Radically polymerisable compound and composition

Abstract

The invention relates to a radically polymerisable compound represented by a structure of formula 1: PG-Sp-PCA-Sp- [OG (O) NH-K-NHC (O) O-Sp-PCA-Sp]n-PG (formula 1), wherein PG = in each case independently selected from a radically polymerisable group, R1 = selected from hydrogen, a C1-C8 alkyl group, an aryl group and an araliphatic group having C6-C8 carbon atoms, R2 = selected from hydrogen, a C1-C4 alkyl group; Sp = in each case independently of one another a spacer group selected from unbranched and branched alkylene with C1-C19 carbon atoms, which may additionally contain oxygen, sulfur and / or -OOC- in the carbon chain, or Sp is absent; PCA = in each case independently of one another a polycyclic group; K = an aliphatic acyclic, saturated or unsaturated unit having C1-C15 carbon atoms, an aliphatic cyclic, saturated or unsaturated unit having C3-C15 carbon atoms, or an aromatic or araliphatic unit having C6-C14 carbon atoms; n = 1 to 9. The invention also relates to a process for preparing such a compound, a radically polymerisable composition containing such a compound, the use thereof and a cured dental material.

Description

[0001]12.03.2024 / MR Radically polymerizable compound and composition The invention relates to a radically polymerizable compound, a process for producing such a compound, a radically polymerizable composition containing such a compound, the use of such compounds, and a cured dental material. Radically polymerizable dental materials primarily contain (meth)acrylate monomers. For restorative and prosthetic dental materials, such as dental fillings or dentures, dimethacrylate systems are usually used due to their properties, such as rapid radical polymerization, good mechanical properties, and aesthetic appearance. Common monomers include, for example,Linear aliphatic or aromatic group-containing structures with terminal methacrylate functionalities that have a high molecular weight, such as 2,2-bis-[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (BisGMA) and 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyl-bis(2-methylacrylate) (UDMA). For some time now, there has been an effort to largely avoid the use of BisGMA or other monomers with structural elements derived from bisphenol A and to replace them, at least partially, with other compounds. The focus here is primarily on urethane monomers and oligomers. UDMA is the most widely used commercially as at least a partial replacement for BisGMA in the field of dental materials. Monomers such as BisGMA and UDMA, although widely used in commercial radically polymerizable compositions for the production of dental materials, have some disadvantages.They are generally highly viscous to solid substances. Therefore, mixtures with monomers with a significantly low viscosity, such as triethylene glycol dimethacrylate (TEDMA), are used. TEDMA is a very flexible, low-molecular-weight monomer with a low viscosity (of 0.01 Pa s at 23°C) and exhibits high mobility during polymerization, which favors the polymerization conversion. However, the polymerizable compositions containing these monomer mixtures and the dental materials obtained from them exhibit several problematic properties that can impair their clinical treatment success. For example, compositions containing dimethacrylate monomers exhibit a relatively low polymerization conversion, significant polymerization shrinkage, poor toughness, and undesirable water absorption.The known systems can often only achieve a comparatively low conversion of the double bonds, which not only contributes to poor mechanical properties and wear resistance, but is also detrimental to the toxicology and biocompatibility of the polymerized dental materials. Furthermore, the volumetric shrinkage of the currently used dimethacrylate monomers and the shrinkage stresses of a dental filling can lead to failure of the bond between tooth and filling, resulting in microleakage and subsequent secondary caries, which in turn can significantly reduce the longevity of the restoration. Attempts to increase the double bond conversion to reduce unreacted monomers unfortunately lead to an increase in polymerization shrinkage and shrinkage stress.Low-molecular-weight monomers with oligo[ethyleneoxy] groups, such as TEDMA, which exhibit a certain degree of water solubility and thus bioavailability, are now being critically evaluated due to their toxicological properties and their sensitivity to biodegradative processes. Monomers with the structural element bis-2,2-[p-oxyphenyl]propane, i.e., monomers based on bisphenol A, are also being viewed critically, as dental materials containing monomers or oligomers with these structural elements have been found to release detectable amounts of bisphenol A, which is considered to have toxicologically critical properties. There are various approaches to increasing conversion or reducing volume shrinkage. In dental composites for tooth fillings that contain filler in an organic resin matrix, attempts are being made to reduce volume shrinkage by increasing the filler content.However, if the filler content is too high, it becomes difficult to mix the fillers with the organic resin. Furthermore, the filler content is limited for dental composites, which must have a certain flowability. To increase conversion and reduce polymerization shrinkage, new monomers continue to be developed, such as urethane methacrylate monomers with high molecular weights. The synthesis of these monomers is complex and usually requires purification steps, which leads to limited availability of such monomers. For a given functionality of the monomers, an increase in molecular weight is generally associated with a deterioration in the mechanical properties of the cured dental materials.Furthermore, the increased viscosity of such monomers requires the use of larger amounts of low-viscosity monomers for use in dental composites, which has an adverse effect on shrinkage. EP 2436365 B1 describes low-shrinkage dental composites containing monomer mixtures that contain the monomers (b1) and (b2) in a ratio of 1:20-5:1. The example compositions each contain 4.8-76.6 wt.% bis((meth)acryloyloxymethyl)tricyclo[5.2.1.0. 2,6]decane (b1), 90.9–19.1 wt.% UDMA (b2), and 4.3 wt.% TEDMA (b2). These composites exhibit a polymerization shrinkage of approximately 1.50%, regardless of the ratio (b1) to (b2). If, as in Comparative Example 11, the filler content is reduced and the proportion of TEDMA is increased, the polymerization shrinkage increases. Vaidyanathan et al., Visible light cure characteristics of a cycloaliphatic polyester dimethacrylate alternative oligomer to bisGMA; Acta Biomater Odontol Scand. 2015; 1:59–65, disclose the use of PEM-665 as a BPA-free alternative to BisGMA in combination with 30 or 50 wt.% TEDMA. The polymerization conversions of these mixtures were investigated, with the combinations of PEM with TEDMA exhibiting a higher percentage polymerization conversion than the combinations of BisGMA with TEDMA. There is still a need for radically polymerizable compounds orRadically polymerizable compositions containing compounds that can enable reduced toxicity potential and reduced volume shrinkage while simultaneously providing good mechanical properties of the dental material produced therefrom, and that are readily available. The present invention is therefore based on the object of providing a radically polymerizable compound or a radically polymerizable composition containing such a compound that overcomes the above-mentioned disadvantages of the prior art.In particular, it should be possible to provide a radically polymerizable compound and a radically polymerizable composition with which it is possible to obtain dental materials with reduced polymerization shrinkage and, at the same time, good mechanical properties of the dental material, such as very good flexural strength and tensile strength as well as good fracture toughness, which are also toxicologically safe. Furthermore, it should be possible to obtain a radically polymerizable compound or a radically polymerized composition containing such a compound, which have a refractive index that is particularly suitable for producing materials containing fillers commonly used in the dental field, which have advantageous optical properties, particularly with regard to translucency and opacity.Furthermore, it is also the object of the present invention to provide a process that enables the preparation of such a radically polymerizable compound in a simple manner, with high purity, and without undesirable discoloration. The invention achieves this object by means of a radically polymerizable compound represented by a structure of formula 1: PG-Sp-PCA-Sp-[OC(O)NH-K-NHC(O)O-Sp-PCA-Sp]. n -PG (Formula 1), where PG = each independently selected from a radically polymerizable group, preferably selected from (NR 1 )OC-CR 2 =CH2 and OOC-CR 2 =CH2, preferably selected from OOC-CR 2 =CH2, R 1 = selected from hydrogen, a C1-C8 alkyl group, an aryl group and an araliphatic group having C6-C8 carbon atoms, preferably selected from a C1-C8 alkyl group and a benzyl group, R 2= selected from hydrogen, a C1-C4 alkyl group, preferably selected from hydrogen and methyl; Sp = in each case independently of one another a spacer group selected from unbranched and branched alkylene with C1-C19 carbon atoms, which may additionally contain oxygen, sulfur and / or -OOC- in the carbon chain, or Sp is omitted; PCA = in each case independently of one another a polycyclic group, preferably an aliphatic polycyclic group, more preferably an aliphatic bi- or tricyclic group; K = an aliphatic acyclic, saturated or unsaturated unit with C1-C15 carbon atoms, preferably C3-C13 carbon atoms, more preferably C6-C9 carbon atoms, where the unit may be substituted with one or more aliphatic C1-C3 carbon substituents, an aliphatic cyclic, saturated or unsaturated unit with C3-C15 carbon atoms, preferably C5-C13 carbon atoms, more preferably C6-C13 carbon atoms,where the unit may be substituted by one or more aliphatic C1-C3 carbon substituents, or an aromatic or araliphatic unit with C6-C14 carbon atoms, preferably C6-C13 carbon atoms, where the unit may be substituted by one or more aliphatic C1-C3 carbon substituents; n = 1 to 9, preferably 1 to 6. Preferred embodiments are found in the subclaims. First, some terms used within the scope of the invention will be explained. Within the scope of the present invention, (polymerizable) dental materials are understood to mean materials for (bio)medical use, in particular on dental hard tissue, such as tooth enamel and dentin, or on bone tissue, such as jawbone. In the context of the present invention, the radically polymerizable compounds are monomers in the case where n = 1, and in the cases where n = 2 to 9,are oligomers. K is preferably selected from a linear aliphatic, saturated unit with C6-C9 carbon atoms, where the unit may be substituted by one or more aliphatic C1-C3 carbon substituents, an aliphatic cyclic, saturated unit with C6-C13 carbon atoms, where the unit may be substituted by one or more aliphatic C1-C3 carbon substituents, and an aromatic or araliphatic unit with C6-C13 carbon atoms, which has at least two aliphatic substituents, preferably C1-C3 substituents, on the aromatic ring. Furthermore, K can be 1,3- and 1,4-cyclohexanylene, preferably 1,3-cyclohexanylene. Preferably, the spacer group Sp is selected from methylene, *CH2-(OC2H4), p , *CH2-(OC3H6) p , *(OC2H4) p , *(OC3H6) p , *CH2-(OC(O)-R 5 - ) p , *(OC(O)-R 5 -) p and *SR 5, where p = 1-5, preferably 1-3 and R 5 a C1-C12 alkylene group, preferably a C2-C6 alkylene group. The symbol * indicates the bonding site to the PCA unit. More preferably, the spacer group Sp is methylene. Preferably, the polycyclic PCA group is selected from structures of the following formulas 2 to 13: (Formula 2) (Formula 3) (Formula 4) (Formula 5) (Formula 6) (Formula 7) (Formula 8) (Formula 9) (Formula 10) (Formula 11) (Formula 12) (Formula 13), which may optionally be substituted with one or more C1-C4 alkyl groups. This also includes all stereoisomers of these formulas, in particular enantiomers and diastereomers. Furthermore, the polycyclic group PCA is preferably selected from 2-methyl-3,3-norbornanediyl, 2-ethyl-3,3-norbornanediyl, 2-propyl-3,3-norbornanediyl, 2-butyl-3,3-norbornanediyl, bicyclo[2.2.2]octane-1,4-diyl, bicyclo[2.2.2]octane-2,3-diyl, bicyclo[2.2.2]oct-5-ene-5,6-diyl, 1,3-adamantanediyl, tetracyclo[6.6.2.0 2,7 .0 9,14 ]hexadeca-2,4,6,9,11,13-hexaen-15,16-diyl, 1,4-cubane-diyl, 2,6,6-trimethylbicyclo(3.1.1)heptane-2,3-diyl, and 1,7,7-trimethylbicyclo(3.1.1)heptane-2,3-diyl. In a preferred embodiment, the polycyclic group PCA is an aliphatic tricyclic group, more preferably tricyclo[5.2.1.0 / 2,6]decanylene (TCD) (Formula 2). K is preferably selected from the structures of the following formulas 14 to 26: . Furthermore, K is preferably selected from the following groups: 1,5-naphthylene (from naphthylene-1,5-disocyanate), 2,4,6-triisopropyl-m-phenylene (from 2,4,6-triisopropyl-m-phenylene diisocyanate), 2,5-bis(methanediyl-bicyclo-[2.2.1]-heptane and 2,6-bis(methanediyl-bicyclo-[2.2.1]-heptane (from norbornane-2,5-diylbis(methylene) diisocyanate or norbornane-2,6-diylbis(methylene) diisocyanate). More preferably, K is selected from a structure of formulas 14, 15, 16, 17, 18, 19 and 20. In one embodiment, the radically polymerizable compound is preferably represented by a structure of formula 27: (Formula 27), where R 2= hydrogen or a methyl group; Sp = in each case independently of one another a spacer group selected from unbranched and branched alkylene having C1-C19 carbon atoms, which may additionally contain oxygen, sulfur and / or -OOC- in the carbon chain, or Sp is omitted; PCA = in each case independently of one another a polycyclic group, preferably an aliphatic polycyclic group, more preferably an aliphatic bi- or tricyclic group, even more preferably a tricyclic group, most preferably tricyclo[5.2.1.0 / 2,6]decanylene; K = an aliphatic acyclic, saturated or unsaturated unit with C1-C15 carbon atoms, preferably C3-C13 carbon atoms, more preferably C6-C9 carbon atoms, where the unit may be substituted with one or more aliphatic C1-C3 carbon substituents, an aliphatic cyclic, saturated or unsaturated unit with C3-C15 carbon atoms, preferably C5-C13 carbon atoms, more preferably C6-C13 carbon atoms, where the unit may be substituted with one or more aliphatic C1-C3 carbon substituents, or an aromatic or araliphatic unit with C6-C14 carbon atoms, preferably C6-C13 carbon atoms, where the unit may be substituted with one or more aliphatic C1-C3 carbon substituents may be substituted; r = 1 to 9, preferably 1 to 6. Preferably, the radically polymerizable compound is represented by a structure selected from the following formulas 28-31:. (Formula 29), (Formula 31), where t, u, v and w are each independently 1-9, preferably 1-6; and R 2= selected from hydrogen, a C1-C4 alkyl group, preferably selected from hydrogen and a methyl group. In the radically polymerizable compound represented by a structure selected from the following formulas 28-31, it should be noted that a reversed sense of direction of the tricyclo[5.2.1.0 / 2,6]decanylene groups is also included. The invention further relates to a process for producing a radically polymerizable compound, characterized in that the process comprises the following steps: a) reacting a diol of a polycyclic PCA group with a (meth)acrylic acid ester to form a PCA mono(meth)acrylate which has a hydroxy group, by means of enzymatic catalysis, b) reacting the PCA mono(meth)acrylate containing the hydroxy group from step a) with a diisocyanate compound, preferably using a catalyst.The reaction product PCA mono(meth)acrylate with a hydroxy group from step a) can be prepared by transesterification from PCA di(meth)acrylate and PCA diol, preferably TCD di(meth)acrylate (TCD-D(M)A) and TCD dimethanol. Preferably, the corresponding mono(meth)acrylate, each containing one (meth)acrylate group and one OH group, is formed in a mixture with PCA-D(M)A and residues of PCA dimethanol. Surprisingly, this reaction step makes it possible to produce reaction products that are low in color to colorless, which differ significantly from, for example, acid-catalyzed compounds, which are usually intensely colored. The latter compounds generally require more complex purification prior to use, at least in areas where appearance is also important. The conversion (transesterification) in step a) occurs through enzymatic catalysis. Preferred enzymes are lipases or mixtures of lipases.In a preferred embodiment, CALB is used. In a particularly preferred embodiment, CALB is used immobilized on a support. The diol from step a) is preferably selected from primary and secondary alcohols containing a polycyclic PCA group. Suitable primary diols can be bis(hydroxymethyl)tricyclo[5.2.1.0]. 2,6 ]decane (mixture of isomers), 5-norbornene-2,2-dimethanol, 5-norbornene-2,3-dimethanol, bicyclo[2.2.1]heptane-2,3-dimethanol, 2-methyl-3,3-norbornanedimethanol, 2-ethyl-3,3-norbornanedimethanol, 2-propyl-3,3-norbornanedimethanol, 2-Butyl-3,3-norbornanedimethanol, Bicyclo[2.2.2]octane-1,4-dimethanol, Bicyclo[2.2.2]oct-5-en-5,6-diyldimethanol, Bicyclo[2.2.2]octane-2,3-dimethanol, Tricyclo[3.3.1.1 3,7 ]decane-1,3-diethanol, 1,3-adamantanediethanol, pentacyclopentadecanedimethanol, tetracyclo[6.6.2.0 2,7 .0 9,14]hexadeca-2,4,6,9,11,13-hexaen-15,16-diyldimethanol, 1,4-bis(hydroxymethyl)cubane and [5-(hydroxymethyl)-5,6-dimethyl-6-bicyclo[2.2.1]hept-2-enyl]methanol. Suitable secondary diols can be bicyclo[2.2.1]hept-2-ene-1,2-diol, bicyclo[2.2.1]heptane-1,2-diol, bicyclo[2.2.1]heptane-2,5-diol, bicyclo[2.2.1]heptane-1,4-diol, 2,6,6-trimethyl-bicyclo(3.1.1)heptane-2,3-diol, 1,7,7-trimethyl-bicyclo[2.2.1]heptane-2,3-diol, 2,3-dihydroxynorbornane, 2-(propyl-1,2-diol)-norbornane, tricyclo[5.2.1.0 2,6]decane-3,4-diol and 2,6-dihydroxyadamantane. The diols are generally commercially available. The (meth)acrylic acid ester from step a) is preferably selected from alkyl esters, vinyl esters, aryl esters, and other active esters. Both mono(meth)acrylates and di(meth)acrylates can be used. In the case of mono(meth)acrylates, it is preferred that the resulting monoalcohol be removed from the mixture during the reaction. In the case of di(meth)acrylates, the use of the di(meth)acryloyl ester of the PCA diol is preferred. In this case, the mono(meth)acryloyl ester of the PCA diol is formed in a mixture with the diol and the di(meth)acryloyl ester of the PCA diol. It is particularly advantageous that this mixture is particularly low in color and contains a high proportion of mono(meth)acrylate.which is favorable for the subsequent reaction in step b). A catalyst can be used for step b). Suitable catalysts in step b) are preferably urethanization catalysts. Such catalysts accelerate the reaction rate of the reaction between a hydroxy group and an isocyanate group. Examples of the urethanization catalyst include organotin compounds, such as dimethyltin dineodecanoate, dibutyltin dilaurate, dibutyltin dioctate, and tin octoate; organobismuth compounds, such as bismuth neodecanoate; organic compounds of metals other than tin, such as copper naphthenate, cobalt naphthenate, zinc naphthenate, acetylacetonatozirconium, acetylacetonatoiron, and acetylacetonatogermanium; Amine compounds and their salts, such as triethylamine, 1,4-dizabicyclo-[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undecene, N,N-dimethylcyclohexylamine, pyridine, N-methylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N,N',N'-pentamethyldiethylenetriamine, N,N,N',N'-tetra(340-dimethylaminopropyl)methanediamine, N,N'-dimethylpiperazine, and 1,2-dimethylimidazole; and trialkylphosphine compounds, such as tri-n-butylphosphine, tri-n-hexylphosphine, tricyclohexylphosphine, and tri-n-octylphosphine. Preferred are dibutyltin dilaurate, dimethyltin dineodecanoate, and bismuth neodecanoate. The diisocyanate compound used in step b) is preferably selected from diisocyanates containing aliphatic, cycloaliphatic, polycyclic, araliphatic, or aromatic structural elements. Suitable diisocyanate compounds can be 4,4'-methylenediphenyl diisocyanate (MDI), 4-methyl-m-phenylene diisocyanate and other isomers (TDI), 1,5-naphthylene diisocyanate (NDI), 1,3-bis(isocyanatomethyl)benzene (XDI), 1,3-bis(1-isocyanato-1-methylethyl)benzene (TMXDI), 2,4,6-triisopropyl-m-phenylene diisocyanate (TRIDI), 3,3'-dimethylbiphenyl-4,4'-diyl diisocyanate (TODI), 1,4-Phenylene diisocyanates, hexamethylene diisocyanates (HDI), 2,2,4- and 2,4,4-trimethylhexamethylene-1,6-diisocyanate (TMDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanates and other isomers (IPDI), 4,4'-methylenedicyclohexyl diisocyanate (H12MDI), 2,5- and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (NBDI), 1,4-cyclohexane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane (BIMC), and octahydro-2,5-bis(isocyanatomethyl)-4,7-methano-1H-indene (TCDDI). The diisocyanate compounds are generally commercially available. A ratio of one mole of the hydroxyl group from the PCA mono(meth)acrylate to one mole of the isocyanate group from the diisocyanate compound is preferably 0.5 to 1.5, more preferably 0.8 to 1.2. Even more preferably, this ratio is 1.0. A ratio of a molar amount of all hydroxyl groups to a molar amount of all isocyanate groups in the reaction in step b) is preferably 1.1 to 1.0, more preferably 1.02 to 1.0 The reactions in steps a) and b) can be carried out in an inert solvent or solvent mixture or, if appropriate, even without a solvent. A wide variety of solvents can be used as solvents for step a), as long as they are a solvent that is inert to the reaction. Examples include non-polar hydrocarbon-based solvents such as n-hexane, benzene, toluene and xylene; non-polar halogen-based solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and perchloroethylene; medium-polar ketone-based solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; medium-polar ether-based solvents such as diethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane; and polar solvents such as acetonitrile, tert-butyl alcohol, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone,Dimethyl sulfoxide and sulfolane. These solvents can be used individually or as a mixture. Non-polar solvents and solvents of medium polarity are preferred. A wide variety of solvents can be used as the solvent for step b), as long as they are a reaction-inert solvent. Examples include hydrocarbon-based solvents such as n-hexane, benzene, toluene, and xylene; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester-based solvents such as ethyl acetate and butyl acetate; ether-based solvents such as diethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydrofuran, and dioxane; halogen-based solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and perchloroethylene. and polar solvents such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone,Dimethyl sulfoxide and sulfolane. These solvents can be used individually or as a mixture. The reactions in steps a) and b) can be carried out in a temperature range from 0°C to 100°C. The temperature range between 20°C and 80°C is preferred, more preferably between 40°C and 60°C. The reactions in steps a) and b) can be carried out in the presence of polymerization inhibitors. Polymerization inhibitors prevent the radical polymerization of the (meth)acrylate groups. Examples of polymerization inhibitors are 2,6-di-tert-butyl-4-methylphenol (BHT), hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO), and phenothiazine (PTZ). Following step b), it may be necessary in a further step c)to remove any remaining solvents from the resulting reaction mixture. The present invention further relates to a radically polymerizable composition comprising: a) one or more radically polymerizable compounds according to the invention, preferably according to one of claims 1 to 7; b) optionally one or more further radically polymerizable monomers and / or oligomers which do not fall under the at least one radically polymerizable compound of formula 1; c) optionally at least one initiator or one initiator system for the polymerization; d) optionally one or more stabilizers; e) optionally one or more fillers; f) optionally dental additives. It is preferred that the radically polymerizable composition contains one or more radically polymerizable compounds of formula 1 in a mass fraction of 1-100 wt.%, preferably 2-80 wt.%, preferably 2-65 wt.%,more preferably 10-65 wt.%, based on the total mass of all radically polymerizable monomers and oligomers of the polymerizable composition. Preferably, several compounds of formula 1, selected from monomers (n = 1) and / or oligomers (n = 2-9, preferably n = 2-5), are present in the radically polymerizable composition. One or more of the following constituents can be present in the radically polymerizable composition in each case in the following mass proportions, based on the total mass of the polymerizable composition: a) one or more radically polymerizable compounds of formula 1 from 1 to 99 wt.%, preferably from 2 to 95 wt.%, further preferably from 2 to 80 wt.%, even more preferably 2 to 65 wt.%, even more preferably 10-65 wt.%; b) one or more further radically polymerizable monomers or oligomers,which do not fall under the at least one compound of formula 1, from 0 to 99 wt.%, more preferably from 10 to 99 wt.%, even more preferably from 20 to 98 wt.%, even more preferably from 35 to 90 wt.%; c) the at least one initiator or initiator system for the polymerization from 0 to 5 wt.%, preferably from 0.01 to 5 wt.%; d) the stabilizers from 0 to 5 wt.%, preferably from 0.001 to 5 wt.%, more preferably 0.005-2 wt.- e) the fillers or filler particles from 0 to 95 wt.%, preferably from 1 to 95 wt.%, more preferably from 5 to 92 wt.%; f) the dental additives from 0 to 5 wt.%, preferably from 0.001 to 5 wt.