Radically polymerisable compound and composition

Abstract

The invention relates to a radically polymerisable compound represented by a structure of formula 1: PG1-Sp1-[OC(O)NH-K-NHC(O)O-Ar]n-OC(O)NH-K-NHC(O)O-Sp2-PG2 ( formula 1), and to a radically polymerisable composition, to the use of the radically polymerisable compound or the radically polymerisable composition for producing a polymerisable dental material and to a cured dental material.

Description

[0001] Radically polymerizable compound and composition

[0002] The invention relates to a radically polymerizable compound, a radically polymerizable composition containing such a compound, the use of such compounds and a cured dental material.

[0003] Radically polymerizable dental materials primarily contain (meth)acrylate monomers. Dimethacrylate systems are commonly used for restorative and prosthetic dental materials, such as dental fillings and dentures, due to their properties such as rapid radical polymerization, good mechanical properties, and aesthetic appearance. Commonly used base monomers are 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 (Bis-GMA) and 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyl-bis(2-methylacrylate) (UDMA).

[0004] For some time now, there has been an effort to largely eliminate 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.

[0005] 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 much lower viscosity, such as triethylene glycol dimethacrylate (TEDMA), are used. TEDMA is a very flexible, low-molecular-weight monomer with a low viscosity (0.01 Pa s at 23°C) and high mobility during polymerization, which favors polymerization conversion.

[0006] However, the polymerizable compositions containing these monomer mixtures and the dental materials obtained therefrom 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 currently used dimethacrylate monomers and the shrinkage stress 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 double bond turnover to reduce unreacted monomers unfortunately lead to an increase in polymerization shrinkage and shrinkage stress.

[0007] 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 biodegradation processes. Monomers with the structural element bis-2,2-[p-oxyphenyl]propane, i.e., monomers based on bisphenol-A, are also being critically evaluated, since 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 critical toxicological properties.

[0008] There are various approaches to increasing conversion or reducing volume shrinkage. In dental composites for dental fillings that contain filler in an organic resin matrix, attempts are made to reduce volume shrinkage by increasing the filler content. However, if the filler content is too high, it is difficult to mix the fillers with the organic resin. In addition, the filler content is limited for dental composites, which must have a certain flowability. New monomers are still being developed to increase conversion and reduce polymerization shrinkage, for example 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.Furthermore, the increased viscosity of such monomers requires the use of higher amounts of low viscosity monomers in order to be able to use them for dental composites, which has an adverse effect on shrinkage.

[0009] US 4,952,241 discloses (meth)acrylic acid derivatives containing urethane groups, wherein the end groups of the compounds each have two (meth)acrylate groups. The high functionalization of the chain leads to increased polymerization shrinkage. According to US 4,952,241, however, the functionalization is necessary to achieve sufficient mechanical properties.

[0010] There is therefore a need for novel radically polymerizable compounds or radically polymerizable compositions containing such compounds which can enable a reduced toxicity potential and a reduced volume shrinkage while at the same time providing good mechanical properties of the dental material produced therefrom and which are easily available.

[0011] The present invention is therefore based on the object of providing novel radically polymerizable compounds and a radically polymerizable composition containing such novel compounds which overcome the above-mentioned disadvantages of the prior art.

[0012] 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 as well as good tensile strength and 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 has a refractive index which is particularly suitable for producing materials which contain fillers customary in the dental field and which have advantageous optical properties, in particular with regard to translucency or opacity.In particular, the aim is to achieve a refractive index of the cured resin that allows the production of translucent composites using highly radiopaque fillers whose refractive index is even above 1.53. Furthermore, it should be possible to provide a radically polymerizable composition in which the radical polymerization results in a high conversion of the monomers, so that the materials and devices produced from the radically polymerizable composition have only a low residual monomer content. Furthermore, it should also be possible to provide a polymerized composition produced from the radically polymerizable composition that has only low water solubility and low water absorption.

[0013] The invention solves this problem by a radically polymerizable compound represented by a structure of formula 1 :

[0014] PG 1 -Sp 1 - [OC (O) NH-K-NHC (O) O-Ar ] n -OC (O) NH-K-NHC (O) O-Sp 2 -PG 2

[0015] ( Formula 1 ) , where

[0016] PG 1 , PG 2 = each independently selected from a radically polymerizable group, preferably selected from (NR 1 ) OC-CR 2 =CH2 and OOC-CR 2 =CH2, more preferably selected from OOC- CR 2 =CH2,

[0017] R 1 = selected from hydrogen, a Cl-C8 alkyl group, an aryl group and an araliphatic group with C6-C8 carbon atoms, preferably selected from a Cl-C8 alkyl group and a benzyl group, R 2 = selected from hydrogen, a Cl-C4 alkyl group, preferably selected from hydrogen and methyl;

[0018] Sp 1 , Sp 2= each independently a spacer group selected from unbranched and branched alkylene with Cl-C19 carbon atoms, which may additionally contain oxygen, sulfur and / or -OOC- in the carbon chain;

[0019] 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, wherein the moiety may be substituted with one or more aliphatic C1-C3 carbon substituents;

[0020] Ar = -R 3 -BG-R 4 - , where

[0021] BG = selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, 2,3-naphthylene, 2,6-naphthylene, 1,8-naphthylene, 9,1O-anthracenylene, 1,8-anthracenylene, 9,9-fluorenylene, 9,9-bis(phenyl-4-yl)fluorene and 4,4'-biphenylene, and

[0022] R 3 , R 4 = each independently a spacer group selected from unbranched and branched alkylene with Gl-C6 carbon atoms, where the carbon atoms in the chain may be replaced by O, S or OC (O); and n = 1 to 9, preferably 1 to 6.

[0023] Preferred embodiments are found in the subclaims.

[0024] First, some terms used in the context of the invention will be explained.

[0025] For the purposes of the present invention, (polymerizable) dental materials are understood to mean materials for (bio)medical use, in particular on hard tooth substance, such as enamel and dentine, or on bone tissue, such as the jawbone. A polymerizable dental material is generally a resin-based material which is a mixture of various components that is curable. For the purposes of this invention, a resin essentially consists of a monomer mixture and further components which are soluble in the monomers, such as initiators, stabilizers, etc.

[0026] In the context of the present invention, the radically polymerizable compounds are monomers where n = 1, and oligomers where n = 2 to 9. Nevertheless, monomers and oligomers with n = 1 to 9 are summarized in the context of the invention under the term "monomers," i.e., a monomer mixture comprising a radical compound according to the invention can comprise both a monomer and / or an oligomer.

[0027] In the context of the present invention, a monomer mixture is a mixture which comprises or consists of a1) one or more radically polymerizable compounds according to the invention and optionally a2) one or more further radically polymerizable monomers and / or oligomers which do not fall under the at least one compound of formula 1. Other components of the polymerizable dental material, such as initiator, filler, conventional dental additive, etc., are not components of the monomer mixture.

