Acyl Germanium Photoinitiators And Process For The Preparation Thereof

Abstract

Acyl germanium compound according to general formula [R.sub.mAr(CO)].sub.4Ge and process for the preparation thereof. The compound is suitable as initiator for radical polymerization.

Claims

1. Acyl germanium compound according to general formula (I),
[R.sub.mAr(CO)].sub.4Ge(I) in which the variables have the following meanings: Ar a mono- or polycyclic hydrocarbon radical with 6 to 18 ring-carbon atoms, which can be substituted m times by the R group and which can contain one or more heteroatoms in the ring, wherein m is an integer from 0 to 6 and cannot be greater than the number of substitutable hydrogen atoms in Ar, R is a C.sub.1- to C.sub.20-alkyl group, which can be linear, branched or cyclic, which can be interrupted by one or more O atoms and which can contain a radically polymerizable group, or O.

2. Acyl germanium compound according to claim 1, in which the variables have the following meanings: Ar an aromatic C.sub.6-C.sub.10 radical, which can be substituted m times by R, wherein m is an integer from 1 to 3 and R is a C.sub.1- to C.sub.10-alkyl group, which can be linear, branched or cyclic, which can be interrupted by one or more O atoms, and which can contain a radically polymerizable group.

3. Acyl germanium compound according to claim 1, in which the variables have the following meanings: Ar a phenyl radical, pyridyl radical, naphthyl radical, anthryl radical, anthraquinone-yl radical, which can be substituted m times by R, wherein m is an integer from 1 to 3 and R is a C.sub.1- to C.sub.3-alkyl group, which is linear and which can bear a terminal radically polymerizable group comprising vinyl, acrylate, and/or methacrylate.

4. Composition which, relative to its total mass comprises 0.001 to 5 wt. % of an acyl germanium compound of Formula (I) according to claim 1 and at least one polymerizable binder.

5. Composition according to claim 4 which comprises as polymerizable binder at least one radically polymerizable monomer and/or prepolymer.

6. Composition according to claim 5, which comprises as binder at least one mono- or multifunctional (meth)acrylate or a mixture thereof.

7. Composition according to claim 4, which comprises 0.001-5 wt. % acyl germanium compound of Formula (I), 10 to 99.9 wt.-% polymerizable binder, 0 to 85 wt.-% filler, relative in each case to the total mass of the composition.

8. A process of using an acyl germane according to Formula (I) as initiator for radical polymerization, wherein Formula (I) is:
[R.sub.mAr(CO)].sub.4Ge(I) in which the variables have the following meanings: Ar a mono- or polycyclic hydrocarbon radical with 6 to 18 ring-carbon atoms, which can be substituted m times by the R group and which can contain one or more heteroatoms in the ring, wherein m is an integer from 0 to 6 and cannot be greater than the number of substitutable hydrogen atoms in Ar, R is a C.sub.1- to C.sub.20-alkyl group, which can be linear, branched or cyclic, which can be interrupted by one or more O atoms and which can contain a radically polymerizable group, or O.

9. A process for the preparation of acyl germanes of Formula I, wherein Formula I is
[R.sub.mAr(CO)].sub.4Ge(I) in which a trialkylsilyl germane of Formula (R.sub.3Si).sub.4Ge (II) is reacted in the presence of a base with an arylacyl halide (III) to form I, ##STR00008## wherein: R is an alkyl group with 1 to 6 C atoms, X is F, Cl, Br or I, R has the meaning given in claim 1.

10. The process according to claim 9, in which an alkali metal alcoholate, an alkali metal amide or an alkali metal organic compound is used as base.

11. The process according to claim 9, in which one of the following compounds is used as arylacyl halide of Formula III: ##STR00009##

12. The process according to claim 9, in which the trialkylsilyl germane (R.sub.3Si).sub.4Ge (II) is first reacted with the base to form (R.sub.3Si).sub.4-1GeM, wherein M is a metal ion, and (R.sub.3Si).sub.4-1GeM is then converted with the acyl halide of Formula (III) into a compound of Formula (I).

13. The process according to claim 9, in which the compound of Formula (II) is prepared by reacting a germanium chloride of Formula Cl.sub.4Ge (IV) with a trialkylsilyl chloride of Formula R.sub.3SiCl (V): ##STR00010##

14. The process according to claim 9, in which a trimethylsilyl germane of Formula (Me.sub.3Si).sub.4Ge (II) is first reacted with potassium tert-butylate (KOtBu) and then with an acyl halide of Formula (III) (X=F or Cl).

15. Acyl germanium compound according to claim 2, wherein the radically polymerizable group is selected from vinyl, methacrylate, (meth) acrylamide or N-alkylacrylamide.

16. Acyl germanium compound according to claim 2, wherein the radically polymerizable group in the case of non-cyclic radicals is terminal.

Description

DETAILED DESCRIPTION

[0015] This object is achieved by tetra- or tetrakis-acyl germanes corresponding to general formula (I):

[R.sub.mAr(CO)].sub.4Ge(I)

in which the variables have the following meanings: [0016] Ar a mono- or polycyclic hydrocarbon radical with 6 to 18 ring-carbon atoms, which can be substituted m times by the R group and which can contain one or more heteroatoms in the ring, wherein [0017] m is an integer from 0 to 6 and cannot be greater than the number of substitutable hydrogen atoms in Ar, [0018] R is halogen, NR.sup.1.sub.2, OH, OSiR.sup.2.sub.3, (CO)R.sup.3, CN, NO.sub.2, CF.sub.3, COOR.sup.4, a C.sub.1 to C.sub.20-alkyl, -alkenyl, -alkoxy or -alkenoxy radical, which can be linear, branched or cyclic, which can be interrupted by one or more O atoms and which can bear a radically polymerizable group, or O, wherein [0019] R.sup.1 to R.sup.3 independently of each other are in each case H or a linear or branched C.sub.1- to C.sub.12-alkyl radical and [0020] R.sup.4 is H, a linear or branched C.sub.1- to C.sub.12-alkyl radical or SiR.sup.5.sub.3, wherein [0021] R.sup.5 is a linear or branched C.sub.1 to C.sub.10 alkyl radical.