%. In a preferred embodiment, the radically polymerizable composition is a radically polymerizable dental material. b) further polymerizable monomers or oligomers. The radically polymerizable composition can,In addition to the at least one radically polymerizable compound of formula 1, one or more further radically polymerizable monomers or oligomers that do not fall under the at least one radically polymerizable compound of formula 1. The selection of these further radically polymerizable monomers and oligomers is preferably made depending on which material is to be produced. This also applies to the proportion of the further radically polymerizable monomers and / or oligomers in the radically polymerizable composition. Suitable further radically polymerizable monomers are, for example, selected from bis(methacryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane, bis(acryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane. They can also be monomers,which can be obtained by esterification reaction, for example, according to the preparation examples of EP 0235836 B1 or US 4131729 / DE 2816823. Suitable further radically polymerizable monomers can be selected from urethane (meth)acrylates having two or more (meth)acrylate groups. These are preferably urethane di(meth)acrylates and / or urethane tri(meth)acrylates. Preference is given to urethane (meth)acrylates selected from linear or branched alkylene-functionalized urethane (meth)acrylates and urethane (meth)acrylate-functionalized polyethers. Preference is given to difunctional urethane (meth)acrylates,which are selected from difunctional urethane (meth)acrylates with a bivalent alkylene group and those with a bivalent cyclic aliphatic hydrocarbon group. Such difunctional urethane (meth)acrylates with a bivalent alkylene group are preferably selected from linear or branched urethane di(meth)acrylates functionalized with a bivalent alkylene group, urethane di(meth)acrylate-functionalized polyethers with alkylene group(s), such as bis(methacryloxy-2-ethoxycarbonylamino)alkylene, bis(methacryloxy-2-ethoxycarbonylamino)-substituted polyalkylene ethers. Preference is given to bis(methacryloxy-2-ethoxycarbonylamino)alkylenes which comprise linear or branched C3-C20 alkylene groups, preferably C3-C9 alkylene groups. A methyl-substituted alkylene is also particularly preferred. Furthermore, the other radically polymerizable monomer can be a reaction product of 3-hydroxypropyl methacrylate and trimethylhexamethylene diisocyanate,or a reaction product of 3-hydroxypropyl acrylate and trimethylhexamethylene diisocyanate. Suitable other radically polymerizable monomers are available, for example, under the following trade or brand names: Ebecryl 230 (aliphatic urethane diacrylate), Actilane 9290, Craynor 9200 (di-urethane acrylate oligomer), Ebecryl 210 (aromatic urethane diacrylate oligomers), Ebecryl 270 (aliphatic urethane diacrylate oligomer), Actilane 165, Actilane 250, Photomer 6210 (aliphatic urethane diacrylate), Photomer 6623 (hexafunctional aliphatic urethane resin), Photomer 6891 (aliphatic urethane triacrylate), UDMA, Roskydal LS 2258 (aliphatic urethane acrylate oligomer), Roskydal XP 2513 (unsaturated aliphatic urethane acrylate), Genomer 4256, Genomer 4267 (urethane acrylates), Genomer 4259 (aliphatic urethane dimethacrylate), RCX 18-059 (aliphatic urethane dimethacrylate), UN 1963CG (aliphatic urethane methacrylate),CN 1993CG (aliphatic urethane methacrylate), PRO 21252 (aliphatic urethane acrylate), H1391 (hydroxypropyl urethane dimethacrylate), H1391 (urethane dimethacrylate), X851-1066 (urethane dimethacrylate IP-DI), X726-000 (PEG 400 extended urethane dimethacrylate), urethane methacrylate 11-70 and urethane methacrylate 14-774. Particularly preferred are further radically polymerizable monomers which have a structure of the following formula 32: PG'-Sp'-PCA'-Sp'-PG (Formula 32), where PG' = each independently selected from a radically polymerizable group, preferably selected from (NR, 3 )OC-CR 4 =CH2 and OOC-CR 4 =CH2, preferably selected from OOC-CR 4 =CH2, R 3 = is selected from hydrogen, a C1-C8 alkyl group, an aryl group and an araliphatic group having C6-C8 carbon atoms, preferably selected from a C1-C8 alkyl group and a benzyl group; R 4= selected from hydrogen, C1-C4 alkyl group, preferably selected from hydrogen and a methyl group; Sp' = each independently a spacer group is selected from unbranched and branched alkylene having C1-C19 carbon atoms, which may additionally contain oxygen, sulfur and / or -OOC- in the carbon chain, preferably selected from methylene, *CH2- (OC2H4) q , *CH2-(OC3H6) q, where q = 1-5 and the symbol * denotes the binding site to PCA', or Sp' is omitted; PCA' = each independently represents a polycyclic group, preferably an aliphatic polycyclic group, more preferably an aliphatic bi- or tricyclic group, even more preferably a tricyclic group, most preferably tricyclo[5.2.1.0 / 2,6]decanylene. The monomers of formula 32 can be, in particular, bis(methacryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane and bis(acryloyloxymethyl)tricyclo[5.2.1.0 / 2,6]decane. Suitable further radically polymerizable monomers can also be selected from methyl, ethyl, 2-hydroxyethyl, butyl, benzyl, tetrahydrofurfuryl or isobornyl (meth)acrylate, p-cumylphenoxyethylene glycol methacrylate, bisphenol A di(meth)acrylate, bis-GMA, ethoxylated or propoxylated bisphenol A dimethacrylate (e.g. SR-348c (Sartomer)) with three ethoxy groups, 2,2-bis[4-(2-methacryloxypropoxy)phenyl]propane, di-,Tri- and tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di- and glycerol trimethacrylate, 1,4-butanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and 1,12-dodecanediol di(meth)acrylate. Preferred monomers are 1,6-hexanediol dimethacrylate, benzyl, tetrahydrofurfuryl, or isobornyl methacrylate, p-cumylphenoxyethylene glycol methacrylate, 2,2-bis[4-(2-methacryloxyp-propoxy)phenyl]propane, Bis-GMA, and SR-348C (Sartomer). Suitable further radically polymerizable monomers can be selected, for example, from N-monosubstituted and N-disubstituted acrylamides, such as N-ethylacrylamide and N,N-dimethacrylamide, bisacrylamides, such as N,N'-diethyl-1,3-bis(acrylamido)propane, 1,3-bis(methacrylamido)propane, 1,4-bis(acrylamido)butane, and 1,4-bis(acryloyl)piperazine. The radically polymerizable compositions preferably comprise further radically polymerizable monomers or oligomers,whose viscosity is below the viscosity of the radically polymerizable compound represented by the structure of formula 1. In such a case, the further radically polymerizable monomers or oligomers are so-called diluents. The diluents preferably have viscosities of less than 10 Pa s, more preferably less than 5 Pa s, even more preferably less than 1 Pa s. This is particularly preferred and advantageous for the production of materials by means of vat-based photopolymerization. The radically polymerizable composition preferably comprises one or more further radically polymerizable monomers or oligomers that do not fall under the at least one compound of formula 1, in a mass fraction of 0 to 99 wt.%, more preferably from 10 to 99 wt.%, even more preferably from 20 to 98 wt.%, even more preferably from 35 to 90 wt.%.based on the total mass of the polymerizable composition. In a particular embodiment, it is preferred that the composition does not contain any monomer or oligomer that has a bisphenol A structure. In particular, it does not contain 2,2-bis[4-(2-hydroxy-3-(meth)acryloxypropoxy)phenyl]propane (BisGMA) and / or ethoxylated bisphenol A di(meth)acrylate (BisEMA). For dental adhesives or self-adhesive composite cements, acidic monomers and / or water-soluble monomers can be used in particular. A typical proportion of acidic monomers is known from the prior art. Acidic monomers are compounds that have an acidic group and a radically polymerizable group in one molecule. Examples of radically polymerizable, unsaturated groups are: (meth)acryloyl, (meth)acrylamide, styryl, vinyl, and allyl groups. Examples of acidic groups that can be present in acidic monomers are: carboxylic acid,Carboxylic anhydride, phosphate, thiophosphate, pyrophosphate, thiopyrophosphate, phosphonate, thiophosphonate, and sulfonate groups. The acidic groups can also occur in the form of an acid chloride, an alkali metal salt, an alkaline earth metal salt, or an ammonium salt. Suitable acidic monomers include, for example, 2-(methacryloyloxyethyl)phenyl hydrogen phosphate (phenyl-P); 2-Hydroxyethyl methacrylic dihydrogen phosphate (HEMA phosphates), dipentaerythritol pentamethacrylate phosphate (PENTA), di-2-hydroxyethyl methacrylic hydrogen phosphate (di-HEMA phosphates), 10-methacryloyloxydecyl dihydrogen phosphate (MDP), 1,3-glycerol dimethacrylate phosphate (GDMAP), 2,5-Dimethacryloyloxyethyloxycarbonyl-1,4-benzenedicarboxylic acid (PMDM), butane-1,2,3,4-tetracarboxylic acid di-(2-hydroxyethyl methacrylic) ester (TCB), 4-methacryloyloxyethyl trimellitic acid (4-MET), 4-methacryloxyethyl trimellitic anhydride (4-META), Py- romellitic acid bis-glycerol dimethacrylate (PMGDM) and 11-Me- thacryloyloxy-1,1-undecanedicarboxylic acid (MAC-10). Furthermore, radically polymerizable antibacterial monomers can also be used as additional monomers. c) Initiator or initiator system Suitable initiators or initiator systems are capable of initiating radical polymerization reactions. Such initiators or initiator systems are known to the person skilled in the art. Initiator systems consist of at least one initiator and at least one further compound, such as a coinitiator. These can be distributed among various components of the polymerizable dental material. The dental material according to the invention can be cured thermally, chemically, or photochemically, i.e., by irradiation with UV and / or visible light. Suitable initiators can be, for example, photoinitiators. These are characterized by the fact that they cure by absorbing light in the wavelength range from 300 nm to 700 nm.preferably from 350 nm to 600 nm and particularly preferably from 380 nm to 500 nm and optionally through the additional reaction with one or more coinitiators can cause the curing of the material. Preferred compounds are phosphine oxides, acylphosphine oxides, bisacylphosphine oxides and derivatives thereof, acylgermanes, acylsilanes and tin compounds, as described, for example, in EP 2649981 A1, WO 2017 / 055209 A1, WO 2017 / 060527 A1, EP 3068363 A1, US 2020 / 0087329 A1, EP 3868767 A1, EP 3293215 A1 and EP 3153150 A1, benzoin ethers, benzil ketals, acetophenones, benzophenones, thioxanthones, bisimidazoles, metallocenes, fluorones, α-dicarbonyl compounds, aryldiazonium salts, arylsulfonium salts, aryliodonium salts, ferrocenium salts, salts, phenylphosphonium salts or a mixture of these compounds are used. Particular preference is given to diphenyl-2,4,6-trimethylbenzoylphosphine oxide, phenyl-bis-2,4,6-trimethylbenzoylphosphine oxide, benzoin, benzoin alkyl ethers, benzil dialkyl ketals,α-Hydroxyacetophenone, dialkoxyacetophenone, α-aminoacetophenone, iso-propylthioxanthone, camphorquinone, phenylpropanedione, 5,7-diiodo-3-butoxy-6-fluorone, (eta-6-cumene)(eta-5-cyclopentadienyl)iron hexafluorophosphate, (eta-6-cumene)(eta-5-cyclopentadienyl)iron tetrafluoroborate, (eta-6-cumene)(eta-5-cyclopentadienyl)iron hexafluoroantimonate, substituted diaryliodonium salts, triarylsulfonium salts or a mixture of these compounds. Preferred co-initiators for photochemical curing are tertiary amines, borates, organic phosphites, diaryliodonium compounds, thioxanthones, xanthene, fluorenes, fluorones, α-dicarbonyl compounds, dicarbonyl systems as described in WO 2021 / 048313 A1, condensed polyaromatics, or a mixture of these compounds. Particular preference is given to N,N-dimethyl-p-toluolidine, N,N-dialkylalkylanilines, N,N-dihydroxyethyl-p-toluidine, 2-ethylhexyl-p-(dimethylamino)benzoate,Ethyl p-(dimethylamino)benzoate, butyrylcholine triphenylbutylborate, or a mixture of these compounds are used. So-called thermal initiators can also be used as initiators, which can cure the material by absorbing thermal energy at elevated temperatures. Inorganic and / or organic peroxides, inorganic and / or organic hydroperoxides, α,α'-azobis(isobutyroethyl ester), α,α'-azobis(isobutyronitrile), benzpinacols, or a mixture of these compounds are preferably used. Diacyl peroxides such as benzoyl peroxide or lauroyl peroxide, cumene hydroperoxide, benzpinacol, 2,2'-dimethylbenzpinacol, or a mixture of these compounds are particularly preferred. For chemical curing at room temperature, a redox initiator system is generally used.which consists of one or more initiators and a coinitiator(s) serving as an activator. For reasons of storage stability, individual components of an initiator system are incorporated into spatially separated parts of the dental material according to the invention, i.e., a multi-component, preferably a two-component material is present. The initiator(s) used are preferably inorganic and / or organic peroxides, inorganic and / or organic hydroperoxides, barbituric acid derivatives, malonyl sulfamides, protic acids, Lewis or Broensted acids or compounds that release such acids, carbenium ion donors such as methyl