[0028] It is preferred that the radically polymerizable compound is represented by a structure of formula 2:

[0029] CH2=CR 5 -COO-Sp 1 - [OC (O) NH-K-NHC (O) O-Ar ] n -OC (O) NH-K-NHC (O) O-Sp 2 - OOC-CR 6 =CH2

[0030] ( Formula 2 ) , where

[0031] R 5 , R 6= each independently selected from hydrogen, a Cl-C4 alkyl group, preferably selected from hydrogen and methyl;

[0032] Sp 1 , Sp 2 = each independently a spacer group selected from unbranched and branched alkylene with Cl-C19 carbon atoms, which may additionally contain oxygen, sulfur and / or -OOC- in the carbon chain;

[0033] 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, wherein the unit may be substituted with one or more aliphatic Cl-C3 carbon substituents;

[0034] Ar = -R 3 -BG-R 4 -, where

[0035] BG = selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, 2,3-naphthylene, 2,6-naphthylene, 1,8-naphthylene, 9,10-anthracenylene, 1,8-anthracenylene, 9,9-fluorenylene,

[0036] 9.9-Bis (phenyl-4-yl ) f luoren and 4 , 4 ' -biphenylene, and

[0037] R 3 , R 4 = each independently of one another a spacer group selected from unbranched and branched alkylene having C1-C6 carbon atoms, where the carbon atoms in the chain may be replaced by O, S or OC(O); and n = 1 to 9, preferably 1 to 6.

[0038] Preferably, Ar is selected from 9,9-bis-[(4-(ethoxy-2-yl)-phenyl]-fluorene, 1,3-bis(ethoxy-2-yl)benzene, 1,4-bis(ethoxy-2-yl)benzene, bis(ethyl-2-yl)terephthalate, 1,2-dimethanediylbenzene, 1,3-dimethanediylbenzene, 1,4-dimethanediylbenzene, 9,10-dimethanediylanthracene, 4,4'-dimethanediylbiphenyl, 1,3-di(pentane-3,3-diyl)benzene, 1,4-di(propane-2,2-diyl)benzene and 9,9-bis(methylene)f fluoren . More preferably, Ar is selected from 1,2-dimethanediylbenzene, 1,3-dimethanediylbenzene, 1,4-dimethanediylbenzene,

[0039] 9,10-Dimethanediylanthracene, 4,4'-Dimethanediylbiphenyl, 1,3-Di(pentane-3,3-diyl)benzene, 1,4-Di(propane-2,2-diyl)benzene and 9,9-Bis(methylene)fluorene. Preferred are Sp 1 and Sp 2 each independently selected from a C2-C6 alkylene group, more preferably an unbranched C2-C6 alkylene group.

[0040] Preferably, K is selected from the following structures of formulas 3 to 15 :

[0041] More preferably, K is selected from the following structures of formulas 3 to 6, 10 and 12: (Formula 3) ( Formula

[0042] ( Formula

[0043] ( Formula

[0044] (Formula 10) ( Formula 12) .

[0045] In one embodiment, the radically polymerizable

[0046] Compound preferably by a structure of formulas 16 to

[0047] 22 shown:

[0048] ( Formula 16) ,

[0049] (Formula 21)

[0050] ( Formula 22 ) , where n = each independently 1-9, preferably 1-6; and

[0051] R 7 , R 8 , R 9 , R 10 , R 11 , R12 , R 13 = each independently selected from hydrogen and a methyl group.

[0052] For the radically polymerizable compound represented by a structure selected from the following formulas 16-22, it should be noted that these formulas represent only one isomeric formula with respect to K and that all other isomeric formulas are intended to be included. This refers in particular to the orientation of K as well as the isomerism of the methyl group distribution for K = trimethylhexamethylene, i.e., 2,4,4- and 2,2,4-trimethyl substitution.

[0053] The invention relates to a radically polymerizable composition comprising: a) a monomer mixture comprising: a1) one or more radically polymerizable compounds, preferably according to one of claims 1 to 7, and a2) optionally one or more further radically polymerizable monomers and / or oligomers which do not fall under the at least one compound of formula 1; b) optionally at least one initiator or one initiator system for the polymerization; c) optionally one or more stabilizers; d) optionally one or more fillers; e) optionally additives customary in dentistry.

[0054] More preferably, the radically polymerizable composition contains several compounds of formula 1 selected from monomers (n = 1) and / or oligomers (n = 2-9, preferably n = 2-9), even more preferably selected from monomers (n = 1) and / or oligomers (n = 2-6).

[0055] It is preferred that the radically polymerizable composition contains one or more radically polymerizable compounds of formula 1 in a mass fraction of 0.1-100 wt.%, preferably 1-98 wt.%, more preferably 2-85 wt.%, still preferably 2-65 wt.%, most preferably 10-65 wt.%, based on the total mass of all radically polymerizable monomers and oligomers of the polymerizable composition.

[0056] One or more of the following constituents can be present in the radically polymerizable composition in the following mass proportions, based on the total mass of the polymerizable composition: a1) one or more radically polymerizable compounds of formula 1 from 1 to 99 wt.%, preferably from 2 to 95 wt.%, more preferably from 2 to 80 wt.%, even more preferably from 2 to 65 wt.%, even more preferably from 10 to 65 wt.%; a2) one or more further radically polymerizable monomers and / 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.%; b) the at least one initiator or initiator system for the polymerization from 0 to 5 wt.%, preferably from 0.01 to 5 wt.%; c) the stabilizers from 0 to 5 wt.%, preferably from 0.001 to 5 wt.-%, more preferably 0.005 to 2 wt . -%; d) the fillers or filler particles from 0 to.

[0057] 95% by weight, preferably from 1 to 95% by weight, more preferably from 5 to 92% by weight; e) the dental additives from 0 to 5% by weight, preferably from 0.001 to 5% by weight.

[0058] In a preferred embodiment, the radically polymerizable composition is a radically polymerizable dental material. a2) Further polymerizable monomers or oligomers

[0059] The radically polymerizable composition may, in addition to the at least one radically polymerizable compound of formula 1, also contain one or more further radically polymerizable monomers or oligomers which do not fall under the at least one radically polymerizable compound of formula 1.

[0060] The selection of these additional radically polymerizable monomers and oligomers is preferably made depending on the material to be produced. This also applies to the proportion of the additional radically polymerizable monomers and / or oligomers in the radically polymerizable composition.