[0022] If several R radicals are present (m>1), these can be different or preferably identical. Preferred radically polymerizable groups which can be present as substituents in the R radicals, are vinyl, styryl, acrylate (CH.sub.2CHCOO), methacrylate (CH.sub.2C(CH.sub.3)COO), acrylamide (CH.sub.2CHCONR.sup.6 with R.sup.6H or C.sub.1-C.sub.8-Alkyl), methacrylamide (CH.sub.2C(CH.sub.3)CONH), particularly preferably (meth)acrylate, methacrylamide and/or N-alkylacrylamide. The R radical(s) preferably bear 0 to 3, in particular 0 to 1 radically polymerizable groups. In non-cyclic radicals the polymerizable groups are preferably arranged terminal.

[0023] According to the rules of chemical nomenclature, compounds in which Ar is an unsubstituted group are to be called tetraacyl germanes, while compounds in which Ar is substituted, must be called tetrakis(acyl)germanes. For the sake of simplicity, the term tetraacyl germanes is used here for both compound groups.

[0024] Ar is preferably a polycyclic hydrocarbon radical which contains at least one aromatic ring, particularly preferably an aromatic hydrocarbon radical. Preferred polycyclic hydrocarbon radicals with at least one aromatic ring are anthraquinone and naphthoquinone. In addition to the benzene radical, in particular condensed aromatic groups such as naphthalene, anthracene, phenanthrene and naphthacene groups are preferred as aromatic hydrocarbon radicals.

[0025] Ar can contain one or more, preferably 1 to 2 heteroatoms in the ring. Preferred heteroatoms are O, S and particularly preferably N. Particularly preferred heteroaromatic radicals are pyridine, pyrimidine and quinoline.

[0026] All stereoisomeric forms and mixtures of various stereoisomeric forms such as e.g. racemates are covered by Formula (I) and the other formulae shown herein. The formulae cover only those compounds that are compatible with the chemical valence theory. For example m cannot be greater than the number of substitutable hydrogen atoms in the Ar group. If R is bonded to Ar via two bonds, the maximum number of possible R radicals is correspondingly smaller.

[0027] The indication that a radical can be interrupted by a heteroatom such as O is to be understood to mean that the O atoms are inserted into the carbon chain or the carbon ring of the radical, i.e. are bordered on both sides by carbon atoms. The number of heteroatoms is therefore at least 1 fewer than the number of carbon atoms, and the heteroatoms cannot be terminal. In the case of hydrocarbon radicals which contain carbon atoms and heteroatoms, the number of heteroatoms is always less than the number of carbon atoms, without taking substituents into account.

[0028] Halogen (abbreviated to Hal) preferably stands for F, Cl, Br or I, in particular F, Cl, quite particularly preferably Cl.

[0029] Tetraacyl germanes corresponding to general formula (I) are particularly preferred, in which the variables have the following meanings: [0030] Ar an aromatic C.sub.6-C.sub.10 radical, which can be substituted m times by R, wherein [0031] m is an integer from 1 to 3 and [0032] R is Cl, NR.sup.1.sub.2, OSiR.sup.2.sub.3, (CO)R.sup.3, CN, NO.sub.2, CF.sub.3, COOR.sup.4, or a C.sub.1 to C.sub.10-alkyl, alkenyl, alkoxy or alkenoxy radical, which can be linear, branched or cyclic, which can be interrupted by one or more O atoms, and which can contain a radically polymerizable group, preferably vinyl, methacrylate, (meth) acrylamide or N-alkylacrylamide, wherein the radically polymerizable group in the case of non-cyclic radicals is preferably terminal, wherein [0033] R.sup.1 to R.sup.3 independently of each other are in each case H or a linear or branched C.sub.1- to C.sub.8-alkyl radical and [0034] R.sup.4 is H, a linear or branched C.sub.1- to C.sub.8-alkyl radical or SiR.sup.5.sub.3 and [0035] R.sup.5 is a linear or branched C.sub.1 to C.sub.5 alkyl radical.

[0036] Tetraacyl germanes according to general formula (I) are further preferred, in which the variables have the following meanings: [0037] Ar a phenyl radical, pyridyl radical, naphthyl radical, anthryl radical, anthraquinonyl radical, which can be substituted m times by R, wherein [0038] m is an integer from 1 to 3 and [0039] R is NR.sup.1.sub.2, CN, NO.sub.2, CF.sub.3, a C.sub.1- to C.sub.3-alkyl radical or C.sub.1 to C.sub.3-alkoxy radical, which is preferably linear and which can bear a terminal radically polymerizable group, preferably vinyl, acrylate, methacrylate, wherein [0040] R.sup.1 is H or a preferably linear C.sub.1- to C.sub.3-alkyl radical.

[0041] If Ar is a phenyl radical and m=1, the R radical is preferably located in the para-position relative to the yl position, if m=2 or 3, the R radicals are preferably located in the ortho- and para-position relative to the yl position. The preferred and particularly preferred meanings of the individual variables can be chosen independently of each other in each case.

[0042] Quite particularly preferred are compounds of Formula (I), in which Ar is a phenyl radical, which is substituted by R m times. m is preferably 1-3, particularly preferably 1, and R is preferably an electron donor group, in particular an alkoxy group.

[0043] According to the invention compounds of Formula (I) are preferred which have an absorption maximum at 400 nm to 700 nm, particularly preferably 400 to 550 nm, such as e.g. tetrabenzoyl germanium or tetra(4-methoxybenzoyl)germanium. The absorption spectrum of the compounds of Formula (I) can be adjusted in a targeted manner by the selection of the R group. For example NO.sub.2 or CN substituents bring about a bathochromic shift of the absorption spectrum, i.e. compounds in which one or more of the R radicals are CN, adsorb light with a longer wave length, with the result that the polymerization can be initiated by visible light in the longer wave length range.