triflate or triethyl perchlorate, or a mixture of these compounds. The coinitiator(s) used are preferably tertiary amines, heavy metal compounds, in particular compounds of groups 8 and 9 of the Periodic Table (“iron and copper group”).Compounds with ionically bound halogens or pseudohalogens, such as quaternary ammonium halides, weak Broenstedt acids such as alcohols and water, or a mixture of these compounds are used. The dental material according to the invention can also contain any conceivable combination of the initiators and coinitiators described above. An example of this are so-called dual-curing dental materials, which contain both photoinitiators and optionally the corresponding coinitiators for photochemical curing, as well as initiators and corresponding coinitiators for chemical curing at room temperature. The polymerizable composition or the polymerizable dental material is preferably light-curing. In a preferred embodiment, the polymerizable composition comprises an initiator system that operates in the wavelength range of 395-700 nm,The photoinitiator system preferably initiates the chemical polymerization in a wavelength range of 400-500 nm. A preferred initiator system contains camphorquinone (CQ) as initiator and tertiary aromatic and aliphatic amines as coinitiators. A preferred aliphatic amine is N,N-(dimethylamino)ethyl (meth)acrylate. Preferred aromatic coinitiators are aromatic amines, such as 2-ethylhexyl p-(dimethylamino)benzoate (EHA) or ethyl p-(dimethylamino)benzoate (EDAB). Furthermore, the photoinitiator system can comprise another synergist in addition to camphorquinone and a tertiary amine. Preferred synergists can be diaryliodonium salts, as described in EP 3427716 A1, EP 3888616 A1, EP 3881818 A1 and M. Topa, J. Ortyl, Materials 13, 4093 (2020). In another preferred embodiment, which is particularly suitable for 3D printing applications, the dental material according to the invention contains an initiator system,which initiates the radical polymerization in the wavelength range of 300-500 nm, more preferably in a wavelength range of 350-420 nm, particularly preferably 365-410 nm. Preferred initiator types are those that function according to the Norrish Type 1 mechanism. The at least one initiator or the initiator system for the polymerization can be present in the polymerizable composition in a mass fraction of 0 to 5 wt. %, preferably 0.01 to 5 wt. %, based on the total mass of the polymerizable composition. d) Stabilizer The radically polymerizable composition can contain one or more stabilizers. Such stabilizers are known to the person skilled in the art. Suitable stabilizers are preferably benzotriazoles, triazines, benzophenones, cyanoacrylates, salicylic acid derivatives,ge- hinderte Amin-Lichtstabilisatoren (Hindered Amine Light Stabi- lizers (HALS)) sowie Gemische hiervon. Besonders geeignet sind o-Hydroxyphenylbenzotriazole, wie 2-2H-Benzotriazol-2-yl)-4- methylphenol, 2-(5-Chlor-2H-benzotriazol-2-yl)-4-methyl-6- tert-butyl-phenol, 2-(5-Chlor-2H-benzotriazol-2-yl)-4,6-di- tert-butyl-phenol , 2-(2H-Benzotriazol-2-yl)-4,6-di-tert-pen- tyl-phenol, 2-(2H-Benzotriazol-2-yl)-4-methyl-6-dodecyl-phe- nol, 2-(2H-Benzotriazol-2-yl)-4, 6-bis-(l-methyl-l-phe- nylethyl)-phenol, 2-(2H-Benzotriazol-2-yl)-6-(l-methyl-l-phe- nylethyl)-4-(l,l,3,3-tetramethylbutyl)-phenol, 2-(2H-Benzotri- azol-2-yl)-4-(l,l,3,3-tetramethylbutyl)-phenol und 3-(2H-Ben- zotriazol-2-yl)-5-ter-butyl-4-hydroxy-benzolpropansäureester, o-Hydroxyphenyltriazine, wie 2-(2-Hydroxy-4-hexyloxy-phenyl)- 4,6-diphenyl-1,3,5-triazin oder 2-(2-Hydroxy-4-[2-hydroxy-3- dodecyloxy-propyloxy]-phenyl)-4,6-bis-(2, 4-dimethylphenyl)- l,3,5-triazin, o- Hydroxy-benzophenone, wie 2-Hydroxy-4-octy- loxybenzophenon,Cyanoacrylates such as ethyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate and tetrakis-[(2-cyano-3,3-diphenylacryloyl)oxymethyl]-methane, hindered amine light stabilizers (HALS) such as N,N'-bisformyl-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)-hexamethylenediamine, bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, bis-(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate and methyl-(1,2,2,6,6-pentamethyl-4-piperidyl)- ridyl) sebacates, salicylic acid esters, and mixtures thereof. Other suitable stabilizers are phenols, such as hydroquinone monomethyl ether (HQME), 2,6-di-tert-butyl-4-methylphenol (BHT), or tert-butylhydroxyanisole (BHA). 2,6-di-tert-butyl-4-methylphenol (BHT) can be used as a stabilizer. The stabilizers can be present in the radically polymerizable composition in a mass fraction of 0 to 5 wt.%, preferably 0.001 to 5 wt.%, more preferably 0.005 to 2 wt.%.based on the total mass of the polymerizable composition. In one embodiment, the radically polymerizable composition can comprise stabilized radicals. Suitable stabilized radicals are preferably those such as 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) and bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl) sebacate. Bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl) sebacate is particularly preferred. The stabilized radicals are preferably present in a mass fraction of 0.005 to 0.01 wt. % in the radically (photo)polymerized compositions, based on the total mass of the polymerizable composition. e) Fillers The radically polymerizable composition can comprise fillers or filler particles. The filler particles are not restricted to a particular particle shape. Rather, fillers can be spherical, scaly, plate-like, needle-like,sheet-like or irregular shapes are very well suited for use. The filler particles preferably have an average particle diameter of 5 nm to 100 µm, more preferably 5 nm to 50 µm. Suitable fillers can be selected from a wide variety of materials commonly used in dental materials or products. By selecting the filler, the fluidity, viscosity, consistency, color, radiopacity, and mechanical stability of a composition or dental material can be adjusted. Based on their chemical nature, fillers can be roughly divided into three different classes: inorganic fillers, organic fillers, and organic-inorganic composite fillers. The fillers can be used not only individually,They can also be used in combination with each other. Ground powders of natural or synthetic glasses or crystalline inorganic substances in various sizes and states (monodisperse, polydisperse) can be used as inorganic fillers. Suitable materials include quartz, cristobalite, glass ceramics, feldspar, barium silicate glasses (such as those available under the trade names Kimble RAY-SORB T3000, Schott 8235, Schott GM27884, Schott G018-053, and Schott GM39923), barium fluorosilicate glasses, strontium silicate glasses, strontium borosilicate glasses (such as those available under the trade names RAY-SORB T4000, Schott G018-093, Schott G018-163, and Schott GM32087), lithium aluminum silicate glasses, barium glasses, calcium silicates, sodium aluminum silicates, fluoroaluminum silicate glasses (such as those available under the trade names Schott G018-091 and Schott G018-117),Zirconium or cesium boroaluminosilicate glasses (such as those available under the trade names Schott G018-307, G018-308, and G018-310), zeolites, and apatites. The fillers preferably have an average particle size d50 of 0.01-15 µm, more preferably an average particle size d50 of 0.2-5 µm, and particularly preferably an average particle size of 0.2-1.5 µm. It may be preferred that the average particle size d50 be between 0.1-0.5 µm. In such cases, it is particularly preferred that the average particle size d90 be less than 1.0 µm. Furthermore, discrete, non-agglomerated, non-aggregated, organically surface-modified nanoparticles can be used to achieve a more uniform filling of the dental material,and to increase hardness and abrasion resistance. Nanoparticles in this context are understood to be spherical particles with an average particle size of less than 200 nm. The average particle size is preferably less than 100 nm and particularly preferably less than 60 nm. The smaller the nanoparticles, the better they can fulfill their function of filling the voids between the larger particles. The materials for the nanoparticles are preferably oxides or mixed oxides and are preferably selected from the group consisting of oxides and mixed oxides of the elements silicon, titanium, yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, ytterbium, lanthanum, cerium, aluminum, and mixtures thereof. The preferred oxide nanoparticles are not agglomerated. To enable good integration of the nanoparticles into the polymer matrix of a composite material,The surfaces of the nanoparticles are organically modified. The surface treatment of the fillers is preferably carried out with a silanizing agent. Methacryloxypropyltrimethoxysilane is particularly suitable as an adhesion promoter. Commercially available nanoscale, non-agglomerated, and non-aggregated silica sols that can be used are, for example, sold under the names "NALCO COLLOIDALSILICAS" (Nalco Chemical Co.), "Ludox colloidal silica" (Grace), or "Highlink OG" (Clariant). Submicron fillers or microfillers consisting of agglomerated, nanoscale particles can also be used, especially if their specific surface area (determined according to Brunauer, Emmet, Teller) is in the range between 100 and 400 µm. 2 / g. Fumed silica or wet-precipitated silica are preferred. Suitable, usable products of non-surface-treated silica fillers are commercially available under the names AEROSIL™ ("OX50", "90", "130", "150", "200", "300" and "380", "R8200" from Evonik Industries AG, Essen, Germany), Cab-O-Sil ("LM-150", "M-5", "H-5", "EH-5" from Cabot Corp., Tuscola, IL), HDK™ ("S13", "V15", "N20", "T30", "T40" from Wacker-Chemie AG, Munich, Germany) and Orisil™ ("200", "300", "380" from Orisil, Lviv, Ukraine). Particularly advantageous abrasion and gloss resistance properties of the composition or a dental material can be achieved through the use of aggregated, nanoscale particles based on mixed oxides of silicon dioxide and zirconium dioxide. A suitable filler can be produced using a process described, for example, in US Pat. No. 6,730,156 (Example A).The filler produced in this way can then be surface-treated using a process as described in US Pat. No. 6,730,156 (e.g., Preparation Example B). The use of spherical submicroparticles based on silicon-zirconium mixed oxides, as described in DE 19524362 A1 or US2020 / 0121564 A1, can be particularly advantageous for achieving high filler contents with simultaneously high aesthetics and abrasion resistance. The aggregated fillers preferably have an average particle size of 1-15 µm, more preferably an average particle size of 1-10 µm, and even more preferably an average particle size of 2-5 µm. In addition, significant amounts of selected, radiopaque fillers may be present. The addition of radiopaque particles to the polymerizable composition or dental material is advantageous because it allows the differentiation between intact tooth structure and the restoration.Suitable radiopaque fillers contain particles of metal oxides, metal fluorides, or barium sulfate. Oxides and fluorides of heavy metals with an atomic number greater than 28 are preferred. The metal oxides and fluorides should be selected so that they have as little influence as possible on the color of the restoration. Metal oxides and fluorides with an atomic number greater than 30 are more suitable. Suitable metal oxides are oxides of yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, lanthanides (elements with an atomic number from 57 to 71), cerium, and combinations thereof. Suitable metal fluorides include yttrium trifluoride and ytterbium trifluoride.Particularly preferred here are irregularly shaped or spherical YbF3 or YF3 particles with an average primary particle size of 40 nm to 1.5 µm, and particularly preferred are core-shell combination products consisting of a YF3 or YbF3 core and a SiO2 shell, with the SiO2 shell surface most preferably being silanized. In particular, such a core-shell combination product has a refractive index of 1.48 to 1.54 and a measured average particle size of the agglomerated particles between 0.5 and 5 µm. Examples of suitable organic fillers are filled and unfilled, powdered polymers or copolymers based on polymethyl methacrylate (PMMA), polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate (PBMA), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyurethanes (PU), polyurea, methyl methacrylate-ethyl methyl acrylate copolymer, ethylene vinyl acetate copolymer, and styrene-butadiene copolymer.Furthermore, the organic filler can contain a biologically active component, a specific pigment, a polymerization initiator, a stabilizer, or something similar that has been added during the manufacturing process. The organic fillers can be used alone or as mixtures. Advantageous polishing properties with a simultaneous higher filler content can be achieved in the composition or in the dental materials when so-called organic-inorganic composite fillers are used. These fillers can be produced by processing a polymerizable monomer