found C (%) 67.8 H (%) 10.0

OH number: 238 mg KOH / g.

IR (film on KBr):

3600-3200 cm ^-1 V (OH).
1000-1100 cm ^-1 V (CO) and V (Si-O-Si).
1250 cm ^-1 V (Si-CH₃).

Example 3 1,3-bis [3 (4) (methacryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] - decan-8 (9) -yl] -1,1,3,3-tetramethyl-disiloxane

492.5 g of the product from Example 2 are dissolved in 1000 ml of dry dichloromethane. After addition of 247.7 g of distilled triethylamine and 383 mg of 2,6-di-tert-butyl-4-methylphenol, 257.5 g of freshly distilled methacrylic acid chloride are added dropwise at 10 ° C. When the addition is complete, the mixture is stirred at room temperature for 6 hours. Then it is filtered. The filtrate is washed with saturated sodium bicarbonate solution, with 10% hydrochloric acid solution and then until the aqueous phase has neutralized with water. The organic phase dried over sodium sulfate is stirred with activated carbon, filtered and then filtered through silica gel 60. The filtrate is concentrated in vacuo to constant weight. 503 g of the dimethacrylate are obtained as a low-viscosity, colorless liquid ( η 25 ° C. = 803 mPas).
Hydroxyl number: <5 mg KOH / g.

Example 4 Bis-methacrylate of the condensation product from 1 mol of the Diols from Example 2 and 2 moles of ethylene oxide A) Preparation of the condensate

462 g of 1,3-bishydroxymethyl-tricyclo [5.2.0.1 ^2,6 ] decanyl-1,1,3,3-tetramethyldisiloxane (mixture of isomers) and 600 are in a heatable stirred autoclave which is provided with an azeotropic dewatering device g of toluene and the air replaced with nitrogen. 2.9 g of 50% strength aqueous potassium hydroxide solution are added at 80 ° C. 88 g of ethylene oxide are then slowly metered in at 100 to 115 ° C. and 0.4 to 0.6 bar and the mixture is subsequently stirred at 100 to 105 ° C. for 3 hours. The reaction product is neutralized with 29 g of water and 10.2 g of a 12.5% aqueous sulfuric acid. Then, after adding a filter aid and an antioxidant (0.05% 2,6-bis-t-butyl-p-cresol), the water is distilled off in vacuo at 70 to 90 ° C. and the separated salts are filtered off together with the filter aid.

The neutral product is freed from about 1 g of volatile constituents by vacuum distillation up to an internal temperature of 150.degree.
Molar mass: 545.
Hydroxyl number: 208 mg KOH / g.

Acrylic acid ester of product A

200 g of product A are dissolved in 500 ml of toluene. 0.125 g of Jonol and 75.7 g of triethylamine are added, and 67.9 g of acrylic acid chloride are added dropwise at room temperature. After 24 hours at room temperature, the product is isolated as in Example 3.
Yield: 191 g.
Viscosity: (25 ° C) ∼ 300 mPas.
Hydroxyl number: <2 mg KOH / g.

Example 5 1,3-bis [(2-methacryloyloxyethyl-1) carbamoyloxymethyltricyclo (5.2.1.0 ^2,6 ) decan-8 (9) -yl] -1,1,3,3-tetramethyldisiloxane

21.1 g of the product from Example 2 are transferred to 100 ml P₄O₁₀ distilled chloroform dissolved. After adding 20 mg of 2,6-di-tert-butyl-4-methylphenol and 0.1 g of tin octoate 14.16 g of 2-isocyanatoethyl methacrylate are added dropwise. The mixture is stirred at 50 ° C until the NCO groups (IR spectroscopic control) fully implemented are (after about 15 hours). After removing the solvent a colorless oil is obtained quantitatively.