[0044] Tetraacyl germanes of general formula (I) are not known from the state of the art and cannot be prepared with conventional processes. These compounds are characterized by a high reactivity, i.e. an excellent polymerization-initiating effect and a good through-curing depth upon irradiation with visible light. This is of great advantage not only in the case of dental materials and in particular in the case of dental filling composites, but also in the case of non-dental uses.

[0045] It was surprisingly found that (arylacyl).sub.k(alkyl).sub.4-kgermanes of Formula I can be prepared by reacting (trialkylsilyl)germanes of Formula (R.sub.3Si).sub.kGeR.sub.4-k (II) in the presence of a base and an arylacyl halide (III).

##STR00001##

wherein: [0046] R is an alkyl group with 1 to 6, preferably 1 to 4 C atoms, particularly preferably CH.sub.3, [0047] R is an alkyl group with 1 to 12, preferably 1 to 6, particularly preferably 1 to 4 C atoms, quite particularly preferably CH.sub.3, C.sub.2H.sub.5 or C.sub.4H.sub.9, [0048] X is F, Cl, Br or I, preferably F or Cl, [0049] k is an integer from 1 to 4 and [0050] R has the meaning given above.

[0051] In the case of R and R linear alkyl groups are preferred in all cases.

[0052] Alkali metal alcoholates, particularly preferably potassium tert-butylate, alkali metal amides, particularly preferably lithium diisopropylamide, or alkali metal organic compounds, particularly preferably n-butyllithium, are preferably used as bases.

[0053] Preferred arylacyl halides of Formula III are derived directly from the preferred and particularly preferred definitions of the Ar and R groups. The following compounds are examples of this:

##STR00002##

[0054] Preferably, trimethylsilyl germane (R.sub.3Si).sub.kGeR.sub.4-k (II) is firstly reacted with the base to form (R.sub.3Si).sub.k-1R.sub.4-kGeM, wherein M is a metal ion, preferably an alkaline earth and in particular an alkali metal ion, and (R.sub.3Si).sub.k-1R.sub.4-kGeM is then converted with the acyl halide of Formula (III) into a compound of Formula (R.sub.3Si).sub.k-1R.sub.4-kGe(CO)ArR.sub.m. In this way the (R.sub.3Si)-groups of Formula (II) are successively exchanged for (CO)ArR.sub.m radicals. The intermediate products (R.sub.3Si).sub.k-1R.sub.4-kGeM are preferably not isolated.

[0055] With the process according to the invention acyl germanes of Formula (I) can be prepared with a high purity and with good yields. A particular advantage is that the use of costly protective group technology, using sulphur-containing protective groups can be avoided. Sulphur-containing impurities can be removed from the products only with great difficulty, and even small traces of sulphur-containing radicals lead to an unpleasant odour of the end product.

[0056] The starting materials (R.sub.3Si).sub.kGeR.sub.4-k (II) required for the synthesis of the acyl germanes of Formula (I) can preferably be prepared by reacting the corresponding germanium chlorides Cl.sub.kGeR.sub.4-k (IV) with a trialkylsilyl bromide of Formula R.sub.3SiBr or preferably a trialkylsilyl chloride of Formula R.sub.3SiCl (V):

##STR00003##

[0057] For this, R.sub.3SiBr or preferably R.sub.3SiCl (preferably 0.9 to 1.1 k, particularly preferably 0.99 k equivalents) is preferably first added to a suspension of finely dispersed Li (preferably 1.7 to 2.2 k, particularly preferably 1.85 k equivalents) in a suitable solvent, and a solution of the germanium chloride (preferably 1 equivalent) is then added slowly. An ether, particularly preferably THF is preferably used as solvent in each case. The quantity of solvent used is preferably 20 to 40 ml/g Li, quite particularly preferably 30 ml/g Li, or 1 to 5 ml/g GeCl.sub.4, quite particularly preferably 2.5 ml/g GeCl.sub.4. The reaction temperature is preferably +30 to 100 C., particularly preferably 78 C. The working up of the product mixture is preferably carried out by filtration, preferably through diatomaceous earth)(Celite, acid hydrolysis, preferably with a mixture of H.sub.2SO.sub.4/ice, phase separation and subsequent removal of the solvent, preferably by distillation. The products can advantageously be isolated by crystallization, sublimation or distillation.

[0058] According to a particularly preferred embodiment of the process according to the invention, acyl germanes of Formula (I) can be prepared by reacting trimethylsilyl germanes (Me.sub.3Si).sub.kGeR.sub.4-k (II) with potassium tert-butylate (KOtBu) and then reacting the intermediate with an acyl halide (III) (X=F or Cl):

##STR00004##

[0059] For forming (Me.sub.3Si).sub.k-1R.sub.4-kGeK, (Me.sub.3Si).sub.kGeR.sub.4-k (preferably 1 equivalent) and KOtBu (preferably 0.9 to 4 equivalents, particularly preferably 1.1 equivalents) are preferably first dissolved in a suitable solvent and stirred until the reaction is completed. An ether is preferably used as solvent, particularly preferably DME (dimethoxyethane). The quantity of solvent used is preferably 10 to 60 ml/g KOtBu, particularly preferably 20 ml/g KOtBu. The reaction temperature is preferably +80 to 30 C., particularly preferably +25 C., the reaction time is preferably 0.5 to 3 hours, particularly preferably 1 hour.

[0060] The acyl halide (III) (preferably 1.0 to 1.5 equivalents) is then added and stirred until the reaction is complete, in order to obtain the acyl germane of Formula (I). The acyl halide (III) can be used both as such and in solution, wherein the quantity of solvent is preferably 0 to 200 ml, particularly preferably 100 ml/mmol acyl halide. An ether, particularly preferably diethylether, is preferably used as solvent. The reaction temperature is preferably +30 to 100 C., quite particularly preferably 78 C. The reaction time is preferably 0.5 to 48 hours, particularly preferably 24 hours. The working up of the product mixture is preferably carried out by acid hydrolysis, preferably with a mixture of H.sub.2SO.sub.4/ice, phase separation and removal of the solvent e.g. by distillation. The product can be isolated by column chromatography and by crystallization, preferably only by crystallization.