with an inorganic filler into a paste, subsequently curing it through polymerization, and then finely grinding it before being used as a filler. Microfillers are preferably used as the inorganic filler here.After grinding, the fillers preferably have an average particle size of 0.05-100 µm, more preferably an average particle size of 0.5-50 µm, even more preferably an average particle size of 1-30 µm. The average particle size is preferably determined by means of static and / or dynamic light scattering of the particles in a dispersion with a suitable dispersant (e.g. Coulter LS, Beckman Coulter GmbH, Krefeld, Germany and / or e.g. Zetasizer, Malvern Panalytical GmbH, Kassel, Germany). Field-flow fractionation (e.g. AF2000 AT, Postnova Analytics GmbH, Landsberg, Germany) or calibration with particle size standards is particularly preferably used for this purpose. The average particle size can also be determined by microscopy, in particular electron microscopy. The absolute particle size and preferably the d50 value are preferably stated.It is preferred that the fillers in the radically polymerizable composition or in the dental material are surface-modified. For this purpose, for example, the described inorganic or organic-inorganic composite fillers are subjected to a surface treatment before use in order to improve the compatibility, affinity, and incorporability of the fillers into the resin mixture. As a result of this treatment, the surfaces of the inorganic particles are organically modified, i.e., the surfaces have organic structural elements. All methods known to the person skilled in the art can be used here. Silanizing agents are preferred for inorganic fillers that carry OH groups on the surface.Examples include γ-methacryloxyalkyltrimethoxysilane (number of C atoms between the methacryloxy group and the silicon atom: 3 to 12), γ-methacryloxyalkyltriethoxysilane (number of C atoms between the methacryloxy group and the silicon atom: 3 to 12), or silicone compounds such as vinyltrimethoxysilane, vinylethoxysilane, and vinyltriacetoxysilane. Methacryloxypropyltrimethoxysilane is particularly preferred as a silanizing agent. Inorganic fillers that bear few or no OH groups on their surface are preferably surface-treated with other surface modifiers, such as titanates, aluminates, zircoaluminates, surfactants, fatty acids, organic acids, inorganic acids, or metal alkoxides. Organic compounds containing N-, P-, S- and / or O-containing functional groups (e.g.Polyols, sulfoxides, phosphinic acid esters, phosphonic acid esters, trialkylphosphines, carboxylic acids and carboxylic acid esters) are particularly preferred. 10-Methacryloyloxydecyl dihydrogen phosphate is particularly suitable here. Particularly in the case of agglomerated nanofillers based on silicon dioxide, the surface modifications can consist of radically reactive groups, such as the aforementioned methacryloyloxyalkyl groups, or also radically unreactive groups. Suitable unreactive groups are, for example, trimethylsilyl, dimethylsilylene or methylsilylidene groups, which can be applied to the surface by silanization, for example with hexamethyldisilazane, dimethyldimethoxysilane or methyltrimethoxysilane. Suitable unreactive surface-modified agglomerated nanofillers are commercially available, for exampleunder the names Aerosil R8200, Aerosil R812S, Aerosil R805, Aerosil R202, Aerosil R974 (Evonik Industries AG, Essen, Germany) or HDKH2000, HDKH200 / 4 (Wacker Chemie, Burghausen, Germany). Furthermore, the agglomerated nanofillers can preferably be modified with groups that are reactive in radical processes, e.g., methacryloyl groups. A commercially available product of a radically reactive modified agglomerated nanofiller is available under the name Aerosil R7200 (Evonik Industries AG, Essen, Germany). Preferably, the agglomerated nanofillers can be largely deagglomerated, as described, for example, in EP 1720206. The radically polymerizable composition according to the invention can have a mass fraction of filler or filler particles of 0 to 95 wt.%, preferably of 1 to 95 wt.%, more preferably of 5 to 92 wt.%, even more preferably of 15 to 85 wt.-%, based on the total mass of the polymerizable composition. The amount of filler fraction can be selected depending on the indication of the dental product. This means that the highest possible filler quantities can be used for stable, moldable filling composites, for dental compositions for the production of inlays, onlays or overlays as well as for compositions for the production of dental CAD-CAM materials. As a rule, these compositions have filler contents of 75 wt.% to 92 wt.%, based on the total composition. Flowable dental composites, luting composites, core build-up materials, crown and bridge materials generally have an average filler range of 40 to 80 wt.%, based on the total composition, whereas for dental varnishes, dental sealing materials, dental infiltrants or dental adhesives, fillers in the range of 1 to 40 wt.-%, based on the total composition. The filler ranges given above are only guidelines; there may be deviations depending on the choice of filler. In a preferred embodiment, the radically polymerizable composition contains a selection of microfillers such that the refractive index difference between the microfillers and the other components of the polymerized composition (polymer matrix) is as small as possible. Δn is preferably ≤ 0.03, more preferably ≤ 0.02, more preferably ≤ 0.01. f) Dental additives The radically polymerizable composition can contain other dental additives. Suitable dental additives are preferably those that can be contained in radically polymerizable dental and dental technology materials. Dental additives are known to the person skilled in the art.Solvents or solvent mixtures, for example, can be used as conventional dental additives. For example, the use of a mixture of water and water-miscible solvents, such as ethanol or acetone, is preferred for the production of dental adhesives. Furthermore, the radically polymerizable composition can contain, for example, pharmacologically active compounds such as antibacterial compounds, chlorhexidine, or other enzyme-inhibiting agents. The composition can also contain, as a conventional dental additive, one or more fluoride-releasing substances in finely distributed, particulate form. Fluoride-releasing substances can be water-soluble fluorides such as sodium fluoride or amine fluoride. Other suitable fluoride-releasing substances are poorly soluble fluorides of the 2nd main group. Fluoride-containing glasses are also suitable fluoride sources.Other suitable additives are fine-particulate substances that release calcium and / or phosphate and thus have a remineralizing effect. Suitable remineralizing substances are calcium phosphate compounds such as hydroxyapatite, brushite, monocalcium phosphate, fluorapatite, and bioactive glasses such as those mentioned in DE10111449A1, DE102005053954A1, or US9517186B2. The dental material according to the invention can contain a colorant or colorant mixture selected from fluorescent dyes, fluorescent pigments, organic color pigments, inorganic color pigments, and mixtures thereof. A fluorescent colorant or pigment is preferably an organic fluorescent dye or an organic fluorescent pigment, in particular a non-polymerizable, organic fluorescent colorant optionally comprising arylcarboxylic acid esters, such as diethyl 2,5-dihydroxyterephthalate, arylcarboxylic acids, coumarin, rhodamine, naphthalene linimide or derivatives thereof.Inorganic fluorescent pigments can be, for example, CaAl4O7:Mn2+ (Ba0.98Eu0.02)MgAl. 10 O 17 , BaMgF4:Eu 2+, Y(1.995)Ce(0.005)SiO5. As color pigments, the dental material according to the invention can comprise organic pigments and inorganic pigments, such as N,N'-bis(3,5-xylyl)perylene-3,4:9,10-bis(dicarbimide), copper phthalocyanine, titanate pigment, in particular chromium antimony titanate (rutile structure), spinel black, in particular pigments based on iron oxide (Fe2O3) or iron oxide black (Fe3O4), where iron is partially substituted by chromium and copper or nickel and chromium or manganese, zinc iron chromium spinel brown spinel, ((Zn,Fe)(Fe,Cr)2O4) cobalt zinc aluminate blue spinel and / or titanium oxide. The additives customary in dentistry can be contained in the polymerizable composition in a mass fraction of 0 to 5 wt.%, preferably 0.001 to 5 wt.%, based on the total mass of the radically polymerizable composition.The invention has the advantage that the radically polymerizable compound according to the invention and also the radically polymerizable composition according to the invention overcome the previously mentioned disadvantages of the prior art. The radically polymerizable compounds and the radically polymerizable composition have excellent properties that are particularly necessary or desirable for the production of dental materials. In addition, the invention has the surprising advantage that the radically polymerizable compounds according to the invention can be synthesized by the production process according to the invention not only cost-effectively, but also in high purity and without undesired discoloration. Furthermore, the radically polymerizable compositions have a high conversion of the monomers during radical polymerization.As a result, dental materials and devices produced from the radically polymerizable compositions contain only a low residual monomer content. Furthermore, the radically polymerizable composition can be produced from monomers that are readily available and have a reduced toxicity potential. Since the radically polymerizable compositions preferably do not comprise any compounds containing a bisphenol A group and / or another bisphenol group, it can also be largely ruled out that the resulting dental materials and devices produced therefrom have any harmful effects on health. The use of the radically polymerizable compounds orThe use of the radically polymerizable composition for producing a dental material leads to reduced polymerization shrinkage combined with good mechanical properties of the resulting dental material. This means that the radically polymerizable compositions exhibit low polymerization shrinkage and reduced shrinkage stress. The radically polymerized compositions and the dental materials produced therefrom exhibit good mechanical properties, such as, in particular, very good flexural strength and tensile strength, as well as good fracture toughness. These advantageous properties of the radically polymerizable compound according to the invention and the corresponding compositions are surprising in view of the molecular sizes and structures of the radically polymerizable compounds, since the person skilled in the art would expect a reduced crosslinking density and flexural strength associated with them.The radically polymerizable compounds or compositions surprisingly exhibit a refractive index that is particularly suitable for producing dental materials containing fillers commonly used in the dental field, which exhibit desired optical properties, particularly with regard to translucency or opacity. In addition, the radically polymerized compositions (i.e., the resulting dental material) exhibit only low water solubility and low water absorption, which is also advantageous.The invention also relates to the use of the radically polymerizable compound, preferably according to one of claims 1 to 7, or the radically polymerizable composition, preferably according to one of claims 9 to 12, for producing a polymerizable dental material, preferably a dental composite, dental cement, self-adhesive dental cement, dental varnish, core build-up, root canal filling, filling, underfilling, luting, crown, bridge, restoration, orthodontic and / or prosthetic material. The filling material can be a moldable and / or flowable filling material, preferably a moldable filling material. In a preferred embodiment, the polymerizable dental material is used as a 3D printing material.In this way, orthodontic materials, aligners, splint materials, denture base materials, model materials, crown and bridge materials, drilling templates, gingival masks, tray materials, mouthguards, and / or veneers can be produced from the polymerizable dental material using a 3D printer. Furthermore, the present invention also relates to a dental material produced from a radically polymerizable composition according to the invention, preferably according to one of claims 9 to 12. The invention further relates to a radically polymerizable dental material according to the invention for use in a therapeutic method as a dental composite, dental cement, dental varnish, filling, base, luting, core buildup, root canal filling, crown, bridge, restoration, orthodontic, and / or prosthetic material.The invention also relates to a cured dental material produced from a polymerizable composition according to the invention, preferably according to one of claims 9 to 12. The cured dental material can be produced in a process in which a radically polymerizable composition is provided which cures or is cured completely or partially. In a particular embodiment, the radically polymerizable composition can be 3D-printed before curing. The invention will now be described by way of example using some advantageous embodiments with reference to the attached figure. It shows: Fig. 1: GPC diagram showing the peak of a radically polymerizable compound of formula 31 according to the invention. Fig. 2: GPC diagram showing the peak of a radically polymerizable compound of formula 33 according to the invention. Examples 1.Chemicals and their pretreatment / use The following chemicals were used in the preparation of the examples (Table 1) and were processed as described in this section before further use. Table 1: Compounds and substances used in the examples. TCD-DM 4,8-Bis(hydroxymethyl)tricyclo[5.2.1.0. 