IR spectrum (film on KBr):

3200 to 3500 cm ^-1 V (NH) 1710 to 1720 cm ^-1 V (C = O), ester + amide I 1640 cm ^-1 V (C = C) 1510 cm ^-1 amide II 1265 cm ^-1 Si-CH₃ 1050 cm ^-1 Si-O-Si

Example 6 1,3- [3,4 (bis-acryloyloxymethyl) tricyclo (5.2.1.0 ^2,6 ) decan-8 (9) -yl] -1,1,3,3-tetramethyldisiloxane

300 g of the product from Example 2 are in 500 ml (about P₄O₁₀ distilled) dichloromethane dissolved. After encore of 222 mg of 2,6-di-tert-butyl-4-methylphenol and 158 g freshly distilled triethylamine are 145 g at 10 ° C Acrylic acid chloride added dropwise. After the addition is complete Stirred for 6 hours at room temperature. The workup the reaction mixture takes place analogously to Example 3. 317 g of the diacrylate are obtained. The ester is colorless and has a comparable to the methacrylate from Example 3 Viscosity.

Elemental analysis:

calcd. C 67.4 H 8.8 Si 9.8 O 14.0%; found C 67.8 H 8.9 Si 9.6 O 13.7%.

Molar mass (osmometric):

about 570 found 562

Example 7 Production of a urethane methacrylate

72.73 g of hexamethylene diisocyanate and 0.2 g of dibutyltin dilaurate are dissolved in 100 ml of chloroform and heated to 40 ° C. A mixture of 0.14 g of 2,6-di-tert-butyl-4-methylphenol and 98.7 g of glycerol dimethacrylate is slowly added dropwise at this temperature. After half of the NCO equivalents have been converted (NCO determination by reaction with dibutylamine and back titration of the excess dibutylamine with 0.1N hydrochloric acid), 100 g of bis (tricyclo [5.2.1.0 ^2.6 ] decane-8 (9 ) -yl) -1,1,3,3-tetramethyl-disiloxane, dissolved in 200 ml of chloroform, added dropwise. The mixture is stirred at 40-60 ° C. until the NCO groups have completely converted. After the addition of triethylene glycol dimethacrylate, the product is freed from the solvent, so that a monomer mixture containing 72% by weight of the methacrylic acid ester according to the invention is formed.

Examples of use Example 8 Manufacture of a dental filling material

A monomer solution is made, the following The composition has:

Connection parts by weight

Monomer from Example 3100 p-dimethylaminobenzenesulfonic acid N, N-diallylamide 0.5 2,3-Bornanedione 0.2 Benzyl dimethyl ketal 0.125

The monomer solution hardens by irradiation with a commercial dental lamp (Translux®) for one Exposure time of 60 seconds to a colorless Plastic made of compared to known dental materials significantly improved abrasion resistance having.

The monomer solution can be used as tooth enamel.  

Example 9 Production of a light-curing dental filling compound

45 parts by weight of the monomer solution from Example 8 0.1 part by weight of Tinuvin P was added.

This mixture is mixed with 55 parts by weight of a 5% 3-methacryloyloxypropyltrimethoxysilane silanated fumed silica (specific surface: 50 m² / g) in processed into a paste in a vacuum using a duplex kneader.

The material obtained can be exposed to a dental lamp using visible light Cure (60 seconds) to a shaped body.

Example 10

A monomer solution is prepared analogously to Example 8 but instead of the monomer from Example 3 the urethane methacrylate from Example 5 is used.

On a light-cured sample of this monomer solution a flexural strength of 64 N / mm² and a flexural modulus of 1,852 N / mm² measured. (Test according to DIN 13 922). The diametric tensile strength is 35 N / mm².

This plastic also has an improved result Abrasion resistance.

It is particularly suitable as a tooth filling material.  

Example 11 Production of a light-curing dental filling compound

It becomes a solution of 100 parts by weight of the monomer mixture from Example 7, 0.2 part by weight of camphorquinone, 0.1 part by weight of benzil dimethyl ketal and 0.5 part by weight 4-N, N-Dimethylamino-benzenesulfonic acid bisallylamide prepared. 40 parts by weight of this mixture are with 60 parts by weight of one with 5% 3-methacryloyloxypropyltrimethoxysilane silanized highly disperse silica (BET surface area 50 m² / g) in a duplex kneader in the Vacuum processed into a paste.

The material can be exposed by exposure to a dental lamp using visible light (60 seconds) harden to the finished dental material.

A molded body with the following properties is obtained: Flexural strength 93 N / m², flexural modulus 4700 N / mm.