[0061] It is preferred that the monomer mixture comprises as a further radically polymerizable monomer a2) bis ((meth)acryloyloxymethyl) tricyclo [5 . 2 . 1 . 0 / 2 , 6 ] decane (hereinafter referred to as tricyclodecanedimethanol di (meth)acrylate) and / or a compound represented by a structure selected from the formula 23:

[0062] ( Formula 23 ) , where

[0063] R 14 , R 15 = each independently selected from hydrogen and a methyl group, and

[0064] R 16 , R 17= each independently selected from - ( OC2H4) P -O- and - (OC3H7) pO- . It is preferred that the radically polymerizable composition contains the compounds selected from tricyclodecanedimethanol di(meth)acrylate and / or compounds represented by a structure of formula 23 in a mass fraction of 20-90 wt.%, preferably 20-60 wt.%, more preferably 30-55 wt.%, based on the total mass of all radically polymerizable monomers and oligomers of the polymerizable composition.

[0065] 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 in EP 0235836 B1 or US 4131729 / DE 2816823.

[0066] 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. Urethane (meth)acrylates are preferably selected from linear or branched alkylene-functionalized urethane (meth)acrylates and urethane (meth)acrylate-functionalized polyethers.

[0067] Preference is given to difunctional urethane (meth)acrylates selected from difunctional urethane (meth)acrylates having a bivalent alkylene group and those having a bivalent cyclic aliphatic hydrocarbon group. Such difunctional urethane (meth)acrylates having 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 having alkylene group(s), such as bis(methacryloxy-2-ethoxycarbonylamino)alkylene, bis(methacryloxy-2-ethoxycarbonylamino)-substituted polyalkylene ethers. Preferred are bis(methacryloxy-2-ethoxycarbonylamino)alkylenes comprising linear or branched C3-C2O-alkylene groups, preferably C3-C9-alkylene groups. Methyl-substituted alkylene is also particularly preferred.

[0068] Furthermore, the further radically polymerizable monomer can be a reaction product of 3-hydroxyethyl methacrylate or 3-hydroxypropyl methacrylate and 2,2,4-trimethylhexamethylene diisocyanate, or a reaction product of 3-hydroxyethyl acrylate or 3-hydroxypropyl acrylate and trimethylhexamethylene diisocyanate.

[0069] 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), GN 1993CG (aliphatic urethane methacrylate), PRO 21252 (aliphatic urethane acrylate),H1391 (Hydroxypropyl- urethandimethacrylat ) , H1391 (Urethandimethacrylat) , X851-1066 (Urethanedimethacrylat IP-DI) , X726-000 (PEG 400 extended Urethandimethacrylat ) , Urethanmethacrylat 11-70 und, Urethan- methacrylat 14-774 .,

[0070] 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-butanedioldi(meth)acrylate, 1,1O-decanedioldi(meth)acrylate and 1,12-dodecanedioldi(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).

[0071] Suitable further radically polymerizable monomers can, for example, be selected 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.

[0072] 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.

[0073] In a particular embodiment, it is preferred that the composition does not contain any monomer or oligomer having 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).

[0074] For dental adhesives or self-adhesive composite cements, acidic monomers and / or water-soluble monomers can be used. A typical proportion of acidic monomers is known from the prior art. Acidic monomers are compounds that contain 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 are, for example, 2-(methacryloyloxyethyl)phenyl hydrogen phosphate (phenyl-P); 2-Hydroxyethyl methacrylic dihydrogen phosphate (HEMA phosphate), dipentaerythritol pentamethacrylate phosphate (PENTA), di-2-hydroxyethyl methacrylic hydrogen phosphate (di-HEMA phosphate), 1 O-methacryloyloxydecyl dihydrogen phosphate (MDP), 1, 3-Glycerol dimethacrylate phosphate (GDMAP), 2, 5-dimethacryloyloxyethyloxycarbonyl-l, 4-benzenedicarboxylic acid (PMDM), butane-1, 2, 3, 4-tetracarboxylic acid di- (2-hydroxyethyl methacrylic) ester (TCB), 4-methacryloyloxyethyl trimellitic acid (4-MET), 4-Methacryloxyethyltrimellithanhydride (4-META), Py- romellitic acid bis-glycerol dimethacrylate (PMGDM) and 11-methacryloyloxy-1,1-undecanedicarboxylic acid (MAC-10).

[0075] Furthermore, radically polymerizable antibacterial monomers can also be used as additional monomers.

[0076] The radically polymerizable composition preferably comprises one or more further radically polymerizable monomers or oligomers which 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. b) Initiator or initiator system

[0077] Suitable initiators or initiator systems are capable of initiating radical polymerization reactions. Such initiators or initiator systems are known to those skilled in the art.

[0078] Initiator systems consist of at least one initiator and at least one further compound, such as a coinitiator. These can be distributed across various components of a polymerizable dental material. The polymerizable composition according to the invention or the polymerizable dental material 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 can cure the material 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 by additional reaction with one or more coinitiators.Preferred here 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, a-dicarbonyl compounds, aryldiazonium salts, arylsulfonium salts, aryliodonium salts, ferrocenium salts, phenylphosphonium salts or a mixture from these compounds.

[0079] Diphenyl-2, 4, 6-trimethylbenzoylphosphine oxide, phenyl-bis-2, 4, 6-trimethylbenzoylphosphine oxide, benzoin, benzoin alkyl ethers, benzil dialkyl ketals, a-hydroxyacetophenone, dialkoxyacetophenones, a-aminoacetophenones, isopropylthioxanthone, are particularly preferred. Camphorquinone, phenylpropanedione, 5, 7-diiodo-3-butoxy-6-fluorone, (eta-6-cumene) (eta-5-cyclopentadienyl) iron hexafluorophosphate, (eta-6-cumene) (eta-5-cyclopentadienyl) iron tetraf luoroborate, (eta-6-cumene ) ( eta-5-cyclopentadienyl ) iron hexaf luoroantimonate, substituted diaryliodonium salts, triarylsulfonium salts or a mixture of these compounds.

[0080] Preferred coinitiators for photochemical curing are tertiary amines, borates, organic phosphites, diaryliodonium compounds, thioxanthones, xanthene, fluorenes, fluorones, a-dicarbonyl compounds, dicarbonyl systems as described in WO 2021 / 048313 A1, condensed polyaromatics or a mixture of these compounds. Particularly preferred are N,N-dimethyl-p-toluolidine, N,N-dialkyl-alkylanilines, N,N-dihydroxyethyl-p-toluidine, 2-ethylhexyl-p-(dimethylamino)-benzoate, ethyl-p-(dimethylamino)-benzoate, 2-dimethylaminoethyl methacrylate, polyethers provided with 4-(dimethylaminobenzoyl) groups such as the polymer available under the trade name Genopol 19-265 (GAS 2067275-86-7), butyrylcholine triphenyl butylborate or a mixture of these compounds.