[0061] Analogously, monoacyltrialkyl germanes, bisacyldialkyl germanes and trisacylmonoalkyl germanes can be produced directly and without protective group technology by reacting mono, bis-, tris- or tetra(trialkylsilyl)germanes of Formula (II) with acyl halides of Formula (III).

[0062] Tetraacyl germanes of Formula (I) with k=4 are accessible by this process for the first time. For this, a trialkylsilyl germanium of Formula (R.sub.3Si).sub.4Ge is reacted, in the presence of a base, with an aromatic aryl halide of Formula (III) in the manner described above. The trialkylsilyl germanium (R.sub.3Si).sub.4Ge can be prepared as described by reacting germanium tetrachloride with R.sub.3SiCl and metallic Li.

[0063] Tetraacyl germanes of Formula (I) can be prepared particularly advantageously as described above, by reacting tetrakis(trimethylsilyl)germanium (Me.sub.3Si).sub.4Ge with potassium tert-butylate (KOtBu) and then reacting with an acyl halide of Formula (III) (X=F or Cl):

##STR00005##

[0064] The acyl halide (III) is preferably added in a quantity of from 1.0 to 5 equivalents, particularly preferably 4.1 equivalents, and stirred until the reaction is complete. The acyl halide can be used as described both as such and in solution.

[0065] The tetraacyl germanes of general formula (I) and the (acyl).sub.k(alkyl).sub.4-kgermanes of Formula (I) are particularly suitable as photoinitiators for polymerization, in particular as initiators for radical polymerization, photoaddition and for thiol-ene reaction (polyaddition). It has been found that with these initiators, upon irradiation with light, a high through-curing depth can be achieved, without the initiators leading to discolorations. This is a great advantage in many technical and particularly medical materials.

[0066] The compounds of general formulae (I) and (I) are particularly suitable for the preparation of dental materials, bone cements and quite particularly of contact lenses, intraocular lenses or other medical shaped parts, such as e.g. ear shells, cartilage implants and artificial tissue parts.

[0067] The great through-curing depth upon curing with light in the visible wavelength range is also a substantial advantage in technical applications. The initiators of Formulae (I) and (I) are therefore also suitable for a plurality of non-medical uses, such as for example for the preparation of printing inks or paints, varnishes, adhesives, for the preparation of printing plates, integrated circuits, photoresists, soldering masks, inks for colour printers, as materials for holographic data storage, for the preparation of nanosized microelectromechanical elements, optical waveguides, shaped parts and for the optical preparation of information carriers. A main field of application is use as photoinitiator in the stereolithographic preparation of technical shaped parts, e.g. of precision shaped parts and ceramic green bodies.

[0068] The compositions according to the invention preferably contain, relative to the total mass of the composition, 0.001 to 5 wt.-%, particularly preferably 0.01 to 1.0 wt.-% of the acyl germanium compound of Formula (I) or (I). In addition to the acyl germanium compound of Formula (I) or (I) the compositions preferably also contain a polymerizable binder. Preferred binders are radically and/or cationically polymerizable monomers and/or prepolymers, particularly preferably radically polymerizable monomers, radically polymerizable prepolymers or a mixture thereof.

[0069] Mono- or multifunctional (meth)acrylates or mixtures thereof are particularly suitable as radically polymerizable binders. By mono-functional (meth)acrylic compounds is meant compounds with one, by polyfunctional (meth)acrylates compounds with two or more, preferably 2 to 3, polymerizable groups.

[0070] Examples in this respect are methyl, ethyl, hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl (meth)acrylate, bisphenol A di(meth)acrylate, bis-GMA (an addition product of methacrylic acid and bisphenol A diglycidyl ether), UDMA (an addition product of 2-hydroxyethyl methacrylate and 2,2,4-trimethyl hexamethylene diisocyanate), di-, tri- or tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, as well as glycerol di- and tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate or 1,12-dodecanediol di(meth)acrylate. Compositions which contain at least one radically polymerizable monomer with 2 or more, preferably 2 to 3 radically polymerizable groups, are particularly preferred. Polyfunctional monomers have cross-linking properties.

[0071] Hydrolytically stable diluting monomers such as hydrolytically stable mono(meth)acrylates can also be used as radically polymerizable binders, e.g. mesitylmethacrylate or 2(alkoxy-methyl)acrylic acids, e.g. 2-(ethoxymethyl)acrylic acid, 2-(hydroxymethyl)acrylic acid, N-mono- or -disubstituted acryl amides, such as e.g. N-ethylacrylamide, N,N-dimethacrylamide, N-(2-hydroxyethyl)acrylamide or N-Methyl-N-(2-hydroxyethyl)acrylamide, or N-monosubstituted methacrylamides, such as e.g. N-ethyl-methacrylamide or N-(2-hydroxyethyl)methacrylamide and also N-vinylpyrrolidone or allyl ether. Preferred examples of hydrolytically stable cross-linking monomers are urethanes of 2-(hydroxymethyl)acrylic acid and diisocyanates, such as 2,2,4-trimethylhexamethylene diisocyanate or isophorone diisocyanate; cross-linking pyrrolidones, such as e.g. 1,6-bis(3-vinyl-2-pyrrolidonyl) hexane, or commercially accessible bisacrylamides such as methylene or ethylene bisacrylamide, or bis-(meth)acrylamides, such as e.g. N,N-diethyl-1,3-bis(acrylamido) propane, 1,3-bis(methacrylamido) propane, 1,4-bis(acrylamido) butane or 1,4-bis(acryloyl) piperazine which can be synthesized by reaction from the corresponding diamines with (meth)acrylic acid chloride.