By using filler mixtures from silanized highly disperse silica and silanized ceramics (with an average particle diameter of about 4 µm) Depending on the intended use, the mechanical properties be adjusted.

Claims (17)

1. (Meth) acrylic acid ester of tricyclodecane group-containing siloxanes of the formula wherein R¹ and R² are the same or different and represent hydrogen, lower alkyl, halogen or trifluoromethyl, R³ represents lower alkyl, cycloalkyl, cycloalkyl-alkyl or optionally substituted aryl or aralkyl, Z for the group stands in the
R¹² and R¹³ are the same or different and are hydrogen or methyl,
p stands for a number from 0 to 20 and
Q represents a single bond or a radical of the formula means in the
W represents an alkylene chain,
or a residue of the formula means in the
E is a divalent, straight-chain or branched aliphatic radical having 2 to 24 carbon atoms, an aromatic radical having 6 to 26 carbon atoms, an araliphatic radical having 7 to 26 carbon atoms or a cycloaliphatic radical having 6 to 26 carbon atoms, the aliphatic, aromatic, araliphatic and / or cycloaliphatic radicals can contain 1 or 2 oxygen bridges, and several of the aliphatic, aromatic, araliphatic and / or cycloaliphatic radicals can be connected via optionally substituted methylene groups, and
G denotes a divalent straight-chain or branched aliphatic hydrocarbon radical with 3 to 15 carbon atoms, which may optionally contain 1 to 3 oxygen bridges and may optionally be substituted by 1 to 4 additional (meth) acryloyloxy radicals,
A stands for a siloxane chain, which consists of structural elements of the formula and the end group consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are lower alkyl, cycloalkyl, cycloalkylalkyl and optionally substituted aryl or aralkyl,
the radicals R⁵, R⁷ and R⁸ also for the group in the
R¹, R² and Z have the meaning given above,
stand,
R¹⁰ represents lower alkyl and
where the sum of the structural elements m independently of one another stands for a number from 0 to 600, and
B can have the same scope as A,
where the radicals R⁴ to R¹⁰ in the chains A and B can be different,
or stands for lower alkyl. 2. (meth) acrylic acid ester of tricyclodecane group-containing siloxanes according to claim 1, wherein R¹ and R² are the same or different and are hydrogen, lower alkyl, halogen or trifluoromethyl, R³ lower alkyl, cycloalkyl (C₅ to C₇), cycloalkyl-alkyl (C₆ to C₁₃) or optionally substituted aryl (C₆ to C₁₂) or aralkyl (C₇ to C₁₈) means Z for the group in which R 12 and R 13 are identical or different and denote hydrogen or methyl,
p stands for a number from 0 to 20 and
Q represents a single bond or a radical of the formula means in the
W represents an alkylene chain with 2 to 8 carbon atoms,
or a residue of the formula means in the
E is a divalent, straight-chain or branched aliphatic radical with 2 to 12 carbon atoms, an aromatic radical with 6 to 18 carbon atoms, or a cycloaliphatic radical with 6 to 14 carbon atoms, the aliphatic, aromatic and / or cycloaliphatic radicals containing 1 or 2 oxygen bridges can, and where several of the aliphatic, aromatic, and / or cycloaliphatic radicals can be connected via optionally substituted methylene groups, and
G denotes a divalent straight-chain or branched aliphatic hydrocarbon radical with 3 to 10 carbon atoms, which may optionally contain 1 to 3 oxygen bridges and may optionally be substituted by 1 to 4 additional (meth) acryloyloxy radicals,
A stands for a siloxane chain consisting of m structural elements of the formula and the end group consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are the same or different and are lower alkyl, cycloalkyl (C₅ to C₇), cycloalkyl-alkyl (C₆ to C₁₃) and optionally substituted aryl (C₆ to C₁₂) or aralkyl (C₇ to C₁₈) ,
the radicals R⁵, R⁷ and R⁸ also for the group in the
R¹, R² and Z have the meaning given above,
stand,
R¹⁰ represents lower alkyl and
where the sum of the structural elements m independently of one another stands for a number from 0 to 200, and
B can have the same meaning as A,
where the radicals R⁴ to R¹⁰ in the chains A and B can be different,