[0081] So-called thermal initiators can also be used as initiators, which can cure the material by absorbing thermal energy at elevated temperature. Preferably, inorganic and / or organic peroxides, inorganic and / or organic hydroperoxides, a,a'-azobis(isobutyroethyl ester), a,a'-azobis(isobutyronitrile), benzpinacols, percarbonates, peresters or a mixture of these compounds are used. Particular preference is given to using diacyl peroxides such as benzoyl peroxide or lauroyl peroxide, cumene hydroperoxide, benzpinacol, 2,2'-dimethylbenzpinacol or a mixture of these compounds.

[0082] For chemical curing at room temperature, a redox initiator system is generally used which consists of one or more initiators and a coinitiator or coinitiators acting as an activator. For reasons of storage stability, individual components of an initiator system are incorporated in spatially separate parts of the dental material according to the invention, ie a multi-component, preferably a two-component material is present. The initiator or initiators used are preferably inorganic and / or organic peroxides, inorganic and / or organic hydroperoxides, barbituric acid derivatives, malonyl sulfamides, protonic acids, Lewis or Broensted acids or compounds which release such acids, carbenium ion donors such as methyl triflate or triethyl perchlorate or a mixture of these compounds, and the coinitiator or coinitiators used are preferably tertiary amines, heavy metal compounds, in particular compounds of the 5th, 8 . and the 11 . group of the periodic table ("vanadium , iron and copper group") , compounds with ionogenically bound halogens or pseudohalogens such as quaternary ammonium halides , weak Broenstedt acids such as e.g. alcohols and water or a mixture of these compounds .

[0083] Any conceivable combination of the initiators and coinitiators described above can also be included. An example of this are so-called dual-curing compositions or 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.

[0084] The polymerizable composition or the polymerizable dental material is preferably light-curing. In a preferred embodiment, the polymerizable composition comprises an initiator system that initiates rapid polymerization in the wavelength range of 395-700 nm, more preferably in a wavelength range of 400-500 nm. A preferred initiator system contains camphorquinone (CQ) as initiator and tertiary aromatic and aliphatic amines as coinitiator. 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 Al, EP 3888616 Al, EP 3881818 Al and M. Topa, J.Ortyl, Materials 13, 4093 (2020).

[0085] In another preferred embodiment, which is particularly suitable for 3D printing applications, the dental material according to the invention contains an initiator system that initiates radical polymerization in the wavelength range of 300-500 nm, more preferably in a wavelength range of 350-420 nm, and particularly preferably 365-410 nm. Preferred initiator types are those that function according to the Norrish Type 1 mechanism.

[0086] The at least one initiator or 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. c) Stabilizer

[0087] The radically polymerizable composition may contain one or more stabilizers. Such stabilizers are known to those skilled in the art.

[0088] Suitable stabilizers are preferably benzotriazoles, triazines, benzophenones, cyanoacrylates, salicylic acid derivatives, hindered amine light stabilizers (HALS) and mixtures thereof. Particularly suitable are o-hydroxyphenylbenzotriazoles, such as 2-2H-benzotriazol-2-yl)-4-methylphenol, 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butyl-phenol, 2-(5-chloro-2H-benzotriazol-2-yl)-4, 6-di- tert-butyl-phenol, 2-(2H-benzotriazol-2-yl)-4, 6-di-tert-pentyl-phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-dodecyl-phenol, 2-(2H-benzotriazol-2-yl)-4, 6-bis-( 1-methyl-l-phenylethyl) -phenol, 2- ( 2H-Benzotriazol-2-yl)-6-(1-methyl-l-phenylethyl)-4-(1, 1, 3, 3-tetramethylbutyl)-phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol and 3-(2H-ben- zotriazol-2-yl) - 5-ter-butyl-4-hydroxy-benzenepropanoic acid ester, o-hydroxyphenyltriazines, such as 2- (2-hydroxy-4-hexyloxy-phenyl) - 4,6-diphenyl-1,3,5-triazine or 2-(2-hydroxy-4-[2-hydroxy-3-dodecyloxy-propyloxy]-phenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine, o-hydroxybenzophenones, such as 2-hydroxy-4-octyloxybenzophenone, cyanoacrylates, such as ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate and tetrakis-[(2-cyano-3,3-diphenylacryloyl)oxymethyl]-methane, hindered amine light stabilizers (HALS)), such as N,N'-bis(isopropyl)-N,N ' -bis- (2, 2, 6, 6-tetramethyl-4-piperidin-yl) -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) -sebacate, salicylic acid esters and mixtures thereof.,

[0089] 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, in particular.

[0090] The stabilizers may 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.

[0091] In one embodiment, the radically polymerizable composition may 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.

[0092] The stabilized radicals are preferably present in the radically (photo)polymerized compositions in a mass fraction of 0.005 to 0.01 wt.%, based on the total mass of the polymerizable composition. d) Fillers

[0093] The radically polymerizable composition can comprise fillers or filler particles. The filler particles are not restricted to a specific particle shape. Rather, fillers with a spherical, scaly, platelet-like, needle-like, sheet-like, or irregular shape can be used very well. The filler particles preferably have an average particle diameter of 5 nm to 100 pm, more preferably 5 nm to 50 pm.

[0094] Suitable fillers can be selected from a wide variety of materials commonly used in dental materials or products. The choice of filler can, for example, adjust the fluidity, viscosity, consistency, hue, radiopacity, and mechanical stability of a composition or dental material. 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 but also in combination with one another.

[0095] 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, fluoroaluminium 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 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 pm, preferably an average particle size d50 of 0.2-5 pm, and particularly preferably an average particle size of 0.2-1.5 pm. It may be preferred that the average particle size d50 be between 0.1-0.5 pm. In such cases, it is particularly preferred that the average particle size d90 be less than 1.0 pm. 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.

[0096] 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 are, the better they can fulfill their function of filling the cavities between the coarser 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 sold, for example, under the names "NALCO COLLOIDALS ILICAS" (Nalco Chemical Co.), "Ludox colloidal silica" (Grace), or "Highlink OG" (Clariant).

[0097] 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 m 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™ ("0X50", "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" Wacker-Chemie AG, Munich, Germany) and Orisil™ ("200", "300", "380" Orisil, Lviv, Ukraine).

[0098] 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 method as described in US Pat. No. 6,730,156 (e.g., Production Example B).

[0099] The use of spherical submicroparticles based on silicon-zirconium mixed oxides, as described in DE 19524362 Al or US2020 / 0121564 Al, can be particularly advantageous for achieving high fill levels with simultaneous high aesthetics and abrasion stability.

[0100] The aggregated fillers preferably have an average particle size of 1-15 pm, more preferably an average particle size of 1-10 pm, even more preferably an average particle size of 2-5 pm.

[0101] 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 differentiation between healthy 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 influence the color of the restoration as little as possible. 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, for example:Yttrium trifluoride and ytterbium trifluoride. Irregularly shaped or spherical YbF3 or YF3 particles with an average primary particle size of 40 nm to 1.5 pm are particularly suitable, and core-shell combination products consisting of a YF3 or YbF3 core and a SiO2 shell are particularly preferred, 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 pm.