[0072] Known low-shrinkage radically ring-opening polymerizable monomers such as e.g. mono- or multifunctional vinyl cyclopropanes or bicylic cyclopropane derivatives (cf. DE 196 16 183 C2 or EP 1 413 569 A1) or cyclic allyl sulphides (cf. U.S. Pat. Nos. 6,043,361 or 6,344,556) can also be used as radically polymerizable binders. These monomers can also be used in combination with the di(meth)acrylate cross-linkers listed above. Suitable ring-opening polymerizable monomers are vinyl cyclopropanes, such as 1,1-di(ethoxycarbonyl)- or 1,1-di(methoxycarbonyl)-2-vinyl cyclopropane or the esters of 1-ethoxycarbonyl- or 1-methoxycarbonyl-2-vinyl cyclopropane carboxylic acid with ethylene glycol, 1,1,1-trimethylolpropane, 1,4-cyclohexanediol or resorcinol. Suitable bicyclic cyclopropane derivatives are 2-(bicyclo[3.1.0]hex-1-yl)acrylic acid methyl or ethyl esters or their derivatives which are disubstituted in 3-position, such as (3,3-bis(ethoxycarbonyl)bicyclo[3.1.0]hex-1-yl)acrylic acid methyl or ethyl ester. Suitable cyclic allyl sulphides are the addition products of 2-(hydroxymethyl)-6-methylene-1,4-dithiepane or 7-hydroxy-3-methylene-1,5-dithiacyclooctane with 2,2,4-trimethyl hexamethylene-1,6-diisocyanate or an asymmetrical hexamethylene diisocyanate trimer (e.g. Desmodur VP LS 2294 from Bayer AG).

[0073] Formulations based on vinyl esters, vinyl carbonates and vinyl carbamates are also preferred as radically polymerizable monomers. In addition, styrene, styrene derivatives or divinyl benzene, unsaturated polyester resins and allyl compounds or radically polymerizable polysiloxanes which can be prepared from suitable methacrylic silanes such as e.g. 3-(methacryloyloxy)propyltrimethoxysilane, and which are described e.g. in DE 199 03 177 C2 can be used as monomers.

[0074] Furthermore, mixtures of the previously named monomers with radically polymerizable, acid-group-containing monomers which are also called adhesive monomers can also be used as radically polymerizable binders. Preferred acid-group-containing monomers are polymerizable carboxylic acids, such as maleic acid, acrylic acid, methacrylic acid, 2-(hydroxylmethyl)acrylic acid, 4-(meth) acryloyloxyethyltrimellitic acid anhydride, 10-methacryloyloxydecylmalonic acid, N-(2-hydroxy-3-methacryloyloxypropyl)-N-phenylglycine or 4-vinylbenzoic acid.

[0075] Radically polymerizable phosphonic acid monomers, in particular vinylphosphonic acid, 4-vinylphenylphosphonic acid, 4-vinylbenzylphosphonic acid, 2-methacryloyloxyethylphosphonic acid, 2-methacrylamidoethylphosphonic acid, 4-methacryl-amido-4-methyl-pentyl-phosphonic acid, 2-[4-(dihydroxylphosphoryl)-2-oxa-butyl]-acrylic acid or 2-[2-dihydroxyphosphoryl)-ethoxymethyl]-acrylic acid ethyl or 2,4,6-trimethylphenyl ester are also suitable as adhesive monomers.

[0076] Furthermore, acidic polymerizable phosphoric acid esters, in particular 2-methacryloyloxypropyl mono- or dihydrogen phosphate, 2-methacryloyloxyethyl mono- or dihydrogen phosphate, 2-methacryloyloxyethylphenyl hydrogen phosphate, dipentaerythritol-pentamethacryloyloxyphosphate, 10-methacryloyloxydecyl-dihydrogen phosphate, dipentaerythritol-pentamethacryloyloxyphosphate, phosphoric acid mono-(1-acryloyl-piperidine-4-yl)-ester, 6-(methacrylamido)hexyl dihydrogen phosphate and 1,3-bis-(N-acryloyl-N-propyl-amino)-propane-2-yl-dihydrogen phosphate are suitable as adhesive monomers.

[0077] In addition, polymerizable sulphonic acids are suitable as adhesive monomers, in particular vinyl sulphonic acid, 4-vinylphenyl sulphonic acid or 3-(methacrylamido)propyl sulphonic acid.

[0078] Thiol-ene resins which contain mixtures of mono- or multifunctional mercapto compounds and di- or multifunctional unsaturated monomers, above all allyl or norbornene compounds are particularly suitable as binders curable by polyaddition.

[0079] Examples of mono- or multifunctional mercapto compounds are o, m or p-dimercaptobenzene and esters of thioglycol or of 3-mercaptopropionic acid with ethylene, propylene or butylene glycol, hexanediol, glycerol, trimethylolpropane or pentaerythritol.

[0080] Examples of di- or multifunctional allyl compounds are esters of allyl alcohol with di- or tricarboxylic acids, such as malonic, maleic, glutaric, succinic, adipic, sebacic, phthalic, terephthalic or gallic acid and mono- or trifunctional allyl ethers, such as e.g. diallyl ether, ,-bis[allyloxy]alkane, resorcin or hydroquinone diallyl ether and pyrogallol triallyl ether, or other compounds such as e.g. 1,3,5-triallyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, tetraallyl-silane or tetraallylorthosilicate.

[0081] Examples of di- or multifunctional norbornene compounds are Diels-Alder addition products of cyclopentadiene or furan with di- or multifunctional (meth)acrylates, as well as esters and urethanes of 5-norbornene-2-methanol or 5-norbornene-2-ol with di- or polycarboxylic acids such as e.g. malonic, maleic, glutaric, succinic, adipic, sebacic, phthalic, terephthalic or gallic acid, with, respectively, di- or polyisocyanates, such as hexamethylene diisocyanate or its cyclic trimer, 2,2,4-trimethylhexamethylene diisocyanate, toluylene diisocyanate or isophorone diisocyanate.