or stands for lower alkyl. 3. (Meth) acrylic acid ester of tricyclodecane group-containing siloxanes according to claims 1 and 2, wherein R¹ and R² are the same or different and are hydrogen or lower alkyl, R³ lower alkyl, cycloalkyl (C₅ to C₇), cycloalkyl-alkyl (C₆ to C₁₀) or optionally substituted aryl (C₆ to C₁₁) or aralkyl (C₇ to C₁₁) means Z for the group in which R 12 and R 13 are identical or different and denote hydrogen or methyl,
p represents a number from 0 to 4 and
Q represents a single bond or a radical of the formula means in the
W represents an alkylene chain with 2 to 6 carbon atoms,
or a residue of the formula means in the
E is a divalent, straight-chain or branched aliphatic radical with 2 to 8 carbon atoms, or a cycloaliphatic radical with 6 to 14 carbon atoms and
G denotes a divalent straight-chain or branched aliphatic hydrocarbon radical having 3 to 10 carbon atoms, which may optionally contain 1 oxygen bridge and may optionally be substituted by 1 or 2 additional (meth) -acryloyloxy radicals,
A stands for a siloxane chain, which consists of structural elements of the formula and the end group consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are lower alkyl, cycloalkyl (C₅ to C₇), cycloalkylalkyl (C₆ to C₁₀) and optionally substituted aryl (C₆ to C₁₁) or aralkyl (C₇ to C₁₁) ,
the radicals R⁵, R⁷ and R⁸ also for the group in the
R¹, R² and Z have the meaning given above,
stand,
R¹⁰ represents lower alkyl and
where the sum of the structural elements m independently of one another stands for a number from 0 to 200, and
B can have the same meaning as A,
where the radicals R⁴ to R¹⁰ in the chains A and B can be different,
or stands for lower alkyl. 4. (meth) acrylic acid ester of tricyclodecane group-containing siloxanes according to claims 1 to 3, characterized in that 0.5 to 100 mol% of all silicon atoms are substituted by tricyclo [5.2.10 ^2.6 ] decanyl groups. 5. (Meth) acrylic acid ester of tricyclodecane group-containing siloxanes according to Claims 1 to 4, characterized in that the number m of structural elements is 0 to 50. 6. Process for the preparation of (meth) acrylic acid esters of siloxanes of the formula containing tricyclodecane groups in the
R¹ and R² are the same or different and are hydrogen, lower alkyl, halogen or trifluoromethyl, R³ is lower alkyl, cycloalkyl, cycloalkylalkyl or optionally substituted aryl or aralkyl, Z for the group in which R 12 and R 13 are identical or different and denote hydrogen or methyl,
p stands for a number from 0 to 20 and
Q represents a single bond or a radical of the formula means in the
W represents an alkylene chain,
or a residue of the formula means in the
E is a divalent, straight-chain or branched aliphatic radical having 2 to 24 carbon atoms, an aromatic radical having 6 to 26 carbon atoms, an araliphatic radical having 7 to 26 carbon atoms or a cycloaliphatic radical having 6 to 26 carbon atoms, the aliphatic, aromatic, araliphatic and / or cycloaliphatic radicals can contain 1 or 2 oxygen bridges, and several of the aliphatic, aromatic, araliphatic and / or cycloaliphatic radicals can be connected via optionally substituted methylene groups, and
G denotes a divalent straight-chain or branched aliphatic hydrocarbon radical with 3 to 15 carbon atoms, which may optionally contain 1 to 3 oxygen bridges and may optionally be substituted by 1 to 4 additional (meth) acryloyloxy radicals,
A stands for a siloxane chain consisting of m structural elements of the formula and the end group consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are lower alkyl, cycloalkyl, cycloalkylalkyl and optionally substituted aryl or aralkyl,
the radicals R⁵, R⁷ and R⁸ also for the group in the
R¹, R² and Z have the meaning given above,
stand,
R¹⁰ represents lower alkyl and
wherein the sum of the structural elements m independently of one another stands for a number from 0 to 600, and
B can have the same meaning as A,
where the radicals R⁴ to R¹⁰ in the chains A and B can be different,
or stands for lower alkyl,
found, which is characterized in that poly [hydroxy (alkyleneoxy) methyl-tricyclo- [5.2.1.0 ^2.6 ] decanyl] siloxanes of the formula in the
R¹, R², R³, R¹³, p , A and B have the meaning given above,