2,6 ]decane, mixture of isomers 96%, CAS 26896-48-0, Sigma Aldrich TCDDA Genomer 1231 (Tricyclodecanedimethanol diacrylate), CAS 42594-17-2, Rahn AG, Zurich, Switzerland TCD-MA (Hydroxymethyl)(acryloyloxymethyl)-tricy- clo[5.2.1.0 2,6]decan IPDI isophorone diisocyanate, > 99%, CAS 4098-71-9; TCI Deutschland GmbH, Eschborn, Germany H12MDI 4,4'-diisocyanatodicyclohexylmethane, > 90%, CAS: 5124-30-1; TCI Deutschland GmbH TMXDI 1,3-Bis(1-isocyanato-1-methylethylbenzene, > 97%, CAS: 2778-42-9; TCI Deutschland GmbH H6XDI 1,3-Bis(isocyanatomethyl)cyclohexane, > 99%, CAS: 38661-72-2; Sigma Aldrich TMDI Trimethylhexamethylene diisocyanate, 97%, CAS: 28679-16-5, abcr GmbH, Karlsruhe, Germany CALB Candida Antarctica Lipase B, immobilized on Im- mobead 150; Sigma Aldrich MTBE Methyl tert-butyl ether, 99%, CAS: 1634-04-4 THF Tetrahydrofuran anhydrous, min. 99.9% Toluene Toluene for analysis, 96%, CAS 108-88-3 Toluene-t Toluene dry, 99.8%, CAS 108-88-3 Cyclohexane, > 99%, CAS 110-82-7 Ethyl acetate, > 99.8%, CAS 141-78-6 BHT 2,6-Di-tert-butyl-4-methylphenol e.g. Synthesis, >99%, CAS 128-37-0 DMTND Dimethyltin dineodecanoate, CAS: 68928-76-7 TCDDMA Bis(methacryloyloxymethyl)tricy- clo[5.2.1.0 2,6]decane; CAS 43048-08-4 UDMA 7,7,9-(or 7,9,9-)trimethyl-4,13-dioxo-3,14-dio- xa-5,1 2-diaza-hexadecane-1,16-diol dimethacrylate, CAS 72869-86-4 BisGMA Propane-2,2-diylbis[4,1-phenyleneoxy(2-hydroxypropane-3,1-diyl)] bis(2-methylprop-2-enoate), CAS 1565-94-2 TEDMA Triethylene glycol dimethacrylate, CAS 109-16-0 CQ Camphorquinone EHA 2-ethylhexyl p-(dimethylamino)benzoate BaF Dental glass G018-053 (average particle size 0.7 µm, 6 wt.% silane); Schott AG, Mainz, Germany Drying of TCD-DM The TCD-DM was dried by azeotropic distillation with approximately 2.5 times the volume of toluene until a solution of 83.6 wt. % TCD-DM in toluene was obtained. Unless otherwise stated, the TCD-DM was used in the form of this solution, with weights referring to the TCD-DM. 2. Methods Thin-layer chromatography (TLC) TLC was performed using silica gel as the stationary phase (TLC cards: Polygram Sil G / UV). 254,Macherey-Nagel GmbH & Co. KG, Germany). A sample of the substance to be analyzed was diluted 1:10 with tetrahydrofuran. A mixture of cyclohexane and ethyl acetate 2:1 served as the mobile phase. The developed TLC card was viewed under UV light (254 nm wavelength) and then stained in an iodine chamber. Loss on drying The loss on drying was determined gravimetrically. A sample was dried for 2 hours at 110°C or 2 hours at 50°C in a convection oven and the residue was weighed. Viscosity The viscosity measurements were carried out using a rotational viscometer (Kinexus type, Malvern Instruments GmbH, Germany) with a plate-on-plate geometry (d = 25 mm, gap distance h = 0.1 mm, shear stress ramp 1–50 Pa) at 23°C and the viscosity was determined at a shear stress of 50 Pa. FT-IR spectroscopy FT-IR spectra (types iS10 and iS20, Thermo Scientific Nicolet) were recorded using one ATR unit each.32 scans were taken with a resolution of 4 cm. -1 Liquid chromatography / mass spectrometry coupling (HPLC-MS) This analysis was performed on a Waters Alliance 2695 HPLC system. The following column was used for separation: 250 / 2 Nucleodur C8 ec. The column temperature was 20°C. Elution was carried out at a flow rate of 0.2 ml / min with a gradient of the following mobile phases: 0.1% formic acid in acetonitrile (A) and 0.1% formic acid in water (B). Time [min] 0 0.5 40 45 50 60 Proportion B [%] 70 70 10 10 70 70 Detection was performed using a Waters Micromass ZQ mass detector. Ionization was performed in ESI+ mode. HPLC method for the quantification of TCDDA The TCDDA content HPLCin wt.% in the samples was determined on a Thermo Ultimate 3000 HPLC system. The following column was used for separation: 250 / 4 LiChrospher RP select B (5 µm). The column temperature was 20°C. Elution was carried out at a flow rate of 1 ml / min with a gradient of the following mobile phases: water (A) and methanol (B). Time [min] 0 0.5 14.5 15.0 20.0 Proportion B [%] 70 70 95 70 70 Detection was carried out with a UV detector at 205 nm. The TCDDA reference sample concentration was approximately 25 mg / 50 ml methanol. The sample concentration of the examples was approximately 15 mg / 10 ml methanol. 3 µl of sample were injected for the measurement. The content of monomers and oligomers according to the invention in the samples was calculated as follows: Content required monomer + oligomer (wt%) = 100% - Drying loss (wt%) - TCDDA content HPLC(wt.%) Gel permeation chromatography (GPC) GPC was performed using an Agilent 1200 GPC with RI detector (PSS, Germany). The following column combination (PSS, Germany) was used: pre-column / 100Å / 100Å / 1000Å. THF served as eluent at a flow rate of 1 ml / min. The sample concentration was approximately 5 mg / ml. GPC was performed at 20°C. Determination of the refractive indices The refractive indices of uncured compositions were determined using an Abbe refractometer AR (A. Krüss Optronik, Germany) at 23°C ±1°C against air based on the D-line of sodium light. Triplicate determinations were carried out in each case, and the mean value was calculated. The refractive index of cured compositions was determined according to ISO 489:1999 using an Abbe AR refractometer (A. Krüss Optronik). A drop of cinnamon oil was placed on the specimen and brought into contact with the measuring prism of the refractometer.For each specimen, a triplicate determination was performed, and the mean value was calculated. To prepare the specimens, the composition was placed in a steel mold (8 mm x 20 mm x 0.5 mm) coated with a clear, colorless polyester film (Hostaphan). ® ) covered slide. Another film, followed by another slide, was placed on the resin without bubbles, secured with clamps and cured using a light curing unit (Hi-Lite Power ® ; Heraeus Kulzer) for 90 s. The cured specimen was then removed from the mold. Determination of flexural strength (BF) and Young's modulus (EM) For the determination of flexural strength and Young's modulus, test specimens were produced analogously to ISO 4049:2009. Deviating from this, the test specimens were cured by exposure to a light polymerization device (Hi-Lite Power ®; Heraeus Kulzer). For this purpose, the dental composites in test specimen molds (40 mm x 2 mm x 2 mm) were exposed to light on both sides for 90 s. The test specimens were stored in distilled water at 37°C for 24 hours. The flexural strength and Young's modulus were determined using a Zwick universal testing machine (type Z010 or type Z2.5, Zwick-Roell, Germany). The mean value and standard deviation are given. Measurement of the volume shrinkage of resin mixtures (liquid pycnometer) The volume shrinkage of resin mixtures was determined using liquid pycnometers (Blaubrand, Brand GmbH + Co KG, Germany) via the change in density before and after curing at 20°C. First, the density of the uncured compositions was determined using a 10 ml liquid pycnometer.Higher-viscosity compositions (viscosity >10 Pas) were first heated to 60°C in an oven so that they could then be poured into the pycnometer with as little air bubbles as possible. Air bubbles were also removed by applying a vacuum in the desiccator. The filled pycnometer was then heated to 20°C. Once the measuring temperature was reached, the mass of the filled pycnometer was measured, and the density of the uncured composition was determined from this. To determine the density of the cured compositions, cuboid-shaped test specimens (35 mm x 20 mm x 3 mm) were produced. For this purpose, the uncured compositions were poured into appropriate test specimen molds without any air bubbles and cured from above and below for 90 seconds using a light-curing device (Hi-Lite Power). ®Heraeus Kulzer). The cured test specimens were stored at 23°C for 24 ± 2 hours. To determine the density of the cured compositions, the mass of the cured test specimen m1 and the empty weight of the pycnometer m0 were determined. The pycnometer was then filled 4 / 5 full with distilled, degassed water and heated to 20°C before the cured test specimen was immersed in the pycnometer. The pycnometer was then completely filled with water. When the measuring temperature of 20°C was reached, the pycnometer was closed and dried externally, the mass m3 of the pycnometer filled with water and test specimen was measured, and from this the density of the cured test specimen ρ NA determined according to equation 1: ^^ ^ ^,^^^^ ρ NA= ^^^^,^^^^ ^ ^^^^^^^^ (Equation 1) ^^ = specified volume of the pycnometer used at 20°C In this way, 3 cured test specimens were measured. The volume shrinkage (VS) as the mean value (MW VS ) was calculated from the difference between the density before (ρVA) and the mean value of the densities after curing (MWρNA) (Equation 2). ^^^^^ ^^^^ MW VS = × ^^^^^ (Equation 2) The determination of the standard deviation of the volume shrinkage SD VS was carried out according to equation 3. SD VS = 100 × ρ VA × SDρ NA / MW 2 ρ NA(Equation 3) Measurement of the volume shrinkage of composites (gas pycnometer) The volume shrinkage of the composites was determined using a helium gas pycnometer (Accupyc III 1340, Micromeritics, USA) via the change in density before and after curing. Three density determinations were performed on the uncured composite. For each measurement, approximately 0.3 to 0.4 g of the composite was placed in the measuring chamber of the gas pycnometer, leaving no voids. The weight of the uncured composite was determined using a scale, and the density of the uncured composite was determined from the volume measurement of the gas pycnometer using the AccuPYKII 1340 software. Subsequently, three density determinations were performed on the cured composite. For density determination, two cylindrical test specimens (h = 2 mm, D = 8 mm) of the composite were prepared by curing (90 s from each side) with the HiLite Power light polymerization unit.The test specimen molds were filled without air bubbles and covered with a microscope slide from above and below during curing. After curing, the specimens were demolded, deburred, cleaned with ethanol, and dried with compressed air. Both specimens were then placed on top of each other in the measuring chamber of the gas pycnometer. The weight of the cured composite was determined using a scale, and the density of the cured composite was determined from the volume measurement of the gas pycnometer using the AccuPYKII 1340 software. The density was determined within 15-60 minutes after curing. The volume shrinkage (VS) was recorded as the mean value (MW). VS ) was calculated from the difference between the mean density of the composite before (MWρVA) and the mean density after curing (MWρNA) (Equation 4). ^^^^^ ^^^^^^ Mean volume shrinkage MW VS = 100 % × ^^^^^ (Equation 4) The determination of the standard deviation of the volume shrinkage SD VSwas calculated according to equation 5 from the standard deviation SDρ NA the density of the cured composite and the standard deviation SDρ VA the density of the uncured composite and the corresponding mean values ​​MWρNA and MWρVA. SDVS = 100 / MWρNA 2 ×√((MWρNA 2 × SDρVA 2 )+(MWρVA 2 × SDρNA 2 )) (Equation 5) Conversion Measurement The conversion was determined by FT-NIR spectroscopy (Nicolet iS20, Thermo Scientific) before and after polymerization of a composition in transmission geometry. The conversion, or the progress of the polymerization reaction, was determined by measuring the degree of reduction of the C=C overtone band at 6160-6170 cm -1was determined. For this purpose, the uncured, ie, non-polymerized composition or composite was placed in a cylindrical test specimen (D = 15 mm, h = 1.0 mm), covered with slides from above and below, and then mounted on an IR holder. A spectrum with 12 scans was recorded. Subsequently, the uncured, ie, non-polymerized composition or composite was illuminated for 90 s from each side with the light polymerization device (Hi-Lite Power ® The FT-NIR spectrum of the polymerized composition was recorded within 60 minutes at the latest. The integrals of the C=C overtone band at 6160-6170 cm were then calculated from both spectra using the Omnic IR software (Series 9.11.727; Thermo Scientific). -1determined. The conversion U in % is calculated from both integrals according to equation 6: ^^^^^^ä^^^ ^^^^^^^^^^^^^^^ ^^^^^^^^ Conversion in % = 100% - ^^^^^^ä^^^ ^^^^^^^^^^^^^^^^^ ^^^^^^^^ x100% (Equation 6) 3. Synthesis Examples Example 1 Enzymatic transesterification of TCDDA and TCD-DM to TCD-MA A solution of 24.00 g of TCD-DM and 92.16 g of TCDDA in 80 ml of MTBE was placed in a 250 ml round-bottom flask fitted with a magnetic stirrer bar. 2 g of CALB were added, and the flask was sealed with a CaCl2 drying tube. The mixture was stirred slowly in a water bath at 40°C for 42 hours and left to stand at room temperature (RT) for 128 hours. The mixture was filtered, washed twice with a small amount of MTBE, the filtrate was concentrated on a rotary evaporator, and then dried under fine vacuum. A low-viscosity, colorless oil remained. Yield: 104.5 g. TCD-DM (9.5 g), TCD-MA (21.5 g), and TCDDA (33.6 g) were detected by HPLC-MS. The respective runtimes in minutes are given in parentheses.The loss on drying (2 hours, 50°C) was 0.34 wt.