[0102] 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), polyurethane (PU), polyurea, methyl methacrylate-ethyl methyl acrylate copolymer, ethylene-vinyl acetate copolymer, and styrene-butadiene copolymer. Furthermore, the organic filler may contain a biologically active component, a specific pigment, a polymerization initiator, a stabilizer, or something similar added during the manufacturing process. The organic fillers may be used alone or as mixtures.

[0103] 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 it is 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 pm, more preferably an average particle size of 0.5-50 pm, even more preferably an average particle size of 1-30 pm.

[0104] The mean particle size is preferably determined by means of dynamic light scattering or laser diffraction or static light scattering of the particles in a dispersion with a suitable dispersant (e.g. Coulter LS 13 320 XR, 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 preferred for this purpose. The mean particle size can also be determined by microscopy, in particular electron microscopy. The absolute particle size and preferably the d50 value are preferably stated.

[0105] 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 incorporation of the fillers into the resin mixture. As a result of this treatment, the surfaces of the inorganic particles are organically modified, ie, 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 the inorganic fillers that carry OH groups on the surface. Examples here are Y _Methacryloxyalkyltrimethoxysilanes (number of C atoms between the methacryloxy group and the silicon atom: 3 to 12), γ-methacryloxyalkyltriethoxysilanes (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.

[0106] Inorganic fillers that carry 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 that carry 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 as surface modifiers for salts of barium, strontium, and rare earth metals. 10-Methacryloyloxydecyl dihydrogen phosphate is particularly suitable. 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 even radically unreactive groups. Suitable unreactive groups include, for example:Trimethylsilyl, dimethylsilylene, or methylsilylidene groups, which can be applied to the surface by silanization, e.g., with hexamethyldisilazane, dimethyldimethoxysilane, or methyltrimethoxysilane. Suitable non-reactive surface-modified agglomerated nanofillers are commercially available, e.g., under 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 reactive in radical processes, e.g., methacryloyl groups. A commercially available product of a radically reactively modified agglomerated nanofiller is available under the name Aerosil R7200 (Evonik Industries AG, Essen, Germany).

[0107] Preferably, the agglomerated nanofillers can be largely deagglomerated, as described, for example, in EP 1720206.

[0108] The radically polymerizable composition according to the invention can contain 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.

[0109] The amount of filler fraction can be selected depending on the indication of a dental product. For example, the highest possible filler quantities can be used for stable, moldable filling composites, for dental compositions for the production of inlays, onlays, or overlays, and for compositions for the production of dental CAD-CAM materials. These compositions typically have filler contents of 75% to 92% by weight, based on the total composition. Flowable dental composites, luting composites, core build-up materials, crown, and bridge materials generally have an average filler content of 40 to 80% by weight, based on the total composition, while dental varnishes, dental sealing materials, dental infiltrants, or dental adhesives use fillers in the range of 1 to 40% by weight, based on the total composition.The filler ranges given above are only guidelines; depending on the filler selection, there may be deviations.

[0110] In a preferred embodiment, the radically polymerizable composition contains a selection of microfillers such that the refractive index difference between the microfillers and the remaining components of the polymerized composition (polymer matrix) is as small as possible. An is preferably <0.03, more preferably <0.02, and even more preferably <0.01. e) Dental additives

[0111] The radically polymerizable composition may contain other additives commonly used in dentistry. Suitable additives commonly used in dentistry are preferably those that can be contained in radically polymerizable dental and dental technology materials. Common dental additives are known to the person skilled in the art. Solvents or solvent mixtures, for example, can be used as conventional dental additives. Thus, the use of a mixture of water and water-miscible solvents, such as ethanol or acetone, is preferred for the production of dental adhesives.

[0112] In addition, further components of the radically polymerizable composition may include, for example, pharmacologically active compounds such as antibacterial compounds, chlorhexidine or other enzyme-inhibiting agents.

[0113] The composition may also contain one or more fluoride-releasing substances in finely divided, particulate form as a dental additive. Fluoride-releasing substances may 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.

[0114] Other suitable additives are fine-particulate substances that release calcium and / or phosphate, thereby exerting a remineralizing effect. Suitable remineralizing substances include calcium phosphate compounds such as hydroxyapatite, brushite, monocalcium phosphate, fluorapatite, and bioactive glasses such as those mentioned in DE10111449A1, DE102005053954A1, or US 9517186B2.

[0115] 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 imide, or derivatives thereof. Inorganic fluorescent pigments can be, for example, CaAl4O7:Mn 2+ (BaO .98EuO .02 ) MgAl 10 Oi7 , 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 (Fe2Oa) or iron oxide black (FeaO4), 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.

[0116] The additives customary in dentistry can be contained in the polymerizable composition in a mass fraction of 0 to 5 wt.%, preferably of 0.001 to 5 wt.%, based on the total mass of the radically polymerizable composition.

[0117] The invention has the advantage that the radically polymerizable compound according to the invention and a radically polymerizable composition containing such a compound overcome the aforementioned disadvantages of the prior art. The radically polymerizable compound and the radically polymerizable composition have excellent properties that are particularly necessary or desirable for the production of dental materials. Furthermore, the radically polymerizable composition can be prepared from novel radically polymerizable compounds or monomers that are readily available and have a reduced toxicity potential.Since the radically polymerizable composition preferably does 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 a harmful effect on health due to endocrine effects.

[0118] The use of the radically polymerizable compound or the radically polymerizable composition for producing a dental material leads to reduced polymerization shrinkage and, at the same time, good mechanical properties of the resulting dental material. This means that the radically polymerizable composition has low polymerization shrinkage and preferably reduced shrinkage stress. The radically polymerized compositions or the dental materials produced from the radically polymerizable composition have good mechanical properties, such as, in particular, very good flexural strength as well as good tensile strength and fracture toughness. These advantageous properties of the radically polymerizable compound according to the invention and of the corresponding composition are surprising in view of the molecular sizes and the structures of the radically polymerizable compounds.

[0119] Furthermore, the radically polymerizable compound and the radically polymerizable composition surprisingly have a refractive index that is particularly suitable for producing dental materials containing (radiopaque) fillers commonly used in the dental field, which exhibit desired optical properties, particularly with regard to translucency and opacity. The refractive index of the novel compound allows formulation to yield composites that have good or at least sufficient translucency after hardening. The translucency can be characterized, for example, using suitable measuring devices according to the CieLab method.

[0120] Furthermore, the radically polymerizable composition exhibits a surprisingly high monomer conversion during radical polymerization. As a result, dental materials and devices produced from the radically polymerizable composition contain only a very low residual monomer content. In addition, the radically polymerized composition (i.e., in particular, the produced dental material) exhibits only low water solubility and low water absorption, which is also advantageous.