for the case of the preparation of compounds in which Q represents a single bond with a (meth) acrylic acid derivative of the formula in the
R¹² has the meaning given above and R¹⁴ represents hydroxy, chlorine, methoxy, ethoxy or (meth) acryloyloxy, esterified
or in the case of the preparation of compounds in which Q represents a radical of the formula stands in the
W represents an alkylene chain,
with an isocyanate of the formula in the
R¹² and W have the meaning given above,
reacted in an inert solvent,
or in the case of the preparation of compounds in which Q represents a radical of the formula stands in the
E is a divalent, straight-chain or branched aliphatic radical having 2 to 24 carbon atoms, an aromatic radical having 6 to 26 carbon atoms, an araliphatic radical having 7 to 26 carbon atoms or a cycloaliphatic radical having 6 to 26 carbon atoms, the aliphatic, aromatic, araliphatic and / or cycloaliphatic radicals can contain 1 or 2 oxygen bridges, and several of the aliphatic, aromatic, araliphatic and / or cycloaliphatic radicals can be connected via optionally substituted methylene groups, and
G denotes a divalent straight-chain or branched aliphatic hydrocarbon radical with 3 to 15 carbon atoms, which may optionally contain 1 to 3 oxygen bridges and may optionally be substituted by 1 to 4 additional (meth) acryloyloxy radicals,
with the addition product of 1 mol of a diisocyanate of the formula O = C = NEN = C = O (V) in the
E has the meaning given above,
and 1 mole of a hydoxyalkyl (meth) acrylic acid ester of the formula in which G and R¹² have the meaning given above,
reacted in an inert solvent,
where a stoichiometric equivalence between the NCO groups of the adduct of V and VI and the OH groups of II is said to exist. 7. The method according to claim 6, characterized in that that the reaction with the (meth) acrylic acid Derivative in the temperature range from 0 to 120 ° C carries out.   8. The method according to claim 6, characterized in that that the reaction with the isocyanate in the presence a catalyst and a polymerization Inhibitors in the temperature range from 20 to 100 ° C carries out. 9. Polymers of monomer mixtures containing (meth) acrylic acid esters of tricyclodecane group-containing siloxanes of the formula wherein R¹ and R² are the same or different and represent hydrogen, lower alkyl, halogen or trifluoromethyl, R³ represents lower alkyl, cycloalkyl, cycloalkyl-alkyl or optionally substituted aryl or aralkyl, Z for the group stands in the
R¹² and R¹³ are the same or different and are hydrogen or methyl,
p stands for a number from 0 to 20 and
Q represents a single bond or a radical of the formula means in the
W represents an alkylene chain,
or a residue of the formula means in the
E is a divalent, straight-chain or branched aliphatic radical with 2 to 12 carbon atoms, an aromatic radical with 6 to 18 carbon atoms, or a cycloaliphatic radical with 6 to 14 carbon atoms, the aliphatic, aromatic and / or cycloaliphatic radicals containing 1 or 2 oxygen bridges can, and wherein several of the aliphatic, aromatic and / or cycloaliphatic radicals can be connected via optionally substituted methylene groups, and
G denotes a divalent straight-chain or branched aliphatic hydrocarbon radical with 3 to 10 carbon atoms, which may optionally contain 1 to 3 oxygen bridges and may optionally be substituted by 1 to 4 additional (meth) acryloyloxy radicals,
A stands for a siloxane chain, which consists of structural elements of the formula and the end group consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are lower alkyl, cycloalkyl, cycloalkylalkyl and optionally substituted aryl or aralkyl,
the radicals R⁵, R⁷ and R⁸ also for the group in the
R¹, R² and Z have the meaning given above,
stand,
R¹⁰ represents lower alkyl and
where the sum of the structural elements m independently of one another stands for a number from 0 to 600, and
B can have the same meaning as A,
where the radicals R⁴ to R¹⁰ in the chains A and B can be different,
or stands for lower alkyl. 10. Dental material containing (meth) acrylic acid esters of siloxanes of the formula containing tricyclodecane groups wherein R¹ and R² are the same or different and represent hydrogen, lower alkyl, halogen or trifluoromethyl, R³ represents lower alkyl, cycloalkyl, cycloalkyl-alkyl or optionally substituted aryl or aralkyl, Z for the group in which R 12 and R 13 are identical or different and denote hydrogen or methyl,