%. Example 2 Synthesis of radically polymerizable compounds with a structure of formula 33 In a 250 ml two-necked flask equipped with a magnetic stir bar, internal thermometer, and dropping funnel with a CaCl2 drying tube, 50 g of oil according to Example 1 were placed in 50 g of THF, and 9.55 ml of IPDI were slowly added dropwise at RT. Subsequently, 10 µl of catalyst solution (DMTND in toluene-t, weight ratio 1:1) were added, and the mixture was stirred for 8 hours at 40°C and 85 hours at RT. To convert any remaining isocyanate groups, a further 5.77 g of oil from Example 1 in 5.77 g of THF were added, and the mixture was stirred for 2 hours at 40°C. Subsequently, isocyanate groups were no longer detectable by FT-IR spectroscopy. The reaction mixture was transferred to a 250 ml one-neck flask, and THF was largely removed using a rotary evaporator at 25 mbar and a water bath temperature of 50°C. Further removal of volatile components was carried out under a fine vacuum at 50°C.A colorless, clear oil remained. Yield: 57.68 g. Loss on drying (2 hours, 110°C): 1.69%. Using HPLC-MS, TCDDA (M+H) was isolated after a runtime of 34.0 min. + = 305) and with a running time of 45.4 min a compound of formula 33 (M+H + = 724) were detected. The elution profile of the GPC performed is shown in Fig. 1. TCDDA had an elution volume of 29.8 ml, the compounds of structure 33 with x = 1 of 26.3 ml and with x = 2 – 3 of 25.0 and 24.0 ml, respectively. TCDDA content HPLC : 48.09 wt.% Content of compounds Formula 31: 50.22 wt.% Example 3 Synthesis of radically polymerizable compounds with a structure of formula 34 In a 250 ml two-necked flask equipped with a magnetic stir bar, internal thermometer, and dropping funnel with a CaCl2 drying tube, 30 g of oil from Example 1 in 30 g of THF were initially charged, and 7.17 g of H12MDI were slowly added dropwise at RT. Then, 10 µl of a catalyst solution (DMTND in toluene-t, weight ratio 1:1) were added, and the mixture was stirred for 4 hours at 40°C and 19 hours at RT. To convert any remaining isocyanate groups, a further 11.61 g of oil from Example 1 in 11.61 g of THF were added stepwise (4 steps). After each addition, the mixture was stirred for 3 hours at 45°C and 18 hours at RT. Subsequently, isocyanate groups were no longer detectable by FT-IR spectroscopy. The reaction mixture was transferred to a 250 ml one-neck flask, and THF was largely removed using a rotary evaporator at 25 mbar and a water bath temperature of 50°C.Further removal of volatile components was carried out under a fine vacuum at 50°C. A colorless, clear oil remained. Yield: 42.79 g. Loss on drying (2 hours, 110°C): 2.07%. TCDDA (M+H) was isolated by HPLC-MS at a runtime of 33.6 min. + = 305) and with a running time of 48.6 min a compound of formula 34 (M+H + = 764). GPC: TCDDA had an elution volume of 29.6 ml, the compounds of structure 34 with y = 1 of 26.0 ml, and those with y = 2 and 3 of 24.3 and 23.2 ml, respectively. TCDDA content HPLC : 47.35 wt.% Content of compounds of formula 32: 50.58 wt.% (Formula 34) Example 4 Synthesis of radically polymerizable compounds of formula 35 11.35 g of TMDI in 25 ml of THF and 50 µl of catalyst solution (DMTND in toluene-t, 50:50 wt%) were placed in a 250 ml three-neck flask equipped with a magnetic stir bar, internal thermometer, reflux condenser, dropping funnel, and CaCl2 drying tube. A solution of 50.0 g of the oil from Example 1 in 25 ml of THF was slowly added dropwise at room temperature with stirring. The mixture was then stirred for 5 hours at 45°C and for a further 18 hours at room temperature. To convert remaining isocyanate groups, a further 6.44 g of oil was added stepwise (4 steps) until isocyanate groups were no longer detectable by FT-IR spectroscopy. After each addition, the mixture was stirred for 5 hours at 45°C and 18 hours at RT. The reaction mixture was transferred to a 250 ml one-neck flask and treated with 0.01 g of BHT. The majority of the THF was removed using a rotary evaporator.Further removal of solvent and other volatile components was carried out under a fine vacuum at 50°C. A colorless, clear oil remained. Yield: 55.94 g. Loss on drying (2 hours, 110°C): 0.99%. TCDDA (M+H) was isolated by HPLC-MS at a runtime of 33.7 min. + = 305) and with a running time of 45.2 min a compound of formula 35 (M+H + = 712) were detected. The elution profile of the GPC performed is shown in Fig. 2. TCDDA had an elution volume of 29.8 ml, the compound of the structure of formula 35 with z = 1 of 26.5 ml, and higher oligomers (z = 2 – 4) of 24.9, 23.9, and 23.2 ml. TCDDA content HPLC : 44.97 wt.% Content of compounds Formula 35: 54.04 wt.% (Formula 35) Example 5 Synthesis of radically polymerizable compounds with the structure of formula 36 30 g of oil from Example 1 in 30 g of THF and 0.005 g of BHT were placed in a 250 ml two-necked flask equipped with a magnetic stir bar, internal thermometer, and dropping funnel with a CaCl2 drying tube, and 6.67 g of TMXDI were slowly added dropwise at RT. 10 µl of a catalyst solution (DMTND in toluene-t, weight ratio 1:1) were added, and the mixture was stirred for 4 hours at 40°C and 18 hours at RT. To convert any remaining isocyanate groups, a further 5.22 g of oil from Example 1 and 10 µl of the catalyst solution were added, and the mixture was stirred for 5.5 hours at 40°C and 18 hours at RT. Subsequently, isocyanate groups were no longer detectable by FT-IR spectroscopy. The reaction mixture was transferred to a 250 ml one-neck flask, and THF was largely removed using a rotary evaporator at 25 mbar and a water bath temperature of 50°C. Further removal of volatile components was carried out under a fine vacuum at 45°C.A colorless, clear oil remained. Yield: 33.75 g. Loss on drying (2 h, 110 °C): 1.49%. Using HPLC-MS, TCDDA (M+H) was isolated after a runtime of 34.5 min. + = 305) and at a running time of 45.4 min a compound of the structure of formula 36 (M+H + = 746). GPC: TCDDA had an elution volume of 29.7 ml, the compound of the structure of formula 36 with l = 1 of 26.5 ml and l = 2 – 4 of 24.9, 24.0, and 23.2 ml, respectively. TCDDA content HPLC : 46.06 wt.% Content of compounds of formula 36: 52.45 wt.% Example 6 Synthesis of radically polymerizable compounds with H6XDI In a 100 ml two-neck flask equipped with a magnetic stir bar, internal thermometer, and dropping funnel with a CaCl2 drying tube, 22 g of oil from Example 1 were placed in 15 ml of THF, and 3.89 g of H6XDI in 15 ml of THF were slowly added dropwise at RT. 10 µl of catalyst solution (DMTND in toluene-t, weight ratio 1:1) were added, and the mixture was stirred for 5 hours at 40°C and 18 hours at RT. Subsequently, isocyanate groups were no longer detectable by FT-IR spectroscopy. The reaction mixture was transferred to a 100 ml one-neck flask, a spatula tip of BHT was added, and THF was largely removed on a rotary evaporator. Further removal of volatile components was carried out under a fine vacuum. A colorless, clear oil remained. Yield: 21.48 g Loss on drying (2 hours, 110°C): 1.43% Using HPLC-MS, TCDDA was isolated after a runtime of 34.0 min and the product (M+H) after a runtime of 43.3 min. += 696). GPC: TCDDA had an elution volume of 29.7 ml, the product of 26.6 ml, 25.1 ml, 24.1 ml and 23.4 ml, respectively. It is understood that, starting from the isomers or isomer mixtures of the isocyanates and / or alcohols used, various isomeric structures arise during the syntheses of the radically polymerizable compounds, in particular with regard to the dimethylenetricyclodecane groups and their direction in the polymerizable compounds, e.g. in an oligomer chain. The simple compounds of the structures de6 formulas 33 to 34 shown here are intended, however, to include all of the resulting isomeric compounds. 5. Properties of the radically polymerizable compositions To prepare the compositions, the individual components were mixed using a magnetic stirrer until a homogeneous composition was obtained.Table 2: Composition, viscosity (η), flexural strength (BF), Young's modulus (EM), conversion (U), volume shrinkage (VS), refractive index uncured (n. D VA), refractive index cured (n D NA) of compositions according to the invention (Ex. A, B, C, D) containing the radically polymerizable compounds synthesized in Examples 2-5 (oil from Ex. 2-5) and of comparison compositions (VB A, B) Component Ex. A Ex. B Ex. C Ex. D VB A VB B [wt.%] Ex. 2 97.4 Ex. 3 97.4 Ex. 4 97.4 Ex. 5 97.4 BisGMA 68.2 48.7 TEDMA 29.2 48.7 CQ 1.0 1.0 1.0 1.0 1.0 1.0 EHA 1.598 1.598 1.598 1.598 1.598 1.598 BHT 0.002 0.002 0.002 0.002 η [Pa s] 18.8 13.8 16.6 20.6 BF [MPa] 100±7 129±8 105±8 96±7 EM [GPa] 2.6±0.1 3.3±0.1 2.6±0.1 2.4±0.2 U [%] 72.0 74.4 68.3 - VS [%] 4.4±0.3 4.6±0.2 6.4±0.3 8.2±0.3 n D VA 1.5144 1.5157 1.5121 1.5198 1.5214 1.5046 n DNA 1.5425 1.5463 1.5529 1.5388 Table 3: Composition, flexural strength (BF), Young's modulus (EM), volume shrinkage (VS), refractive index uncured (n D VA), refractive index cured (n D NA) of comparison compositions (VB CF) Component VB C VB D VB E VB F [% by weight] UDMA 77.9 77.9 53.6 53.6 TCDDA 43.8 TCDDMA 19.5 TEDMA 19.5 43.8 CQ 1.0 1.0 1.0 1.0 EHA 1.598 1.598 1.598 1.598 BHT 0.002 0.002 0.002 0.002 BF [MPa] 102±4 94±6 - - EM [GPa] 2.4±0.1 2.5±0.1 - - VS [%] 7.0±0.6 6.9±0.3 - - n D VA 1.479 1.488 1.4940 1.4749 n D NA 1.5100 1.5215 1.5170 1.5108 The inventive examples B and D show a significantly lower volume shrinkage than the comparative examples AF. The conversions, flexural strengths and the modulus of elasticity of the inventive examples are in the range of the comparative examples A-F and in some cases even higher. The difference in the refractive indices of the cured inventive examples B and D compared to the dental glass used (nD= 1.53) is comparable to the difference between the comparative examples AF and the same dental glass. This results in similarly low turbidity of the dental composites for the inventive examples B and D, which lead to very good aesthetic product properties. Production of the dental composites To produce the dental composites, the components oil Example 3, Example 5 or BisGMA and TEDMA were first mixed with CQ, EHA and BHT using a magnetic stirrer until a homogeneous composition was achieved. Subsequently, a total of 75 wt.% BaF, based on the total mass of the dental composite, was successively added, homogenized using a Speedmixer DAC 400-1 VAC-P (Hauschild, Germany) and degassed for 3 min at 20 mbar. The compositions and measurement results are given in Table 4. Table 4: Composition, flexural strength (BF), Young’s modulus (EM), conversion (U) and volume shrinkage (VS) of dental composites (e.g.E, F) containing the radically polymerizable compounds synthesized in Examples 3 and 5 (Ex. 3, Ex. 5) and the comparative composition G (VB G) Component Ex. E Ex. F VB G [wt.%] Ex. 3 24.8325 Ex. 5 24.8325 BisGMA 12.41625 TEDMA 12.41625 CQ 0.0625 0.0625 0.0625 EHA 0.1045 0.1045 0.1045 BHT 0.0005 0.0005 0.0005 BaF 75 75 75 Total 100 100 100 BM [MPa] 133±6 134±6 128±16 EM [GPa] 9.4±0.4 10.3±0.2 9.9±0.2 U [%] 65.0 65.9 73.2 VS [%] 1.9±0.3 2.1±0.1 3.6±0.3 Examples E and F, in which the compounds according to the invention were used, show significantly lower volume shrinkage than Comparative Example G, in which a monomer mixture from the prior art was used. Conversions, flexural strengths, and the elastic moduli of the examples according to the invention are comparable to Comparative Example G.For comparison, the properties of commercially available dental composites known from the prior art with a higher filler content are shown in Table 5. Despite the higher filler content, the shrinkage data for these composites are higher than those for the inventive examples. Table 5: Properties of commercially available dental composites known from the prior art containing BPA-containing polymerizable compositions and 78.5 to 83 wt.% filler. Dental composite BF [MPa] VS [%] (Batch) EM [GPa] Ecosite Elements A2 135±9 2.5±0.1 (#798872) 10.7±0.8 Filtek Supreme XTE 149±15 2.2±0.0 Dentin A2 (#N902487) 11.7±0.4 Tetric EvoCeram A2 118±5 2.3±0.2 (#W97572) 9.2±0.9.