[0082] In addition to the acyl germanium compounds of general formula (I) the compositions according to the invention may advantageously also contain known photoinitiators (cf. J. P. Fouassier, J. F. Rabek (eds.), Radiation Curing in Polymer Science and Technology, Vol. II, Elsevier Applied Science, London and New York 1993) for the UV or visible range, such as e.g.: benzoin ethers, dialkyl benzil ketals, dialkoxyacetophenones, acyl or bisacyl phosphine oxides, -diketones such as 9,10-phenanthrenequinone, diacetyl, furil, anisil, 4,4-dichlorobenzil and 4,4-dialkoxybenzil and camphorquinone.

[0083] For dual curing the compositions according to the invention can also contain, in addition to the tetraacylgermanes of general formula (I) and/or the (acyl).sub.k(alkyl).sub.4-kgermanes of Formula I, azo compounds such as 2,2-azobis(isobutyronitrile) (AIBN) or azobis-(4-cyano valeric acid), or peroxides, such as dibenzoyl peroxide, dilauroyl peroxide, tert-butylperoctoate, tert-butylperbenzoate or di-(tert-butyl)-peroxide. To accelerate initiation by means of peroxides, combinations with aromatic amines can also be used. Redox systems which have already proved worthwhile are: combinations of benzoylperoxide with amines such as N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine, p-dimethylaminobenzoic acid ethyl ester or structurally related systems. In addition, redox systems consisting of peroxides and reducing agents such as e.g. ascorbic acid, barbiturates or sulphinic acids or combinations of hydroperoxides with reducing agents and catalytic metal ions, such as e.g. a mixture of cumene hydroperoxide, thiourea derivative and copper(II)-acetyl acetonate, are also suitable for dual curing.

[0084] According to the invention compositions are preferred which contain one or more fillers, preferably organic or inorganic particulate fillers. Preferred inorganic particulate fillers are amorphous spherical nanoparticulate fillers based on oxides such as pyrogenic silicic acid or precipitated silicic acid, ZrO.sub.2 and TiO.sub.2 or mixed oxides of SiO.sub.2, ZrO.sub.2 and/or TiO.sub.2 with an average particle diameter of from 10 to 200 nm, mini fillers such as quartz, glass ceramic or glass powder with an average particle size of from 0.2 to 5 m and x-ray opaque fillers such as ytterbium trifluoride or nanoparticulate tantalum(V) oxide or barium sulphate. In addition, fibrous fillers such as nanofibres, glass fibres, polyamide or carbon fibres can also be used.

[0085] For non-dental uses, in addition to the above-named materials, homo- and/or copolymers, preferably poly((meth)acrylate)s, vinyl polymers, preferably polystyrene or polyvinyl acetate, or condensation polymers, preferably polyester, are suitable as fillers. These fillers are preferably used as powder with an average particle size between 0.5 and 100 m. They are partially soluble in the monomer.

[0086] Additionally, the compositions according to the invention can, if necessary, contain further additives such as e.g. stabilizers, UV absorbers, dyes or pigments and solvents, such as e.g. water, ethanol, acetone and/or ethyl acetate or slip additives.

[0087] The materials according to the invention preferably contain:

[0088] (a) 0.001 to 5 wt.-% tetraacyl germane(s) of general formula (I),

[0089] (b) 10 to 99.9 wt.-% radically polymerizable binder,

[0090] (c) 0 to 85 wt.-% filler and optionally

[0091] (d) 0 to 70 wt.-% additive(s).

[0092] Unless otherwise indicated, all percentages relate to the total mass of the material.

[0093] Materials which are particularly suitable as dental cements preferably contain:

[0094] (a) 0.001 to 5 wt.-% tetraacyl germane(s) of general formula (I),

[0095] (b) 10 to 50 wt.-% radically polymerizable binder,

[0096] (c) 40 to 70 wt.-% filler and

[0097] (d) 0 to 5 wt.-% additive.

[0098] Materials which are particularly suitable as dental composites preferably contain:

[0099] (a) 0.001 to 5 wt.-% tetraacyl germane(s) of general formula (I),

[0100] (b) 10 to 40 wt.-% radically polymerizable binder,

[0101] (c) 50 to 70 wt.-% filler and

[0102] (d) 0 to 5 wt.-% additive(s).

[0103] Materials which are particularly suitable as dental coating materials preferably contain:

[0104] (a) 0.001 to 5 wt.-% tetraacyl germane(s) of general formula (I),

[0105] (b) 20 to 99.9 wt.-% radically polymerizable binder,

[0106] (c) 0 to 20 wt.-% nanoparticulate fillers and

[0107] (d) 0.01 to 2 wt.-% additive(s),

[0108] (e) 0 to 70 wt.-% solvent.

[0109] Materials which are particularly suitable as dental adhesives preferably contain:

[0110] (a) 0.001 to 5 wt.-% tetraacyl germane(s) of general formula (I),

[0111] (b) 20 to 98.99 wt.-% radically polymerizable binder,

[0112] (c) 0 to 20 wt.-% nanoparticulate fillers

[0113] (d) 0.01 to 2 wt.-% additive,

[0114] (e) 0 to 50 wt.-% solvent and

[0115] (f) 1 to 20 wt.-% radically polymerizable adhesive monomers.

[0116] Materials for dental prostheses or surgical moulded bodies preferably contain:

[0117] (a) 0.001 to 5 wt.-% tetraacyl germane(s) of general formula (I),

[0118] (b) 30 to 99.9 wt.-% radically polymerizable binder,

[0119] (c) 0 to 60 wt.-% filler(s) and optionally

[0120] (d) 0 to 3 wt.-% additive(s).

[0121] Materials for plastic shaped parts preferably contain:

[0122] (a) 0.001 to 5 wt.-% tetraacyl germane(s) of general formula (I),

[0123] (b) 30 to 99.9 wt.-% radically polymerizable binder,

[0124] (c) 0 to 60 wt.-% filler and optionally

[0125] (d) 0 to 15 wt.-% additive(s).

[0126] Materials for ceramic green bodies preferably contain:

[0127] (a) 0.001 to 5 wt.-% tetraacyl germane(s) of general formula (I),

[0128] (b) 0 to 40 wt.-% radically polymerizable binder,

[0129] (c) 40 to 90 wt.-% filler and optionally

[0130] (d) 0 to 20 wt.-% additive(s).