p stands for a number from 0 to 20 and
Q represents a single bond or a radical of the formula means in the
W represents an alkylene chain,
or a residue of the formula means in the
E is a divalent, straight-chain or branched aliphatic radical having 2 to 12 carbon atoms, an aromatic radical having 6 to 18 carbon atoms, or a cycloaliphatic radical having 6 to 14 carbon atoms, the aliphatic, aromatic and / or cycloaliphatic radicals having 1 or 2 oxygen bridges can contain, and wherein several of the aliphatic, aromatic, and / or cycloaliphatic radicals can be connected via optionally substituted methylene groups, and
G denotes a divalent straight-chain or branched aliphatic hydrocarbon radical with 3 to 10 carbon atoms, which may optionally contain 1 to 3 oxygen bridges and may optionally be substituted by 1 to 4 additional (meth) acryloyloxy radicals,
A stands for a siloxane chain consisting of m structural elements of the formula and the end group consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are lower alkyl, cycloalkyl, cycloalkylalkyl and optionally substituted aryl or aralkyl,
the radicals R⁵, R⁷ and R⁸ also for the group in the
R¹, R² and Z have the meaning given above,
stand,
R¹⁰ represents lower alkyl and
where the sum of the structural elements m independently of one another stands for a number from 0 to 600, and
B can have the same meaning as A,
where the radicals R⁴ to R¹⁰ in the chains A and B can be different,
or stands for lower alkyl. 11. Dental material according to claim 10, characterized in that that it is 30 to 100% by weight as a monomer (Meth) acrylic acid ester of tricyclodecane groups containing siloxanes. 12. Dental material according to claims 10 and 11, characterized in that it is (meth) acrylic acid ester of tricyclodecane groups Contains siloxanes and auxiliaries.   13. Use of (meth) acrylic acid esters of siloxanes of the formula containing tricyclodecane groups wherein R¹ and R² are the same or different and represent hydrogen, lower alkyl, halogen or trifluoromethyl, R³ represents lower alkyl, cycloalkyl, cycloalkyl-alkyl or optionally substituted aryl or aralkyl, Z for the group stands in the
R¹² and R¹³ are the same or different and are hydrogen or methyl,
p stands for a number from 0 to 20 and
Q represents a single bond or a radical of the formula means in the
W represents an alkylene chain,
or a residue of the formula means in the
E is a divalent, straight-chain or branched aliphatic radical with 2 to 12 carbon atoms, an aromatic radical with 6 to 18 carbon atoms, or a cycloaliphatic radical with 6 to 14 carbon atoms, the aliphatic, aromatic and / or cycloaliphatic radicals containing 1 or 2 oxygen bridges can, and where several of the aliphatic, aromatic and / or cycloaliphatic radicals can be connected via optionally substituted methylene groups, and
G denotes a divalent straight-chain or branched aliphatic hydrocarbon radical with 3 to 10 carbon atoms, which may optionally contain 1 to 3 oxygen bridges and may optionally be substituted by 1 to 4 additional (meth) acryloyloxy radicals,
A stands for a siloxane chain, which consists of structural elements of the formula and the end group consists of
R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are lower alkyl, cycloalkyl, cycloalkylalkyl and optionally substituted aryl or aralkyl,
the radicals R⁵, R⁷ and R⁸ also for the group in the
R¹, R² and Z have the meaning given above,
stand,
R¹⁰ represents lower alkyl and
wherein the sum of the structural elements m independently of one another stands for a number from 0 to 600, and
B can have the same meaning as A,
where the radicals R⁴ to R¹⁰ in the chains A and B can be different,
or stands for lower alkyl,
in dental materials. 14. Use according to claim 13 in filling materials for teeth. 15. Use according to claim 13 in coating compositions for teeth. 16. Use according to claim 13, as a component in the Manufacture of dentures. 17. Use according to claim 13, as a component for Manufacture of dental moldings.