Claims

Claims 1. Radically polymerizable compound, represented by a structure of formula 1: PG-Sp-PCA-Sp-[OC(O)NH-K-NHC(O)O-Sp-PCA-Sp]n-PG (formula 1), where PG = each independently selected from a radically polymerizable group, preferably selected from (NR 1 )OC-CR 2 =CH2 and OOC-CR 2 =CH2, preferably selected from OOC-CR 2 =CH2, R 1 = selected from hydrogen, a C1-C8 alkyl group, an aryl group and an araliphatic group having C6-C8 carbon atoms, preferably selected from a C1-C8 alkyl group and a benzyl group, R 2= selected from hydrogen, a C1-C4 alkyl group, preferably selected from hydrogen and methyl; Sp = each independently a spacer group selected from unbranched and branched alkylene having C1-C19 carbon atoms, which may additionally contain oxygen, sulfur and / or -OOC- in the carbon chain, or Sp is omitted; PCA = each independently a polycyclic group, preferably an aliphatic polycyclic group, more preferably an aliphatic bi- or tricyclic group; K = an aliphatic acyclic, saturated or unsaturated unit with C1-C15 carbon atoms, preferably C3-C13 carbon atoms, more preferably C6-C9 carbon atoms, where the unit may be substituted with one or more aliphatic C1-C3 carbon substituents, an aliphatic cyclic, saturated or unsaturated unit with C3-C15 carbon atoms, preferably C5-C13 carbon atoms, more preferably C6-C13 carbon atoms, where the unit may be substituted with one or more aliphatic C1-C3 carbon substituents, or an aromatic or araliphatic unit with C6-C14 carbon atoms, preferably C6-C13 carbon atoms, where the unit may be substituted with one or more aliphatic C1-C3 carbon substituents;n = 1 to 9, preferably 1 to 6.

2. Radically polymerizable compound according to claim 1, characterized in that the spacer group Sp is selected from methylene, *CH2-(OC2H4); p , * CH2-(OC3H6) p , *(OC2H4) p , *(OC3H6) p , *CH2-(OC(O)-R 5 -)p, *(OC(O)-R 5 -)p and *SR 5 , where p = 1-5, preferably 1-3 and R 5 one C1-C12 alkylene group, preferably a C2-C6 alkylene group.

3. Radically polymerizable compound according to claim 1 or claim 2, characterized in that the polycyclic group PCA is selected from structures of formulas 2 to 13: (Formula 2) (Formula 3) (Formula 4) (Formula 5) (Formula 6) (Formula 7) (Formula 8) (Formula 9) (Formula 10) (Formula 11) (Formula 12) (Formula 13), which may optionally be substituted with one or more C1-C4 alkyl groups.

4. A radically polymerizable compound according to any one of claims 1 to 3, characterized in that the polycyclic group PCA is an aliphatic tricyclic group, preferably tricyclo[5.2.1.0 / 2,6]decanylene (TCD) (formula 2).

5. A radically polymerizable compound according to any one of claims 1 to 4, characterized in that K is selected from the following structures of formulas 14 to 26: , preferably selected from a structure of formulas 14, 15, 16, 17, 18, 19 and 20.

6. A radically polymerizable compound according to any one of claims 1 to 5, characterized in that the radically polymerizable compound is represented by a structure of formula 27: (Formula 27), where R 2= hydrogen or a methyl group; Sp = in each case independently a spacer group selected from unbranched and branched alkylene with C1-C19 carbon atoms, which may additionally contain oxygen, sulfur and / or -OOC- in the carbon chain, or Sp is omitted; PCA = in each case independently a polycyclic group, preferably an aliphatic polycyclic group, more preferably an aliphatic bi- or tricyclic group, even more preferably a tricyclic group, most preferably tricyclo[5.2.1.0 / 2,6]decanylene; K = an aliphatic acyclic, saturated or unsaturated unit with C1-C15 carbon atoms, preferably C3-C13 carbon atoms, more preferably C6-C9 carbon atoms, where the unit may be substituted with one or more aliphatic C1-C3 carbon substituents, an aliphatic cyclic, saturated or unsaturated unit with C3-C15 carbon atoms, preferably C5-C13 carbon atoms, more preferably C6-C13 carbon atoms, where the unit may be substituted with one or more aliphatic C1-C3 carbon substituents, or an aromatic or araliphatic unit with C6-C14 carbon atoms, preferably C6-C13 carbon atoms, where the unit may be substituted with one or more aliphatic C1-C3 carbon substituents; r = 1 to 9, preferably 1 to 6.

7. A radically polymerizable compound according to any one of claims 1 to 6, characterized in that the radically polymerizable compound is represented by a structure selected from the formulas 28-31: (Formula 28), (Formula 31), where t, u, v and w are each independently 1-9, preferably 1-6; and R 2 = selected from hydrogen, a C1-C4 alkyl group, preferably selected from hydrogen and a methyl group.

8. A process for preparing a radically polymerizable compound, characterized in that the process comprises the following steps: a) reacting a diol of a polycyclic PCA group with a (meth)acrylic acid ester to form a PCA- Mono(meth)acrylate having a hydroxyl group, by means of enzymatic catalysis, b) reacting the PCA mono(meth)acrylate containing the hydroxyl group from step a) with a diisocyanate compound, preferably using a catalyst.

9. A radically polymerizable composition comprising: a) one or more radically polymerizable compounds according to any one of claims 1 to 7; b) optionally one or more further radically polymerizable monomers or oligomers that do not fall under the at least one compound of formula 1; c) optionally at least one initiator or one initiator system for the polymerization; d) optionally one or more stabilizers; e) optionally one or more fillers; f) optionally dental additives.Radically polymerizable composition according to claim 9, characterized in that in the radically polymerizable composition one or more radically polymerizable compounds of the formula 1 in a mass fraction of 1-100 wt.%, preferably 2-80 wt.%, preferably 2-65 wt.%, even more preferably 10-65 wt.%, based on the total mass of all radically polymerizable compounds. Monomers and oligomers of the polymerizable composition are included.

11. The radically polymerizable composition according to claim 9 or 10, characterized in that several compounds of formula 1, selected from monomers (n = 1) and / or oligomers (n = 2-9), are present.

12. The radically polymerizable composition according to any one of claims 9 to 11, characterized in that the radically polymerizable composition is a radically polymerizable dental material. 13.Use of the radically polymerizable compound according to one of claims 1 to 7 or the radically polymerizable composition according to one of claims 9 to 12 for producing a polymerizable dental material, preferably a dental composite, dental cement, self-adhesive dental cement, dental varnish, core build-up, root canal filling, filling, underfilling, fixing, crown, bridge, restoration, orthodontic and / or prosthesis material.

14. Use according to claim 13, characterized in that the polymerizable dental material is used as a 3D printing material, wherein preferably orthodontic materials, aligners, splint materials, denture base materials, model materials, crown and bridge materials, drilling templates, gingiva masks, tray materials, mouth guards or veneers are produced from the polymerizable dental material by means of 3D printing.

15. Cured dental material made from a polymerizable composition according to one of claims 9

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