[0131] The materials according to the invention which contain tetraacyl germanes of general formula (I) as photoinitiator, can be used for the preparation of photopolymerizates, composites, cements, coating materials, primers or adhesives. They are particularly suitable for uses in the medical field, above all for the preparation of dental materials, such as filling composites, fixing cements, adhesives, prosthesis materials, veneering materials, crowns or inlays or coatings.

[0132] The dental materials are suitable primarily for intraoral application by the dentist to restore damaged teeth, i.e. for therapeutic application, e.g. as dental cements, filling composites and veneering materials. However, they can also be used extraorally, for example in the manufacture or repair of dental restorations, such as prostheses, artificial teeth, inlays, onlays, crowns and bridges.

[0133] Furthermore, the materials according to the invention are suitable for medical use in surgery, e.g. in tissue regeneration, for the preparation of hearing aids or in ophthalmology for the preparation of intraocular lenses or contact lenses.

[0134] In technical applications the tetraacyl germanes of general formula (I) can be used as photoinitiator in stereolithography or in 3D printing for the preparation of moulded bodies, prototypes or green bodies, in the field of coatings or in microelectronics e.g. in photoresist technology.

[0135] The invention is described in further detail in the following with reference to examples.

Example 1

[0136] Synthesis of Tetrabenzoyl Germane (TBGe)

##STR00006##

[0137] a) Synthesis of Tetrakis(Trimethylsilyl)Germane [(Me.sub.3Si).sub.4Ge]

[0138] 10.00 g (1.4 mol) lithium was placed in a flask with a dropping funnel and pressure equalizer, and 300 mL dry THF was added. Trimethylchlorosilane (95 ml, 0.75 mol) was rapidly added dropwise and stirred for 10 min. at 78 C. Germanium tetrachloride (21 ml, 0.19 mol, 1:5 diluted in THF) was then added very slowly dropwise at 78 C. (ca. 2 h). Once the addition had ended the reaction solution was heated to room temperature and stirred for a further 12 hours. For working up the reaction mixture was first filtered through Celite and then poured onto 1 M H.sub.2SO.sub.4/ice. After phase separation in the dropping funnel the aqueous phase was extracted 3 times with diethylether, the combined organic phases were dried over anhydrous Na.sub.2SO.sub.4, filtered and the solvent was removed in a rotavapor. For purification the crude product was sublimated (p<mbar; T>150 C.). The yield after sublimation was 26.8 g (Me.sub.3Si).sub.4Ge (42%).

[0139] NMR spectroscopy: .sup.1H(CDCl.sub.3) [ppm]=0.24 (s, Si(CH.sub.3).sub.3). .sup.29Si (CDCl.sub.3): [ppm]=5.33 (SiMe.sub.3).

[0140] b) Synthesis of Tetrabenzoyl Germane (TBGe)

[0141] 3.00 g (8.21 mmol; 1.00 eq.) Tetrakistrimethylsilyl germane and 1.01 g KOtBu (9.03 mmol; 1.1 eq.) were weighed into a Schlenk flask and dissolved in 20 ml ethylene glycol dimethyl ether (DME). The reaction was complete when the reaction solution had a clear yellow to orange colour. After approximately one hour 4.18 g (33.66 mmol, 4.1 eq.) benzoyl fluoride was added by means of a syringe. The reaction solution became black and, after the addition was complete, orange. The reaction solution was then stirred overnight at room temperature. After aqueous working up with 3% H.sub.2SO.sub.4 the phases were separated and the aqueous phase extracted 3 times with diethyl ether. The combined organic phases were dried over anhydrous sodium sulphate and the volatile components removed in a rotary evaporator. The obtained crude product was recrystallized from acetone and 1.70 g pure tetrabenzoyl germane (42%) was obtained as a crystalline, yellow solid (melting point: 82.5-83.0 C.)

[0142] NMR spectroscopy: .sup.1H (CDCl.sub.3): [ppm]=7.99-7.96 (m, 2H, aryl-H), 6.84-6.82 (m, 3H, aryl-H). .sup.13C (CDCl.sub.3): 5 [ppm]=222.01 (GeCOPh), 140.57 (aryl-C1), 133.81 (aryl-C2), 129.15 (aryl-C3), 128.77 (aryl-C4).

[0143] UV-VIS spectroscopy: [nm] ( [L mol.sup.1 cm.sup.1])=403 (1240), 419sh (1050).

[0144] IR spectroscopy: [cm.sup.1]=1639, 1617 (m, CO); 1590, 1574, 1444 (m, C=C); 880, 762, 673 (s, CH).

Example 2

[0145] Synthesis of Tetrakis(2,4,6-Trimethylbenzoyl)Germane (TMGe)

##STR00007##

[0146] 2.77 g (7.66 mmol; 1.00 eq.) (Me.sub.3Si).sub.4Ge and 0.94 g KOtBu (8.4 mmol; 1.1 eq.) were weighed into a Schlenk vessel and dissolved in 15 ml DME. The reaction was complete when the reaction solution had a clear yellow to orange colour. After approximately one hour the obtained solution was slowly added dropwise to a solution, cooled to 78 C., of 1.66 g (0.91 mmol, 1.2 eq.) 2,4,6-trimethylbenzoyl chloride in 80 ml diethyl ether and the obtained mixture stirred overnight at room temperature. After aqueous working up with 3% H.sub.2SO.sub.4 the phases were separated and the aqueous phase extracted 3 times with diethyl ether. The combined organic phases were dried over anhydrous sodium sulphate and the volatile components removed in a rotary evaporator. The formed crude product with a mass of 3.85 g contained 36% tetraacyl germanium and 64% monoacyl germanium compound and was separated by column chromatography over silica gel (gradient: heptane, toluene). Recrystallization from acetone was then carried out, and 1.58 g (24%) tetrakis(2,4,6-trimethylbenzoyl)germane was obtained as a crystalline, yellow solid (melting point: 198-199 C.)