[0121] 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 8 to 13, for producing a polymerizable dental material, preferably a dental composite, dental cement, self-adhesive dental cement, dental varnish, stump build-up, root canal filling, filling, underfilling, fixing, temporary crowns and bridges, crowns, bridges, restorations, orthodontic and / or prosthetic material.

[0122] 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, preferably in a stereolithographic process. For example, the polymerizable dental material can be used in a DLP process. 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.

[0123] 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 8 to 13.

[0124] The invention further relates to a radically polymerizable dental material according to the invention for use in a therapeutic process as a dental composite, dental cement, dental varnish, filling, underfilling, luting, stump build-up, root canal filling, crown, bridge, restoration, orthodontic and / or prosthesis material.

[0125] The invention further relates to a cured dental material produced from a polymerizable composition according to the invention, preferably according to one of claims 8 to 13. The cured dental material can be produced in a process in which a radically polymerizable composition is provided which cures or is cured in whole or in part. In a particular embodiment, the radically polymerizable composition can be 3D-printed before curing. The invention will now be described by way of example with reference to some advantageous embodiments.

[0126] Examples

[0127] 1 . Chemicals The following chemicals were used in the preparation of the examples ( Table 1 ) and were processed as described in this paragraph before further use .

[0128] Table 1 : Compounds and substances used in the examples .

[0129] Catalyst solution: The catalyst solution used for the isocyanate reaction consists of a homogeneous mixture of 50 wt.% DMTND in toluene-t.

[0130] 2. Measurement methods FT-IR spectroscopy

[0131] FT-IR spectra (types iS10 and iS20, Thermo Scientific Nicolet) were recorded using a Smart iTR ATR unit. 32 scans were taken with a resolution of 4 cm -1 recorded .

[0132] Liquid chromatography / mass spectrometry coupling (HPLC-MS)

[0133] Method 1: The 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); linear gradients were observed between the indicated time points.

[0134] Detection was performed using a Waters Micromass ZQ mass detector. Ionization was performed in ESI+ mode.

[0135] Method 2: The analysis was performed on a Waters H-class UHPLC system. The following column was used for separation: Acquity BEH C8 1.7 pm, 2.1 x 50 mm. The column temperature was 50°C. Elution was carried out at a flow rate of 0.5 ml / min with a gradient of the following mobile phases: 0.1% formic acid in water (A) and 0.1% formic acid in acetonitrile (B); linear gradients were observed between the indicated time points.

[0136] Detection was performed using a Waters Xevo G2-XS QTof mass detector. Ionization was performed in ESI+ mode.

[0137] Gel permeation chromatography (GPC)

[0138] GPC was performed using an Agilent 1200 GPC with RI detector (PSS, Germany). The following column combination (PSS, Germany) was used: precolumn / 100 Å / 100 Å / 100 Å. The eluent was THE at a flow rate of 1 ml / min. The sample concentration was approximately 5 mg / ml. GPC was performed at 20°C.

[0139] IH NMR spectroscopy:

[0140] 1H NMR measurements were performed on a Varian Mercury 300 MHz spectrometer. Deuterated chloroform served as the solvent. The residual signal of non-deuterated chloroform at 7.26 ppm was used for spectral calibration.

[0141] Determination of isocyanate or NCQ content:

[0142] The NCO content was determined either by quantitative FT-IR spectroscopy or by titration. For this purpose, the isocyanate groups were reacted with an excess of dibutylamine, and the excess amount of dibutylamine was determined by back-titration with HCl. Bromophenol blue was used as an indicator. The NCO content can then be calculated from the required amount of HCl.

[0143] 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.

[0144] viscosity

[0145] The viscosity measurements were carried out using a rotational viscometer (type Kinexus, Malvern Instruments GmbH, Germany) with a plate-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.

[0146] Determination of refractive indices

[0147] The refractive indices of uncured compositions were determined using an Abbe AR refractometer (A. Krüss Optronik, Germany) at 23°C ±1°C against air, based on the D-line of sodium light. Triplicate determinations were performed in each case, and the mean value was calculated.

[0148] The refractive index of cured compositions was determined according to ISO 489:1999 using an Abbe refractometer AR (A. Krüss Optronik). A drop of cinnamon oil was placed on the specimen and brought into contact with the measuring prism of the refractometer. Triplicate determinations were performed for each specimen, 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) positioned on a slide covered with a clear, colorless polyester film (Hostaphan®). Another film, followed by another slide, was placed bubble-free on the resin, secured with clamps, and exposed to light for 90 s using a light-curing unit (Hi-Lite Power®; Heraeus Külzer). The cured specimen was then removed from the mold. Flexural strength (BF) and Young's modulus (EM) were determined.

[0149] To determine flexural strength and Young's modulus, test specimens were manufactured in accordance with ISO 4049:2009. However, the test specimens were produced by exposure to light using a light polymerization device (Hi-Lite Power®; Heraeus Külzer). For this purpose, the dental composites in the test specimen molds (40 mm x 2 mm x 2 mm) were exposed to light from both sides for 90 s. The test specimens were stored in distilled water at 37 °C for 24 hours. Flexural strength and Young's modulus were determined using a Zwick universal testing machine (type Z 010 or type Z2.5, Zwick-Roell, Germany). The mean value and standard deviation are given.

[0150] Measurement of volume shrinkage of resin mixtures (liquid pycnometer)

[0151] 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.

[0152] 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 filled 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 and then sealed. When the measuring temperature was reached, the mass of the filled pycnometer was measured, and from this the density of the uncured composition was determined.

[0153] To determine the density of the cured compositions, cuboid-shaped test specimens (35 mm x 20 mm x 3 mm) were prepared. The uncured compositions were filled into the appropriate test specimen molds without any air bubbles and cured for 90 seconds from the top and bottom using a light-curing unit (Hi-Lite Power®; Heraeus Külzer). The cured test specimens were stored at 23°C for 24 ± 2 hours.

[0154] To determine the density of the cured compositions, the mass of the cured test specimen ml and the empty weight of the pycnometer mO 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 the density of the cured test specimen p was calculated from this. NA determined according to equation 1 in g / mL: ml x 0.9982

[0155] PnA (Equation 1) ml + 0.9982 xV2+mO-m3

[0156] V2 = specified volume of the pycnometer used at

[0157] 20°C

[0158] In this way, 3 cured test specimens were measured.

[0159] The volume shrinkage (VS) as mean value (MW V s) was calculated from the difference between the density before (pVA) and the mean value of the densities after curing (MWpNA) (Equation 2) .

[0160] MWpNA -pVA

[0161] MW VS (Equation 2)

[0162] MWpNA Determination of the standard deviation of the volume shrinkage SD V s was calculated according to equation 3 .

[0163] SDvs = 100 X p VA X SDp NA / MW 2 p NA ( Equation 3 )

[0164] 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.

[0165] Three density measurements 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 AccuPYKI I 1340 software.

[0166] The cured composite was then subjected to three density determinations. For one density determination, two cylindrical test specimens (h = 2 mm, D = 8 mm) of the composite were produced by curing (90 s on each side) using the HiLite Power light polymerization unit. The test specimen molds were filled to remove any air bubbles and covered from above and below with a slide during curing. After curing, the test specimens were demolded, deburred, cleaned with ethanol and dried with compressed air. Both test 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 AccuPYKI I 1340 software. The density was determined within 15-60 minutes after curing. The volume shrinkage (VS) as mean value (MW Vs) was calculated from the difference between the mean values ​​of the density of the composite before (MWpVA) and the mean value of the densities after curing (MWpNA) (Equation 4) .

[0167] MWpNA -MWpVA

[0168] Mean volume shrinkage MW V s 100%

[0169] MWpNA

[0170] (Equation 4)

[0171] Determination of the standard deviation of volume shrinkage SD V s was calculated according to equation 5 from the standard deviation SDp NA the density of the cured composite and the standard deviation SDpvA of the density of the uncured composite as well as the corresponding mean values ​​MWpNA and MWpVA.

[0172] SDys = 100 / MWp NA 2 x ( (MWp NA 2 x SDp VA 2 ) + (MWp VA 2 x SDp NA 2 ) ) (Equation 5)

[0173] Sales measurement

[0174] 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 -1 was detected.

[0175] For this purpose, the uncured, i.e., unpolymerized, composition or composite was placed in a cylindrical test specimen mold (D = 15 mm, h = 1.0 mm), covered with microscope slides from above and below, and then mounted on an IR holder. A spectrum with 12 scans was recorded. The uncured, i.e., unpolymerized composition or composite was then cured for 90 s from each side using the light-curing unit (Hi-Lite Power®; Heraeus Külzer). 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 IR software Omnic (Series 9.11.727; Thermo Scientific). -1 The conversion U in % is calculated from both integrals according to equation 6:

[0176] Conversion in % 100% Peak area Polymerized material x 100

[0177] Peak area of ​​unpolymerized material (Equation 6)

[0178] turbidity

[0179] Cylindrical test specimens (D = 15 mm, h = 1 mm) were produced from the composites using a metal test specimen mold. For this purpose, the test specimens were exposed from above and below for 90 s using a Hi-Lite Power exposure unit (Külzer). The color properties of the test specimens were then determined using a Konica Minolta CM-36dGV color spectrometer. The color properties were measured in the CIELAB and CIExyY color spaces. The CIELAB color space measures values ​​for L*, a* and b*. In the CIExyY color space, values ​​for brightness (Y) and chromaticity (xy) are determined. The turbidity (Contrast Ratio CR) is calculated from the values ​​measured for the test specimen against a standardized black background (Yb) and against a standardized white background (Yw) according to the following formula: Yb* 100% / Yw = turbidity. Completely translucent test specimens have a turbidity value of 0%, completely opaque test specimens have a value of 100%.

[0180] 3 . Preparation of radically polymerizable compounds

[0181] The following describes, by way of example, the syntheses and characterizations of various radically polymerizable compounds represented by a structure of formula 1 . Example 1

[0182] Synthesis of radically polymerizable compounds of a

[0183] Structure of Formula 24

[0184] In a 250 ml two-neck flask equipped with a magnetic stir bar, internal thermometer, and a 50 ml dropping funnel with a CaCl2 drying tube, 40 g of vestanate and 6 mg of BHT were dissolved in 25 ml of THF at room temperature (RT). A suspension of 7.64 g of 1,4-BDM in 35 ml of THF was added dropwise at RT via the dropping funnel. After the addition was complete, the dropping funnel was removed, 15 μl of catalyst solution was added, and the flask was sealed with a CaCl2 drying tube. The mixture reacted for 6 hours at 45°C and for 86 hours at room temperature. Subsequently, isocyanate groups were no longer detectable by FT-IR spectroscopy.

[0185] For workup, THF was largely removed using a rotary evaporator at 25 mbar and a water bath temperature of 40°C. Further removal of volatile components was carried out under fine vacuum. Yield: 46.5 g. Loss on drying (2 hours, 110°C): 0.92%. A compound of formula 24 (M+H+ = 792) was detected by HPLC-MS (Method 1) with a run time of 10.4 min.

[0186] NMR: 7.27 (s, 4H, arom. ) , 6.38 (d, 2H, acryl . ) , 6.08 (dd, 2H, acryl . ) , 5.79 (d, 2H, acryl.) , 5.01 (s, 4H) , 4.25 (br s, 8H) , 3, 08-2.85 (br, 8H), 1, 64-0, 87 (br, 28H) GPC: 1210 g / mol (Formula 24)

[0187] Example 2

[0188] Synthesis of radically polymerizable compounds of a

[0189] Structure of Formula 25

[0190] In the first synthesis step, 17.79 g of IPDI and 20 g of catalyst solution were placed in a 100 ml two-neck flask equipped with a magnetic stir bar, internal thermometer, a 25 ml dropping funnel with a stopper, and a reflux condenser with a CaCl2 drying tube. 11.77 g of 4-HOBA were added dropwise at room temperature via the dropping funnel. After the addition was complete, the mixture reacted for 4 hours at 40°C and 17 hours at room temperature. Subsequent NCO titration revealed a content of 10.65 wt. % NGO.

[0191] In the second synthesis step, the remaining NCO groups were reacted with 1,4-BDM. For this purpose, 10 μl of catalyst solution was added to the 26.96 g of crude product from the first synthesis step. A suspension of 4.72 g of 1,4-BDM in 39 ml of THF was prepared in a 50 ml dropping funnel and added dropwise to the crude product at room temperature. After the addition was complete, the mixture reacted for 4 hours at 50°C and for 17 hours at room temperature. The NCO content was determined by FT-IR spectroscopy and found to be <0.04 wt.%.

[0192] For workup, THF was largely removed using a rotary evaporator at 25 mbar and a water bath temperature of 40°C. Further removal of volatile components was carried out under fine vacuum. Yield: 31.6 g. Loss on drying (2 hours, 110°C): 1.94%. A compound of formula 25 (M+H+ = 872) was detected by HPLC-MS (Method 1) after a run time of 35.6 min.