[0147] NMR spectroscopy: .sup.1H (CDCl.sub.3): [ppm]=6.57 (s, 2H, Aryl-H), 2.24 (s, 3H, para-CH.sub.3), 2.06 (s, 6H, ortho-CH.sub.3). .sup.13C (CDCl.sub.3): [ppm]=233.40 (GeCOMes), 141.60 (aryl-C1), 139.26 (aryl-C2), 132.88 (aryl-C3), 128.53 (aryl-C4), 21.15 (para-CH.sub.3), 19.13 (ortho-CH.sub.3).

[0148] UV-VIS spectroscopy: [nm] ( [L mol.sup.1 cm.sup.1])=288 (17428), 376 (1475).

[0149] IR spectroscopy: [cm.sup.1]=2917 (w, .sub.asCH.sub.3); 1639, 1608 (m, CO); 1202 (m, .sub.asCH.sub.3); 833, 609 (m, CH.sub.3).

Example 3

[0150] Preparation of Light-Curing Resins Using Tetrabenzoyl Germane (TBGe) or Tetrakis(2,4,6-Trimethylbenzoyl)Germane (TMGe) from Examples 1 and 2

[0151] Various light-curing resin systems were prepared from a mixture (values given in mass-%) of dimethacrylates Bis-GMA (additionproduct of methacrylic acid and bisphenol-A-diglycidyl ether)), UDMA (addition product of 2-hydroxyethyl methacrylate and 2,2,4-trimethyl hexamethylene diisocyanate) and D.sub.3MA (decanediol-1,10-dimethacrylate) and the Ge initiators tetrabenzoyl germane (TBGe), tetrakis(2,4,6-trimethyl benzoyl)germane (TMGe) and dibenzoyl diethyl germane (DBEGe, as reference) (Table 1). The resin systems R1 and R4 (0.29 mmol/100 g) or R2, R3 and R5 (0.59 mmol/100 g) contain the same molar quantity of photoinitiator.

TABLE-US-00001 TABLE 1 Composition of resins R1 to R5 Resin Component R1 R2 R3 R4* R5* TBGe 0.14 0.29 TMGe 0.39 DBEGe 0.10 0.20 Bis-GMA 42.10 42.10 42.10 42.10 42.10 UDMA 37.46 37.31 37.21 37.50 37.40 D.sub.3MA 20.30 20.30 20.30 20.30 20.30 *Comparison example

[0152] Test pieces were prepared from the materials, which were irradiated twice for 3 minutes with a dental light source (Spectramat, Ivoclar Vivadent AG) and thereby cured. The flexural strength and the flexural modulus of elasticity were determined according to ISO standard ISO4049 (DentistryPolymer-based filling, restorative and luting materials) after 24 h storage of the test pieces at room temperature (RT) or after 24 h storage in water (WS) at 37 C. (Table 2).

TABLE-US-00002 TABLE 2 Flexural strength (FS, MPa) and flexural modulus of elasticity (FME, GPa) of polymerized resins R1 to R5 R1 R2 R3 R4* R5* FS, RT 72.7 3.5 81.7 9.5 81.5 5.5 58.5 2.3 79.7 7.5 FS, WS 98.2 8.7 115.2 11.2 101.8 6.1 75.3 3.0 96.4 8.1 FME, RT 1.59 0.12 2.25 0.22 1.89 0.21 1.15 0.07 1.76 0.19 FME, WS 1.15 0.20 2.48 0.10 2.37 0.12 1.54 0.11 2.19 0.20 *Comparison example

[0153] The results in Table 2 prove that the resins R1 and R3 with the tetra(benzoyl)germane TBGe according to the invention as photoinitiator in comparison with the reference resins R4 and R5 based on the known di(benzoyl)germane DBEGe with the same molar concentration of the photoinitiators (compare R1 with R4 or R2 with R5) lead to photopolymerisates with improved strength and a higher modulus of elasticity.

Example 4

[0154] Preparation of Light-Curing Resins Using Tetrabenzoyl Germane (TBGe) or Tetrakis(2,4,6Trimethylbenzoyl)Germane (TMGe) from Examples 1 and 2

[0155] The composite pastes K1 to K5 were prepared from the resins R1 to R5 from Example 3 by means of a roll mill (Exakt model, Exakt Apparatebau, Norderstedt). In each case 36.44 wt. % of resins R1 to R5 were filled with 52.22 wt. % of silanized glass filler GM 27884 (1.0 m, Schott), 4.02 wt. % of silanized glass filler GM G018-056 (1.0 m, Schott), 4.02 wt. % silanized SiO.sub.2ZrO.sub.2 mixed oxide Spherosil (Transparent Materials, USA) 0.80 wt. % of silanized pyrogenic silicic acid OX-50 (Degussa) and 2.50 wt. % ytterbium trifluoride YbF.sub.3 (Sukgyung, South Korea). Analogous to Example 3, test pieces were prepared from the pastes, cured, and the flexural strength and the elastic modulus determined (Table 3).

TABLE-US-00003 TABLE 3 Flexural strength (FS, MPa) and flexural modulus of elasticity (FME, GPa) of the polymerized composite pastes K1 to K5 K1 K2 K3 K4* K5* FS, RT 96.5 9.2 125.4 7.7 114.8 4.6 92.4 6.4 112 6.9 FS, WS 117.4 8.7 129.7 9.9 133.8 4.8 101.9 9.0 123.3 3.5 FME, RT 5.51 0.33 7.13 0.40 6.73 0.37 4.99 0.39 6.20 0.32 FME, WS 6.16 0.46 7.68 0.87 7.36 0.62 5.45 0.64 6.59 0.34 *Comparison example

[0156] The results in Table 3 prove that the composite pastes K1 and K3 with the tetra(benzoyl)germane TBGe according to the invention as photoinitiator in comparison with the reference pastes K4 and K5 based on the known di(benzoyl)germane DBEGe with the same molar concentration of the photoinitiators (compare K1 with K4 or K2 with K5) after curing, lead to composites with an improved strength and higher modulus of elasticity.