[0193] NMR: 7.32 (s, 4H, arom. ) , 6.41 (d, 2H, acryl . ) , 6.09 (dd, 2H, acryl . ) , 5.81 (d, 2H, acryl.) , 5.06 (s, 4H) , 4.17 (t, 4H) , 4.06 (br, 4H) , 3.80 (br, 2H) , 2.91 (br, 4H) , 1.70-0, 86 (br,

[0194] 38H)

[0195] GPC: 1300 g / mol

[0196] (Formula 25)

[0197] Example 3

[0198] Synthesis of radically polymerizable compounds of a

[0199] Structure of Formula 26

[0200] In a 50 ml two-neck flask equipped with a magnetic stir bar, internal thermometer, and reflux condenser with a CaCl2 drying tube, 10.02 g of vestanate and 3 mg of BHT were dissolved in 15 ml of THF at RT, and 5 μl of catalyst solution were added. The mixture was homogenized at RT for 10 min. Then, 1.91 g of 1,2-BDM was added to the batch as a solid. The mixture reacted for 5 hours at 45°C and 18 hours at room temperature. To convert any remaining isocyanate groups, a further 0.14 g of 1,2-BDM and 5 μl of catalyst solution were added. After the addition, the mixture was stirred for 3 hours at 45°C and 20 hours at RT. Subsequently, isocyanate groups were no longer detectable by FT-IR spectroscopy.

[0201] A small sample was taken for analysis. THF was first evaporated in air at room temperature, then in an oven at 50°C.

[0202] Using HPLC-MS (Method 1), a compound of formula 26 (M+H+ = 792) was detected at a runtime of 33.3 min.

[0203] NMR: 7.32 (s, 2H, arom. ) , 7.25 (s, 2H, arom. ) , 6.37 (d, 2H, acryl . ) , 6.08 (dd, 2H, acryl . ) , 5.79 (d, 2H, acryl . ) , 5.12 (s, 4H) , 4.25 (br s, 8H) , 3, 08-2.86 (br, 8H) , 1, 64-0, 82 (br, 28H) GPC: 1020 g / mol

[0204] (Formula 26)

[0205] The bulk of the compound of formula 26 (9.39 g dissolved in 10.37 g THF) was treated with 9.32 g of TCDDA. The THF was largely removed using a rotary evaporator at 25 mbar and a water bath temperature of 40°C. Further removal of volatile components was carried out under medium vacuum. This yielded a 1:1 mixture of formula 26 with TCDDA.

[0206] Loss on drying (2 hours, 110°C): 0.65%

[0207] Example 4

[0208] Synthesis of radically polymerizable compounds of the structure of formula 27

[0209] Analogous to Example 3, 10.01 g of vestanate, 2 mg of BHT, 5 μl of catalyst solution, and 1.91 g of 1,3-BDM were first reacted for 5 h at 45 °C and 17 h at RT. A further 0.08 g of 1,3-BDM and 5 μl of catalyst solution were added to convert any remaining isocyanate groups. After the addition, the mixture was stirred for 5 hours at 45 °C and 16 hours at room temperature. Subsequently, isocyanate groups were no longer detectable by FT-IR spectroscopy. A small sample was taken for analysis. THF was first evaporated in air at room temperature and then in an oven at 50 °C.

[0210] Using HPLC-MS (Method 1) a compound of formula 27 (M+H+ = 792) was detected at a runtime of 33.0 min.

[0211] NMR: 7.31 (br, 4H, arom. ) , 6.42 (d, 2H, acryl . ) , 6.13 (dd, 2H, acryl . ) , 5.84 (d, 2H, acryl.) , 5.08 (s, 4H) , 4.29 (br s, 8H) , 3.14-2.86 (br, 8H) , 1.76-0, 87 (br, 28H)

[0212] GPC: 1140 g / mol

[0213] (Formula 27)

[0214] The bulk of the compound of formula 27 (10.72 g dissolved in 11.98 g THF) was treated with 10.74 g of TCDDA. The THF was largely removed using a rotary evaporator at 25 mbar and a water bath temperature of 40°C. Further removal of volatile components was carried out under medium vacuum. This yielded a 1:1 mixture of formula 27 with TCDDA.

[0215] Loss on drying (2 hours, 110°C): 0.5%

[0216] Example 5

[0217] Synthesis of radically polymerizable compounds of the structure of formula 28

[0218] A 100 ml two-necked flask equipped with a magnetic stir bar, internal thermometer, and a 50 ml dropping funnel with a CaCl2 drying tube was charged with 4.5 g of 9H-F-9,9-DM in 30 ml of THF. A solution of 14.4 g of vestanate in 30 ml of THF was added dropwise at room temperature via the dropping funnel. After the addition was complete, 10 μl of catalyst solution was added to the reaction mixture. The mixture reacted for 5 hours at 40°C and 17 hours at room temperature. To convert any remaining isocyanate groups, a further 0.51 g of 9H-F-9,9-DM and 10 μl of catalyst solution were added. The mixture was stirred for 4 hours at 40°C and 91 hours at room temperature. Subsequently, isocyanate groups were no longer detectable by FT-IR spectroscopy.

[0219] For workup, 5 mg of BHT was added to the mixture, and the tetrahydrofuran was largely removed using a rotary evaporator at 25 mbar and a water bath temperature of 40°C. Further removal of volatile components was performed under a fine vacuum.

[0220] Yield: 19.1 g Loss on drying (2 hours, 110°C): 0.84 % Using HPLC-MS (Method 2) a compound of formula 28 (M+Na + = 902) can be demonstrated.

[0221] NMR: 7.70 (d, 2H, arom. ) , 7.55 (br, 2H, arom. ) , 7.36 (t, 2H, arom. ) , 7.24 (t, 2H, arom.) , 6.38 (d, 2H, acryl . ) , 6.09 (dd, 2H, acryl.) , 5.79 (d, 2H, acrylic.) , 4.3 (br, 12H) , 3.09-2.83 (br, 8H) , 1, 61-0, 64 (br, 28H)

[0222] GPC: 1060 g / mol

[0223] (Formula 28)

[0224] Example 6 Synthesis of radically polymerizable compounds of a

[0225] Structure of Formula 29

[0226] Analogously to Example 5, 8.73 g of 4,4'-9FB2PE in 30 ml of THF were initially charged, and 14.4 g of vestanate in 30 ml of THF and 10 μl of catalyst solution were added. The reaction was carried out for 5 h at 40°C and 43 h at room temperature. To convert any remaining isocyanate groups, a further 3.2 g of 4,4'-9FB2PE and 10 μl of catalyst solution were added. After the addition, the mixture was stirred for 5 hours at 40°C and 19 hours at room temperature. Subsequently, isocyanate groups were no longer detectable by FT-IR spectroscopy.

[0227] For workup, 5 mg of BHT was added to the mixture, and THF was largely removed using a rotary evaporator at 25 mbar and a water bath temperature of 40°C. Further removal of volatile components was carried out under a fine vacuum.

[0228] Yield: 26.3 g Loss on drying (2 hours, 110°C): 0.80% Using HPLC-MS (Method 2) a compound of formula 29 (M+Na + = 1114) can be demonstrated.

[0229] NMR: 7, 69 (d, 2H, arom. ) , 7.30 (m, 4H, arom. ) , 7.19 (d, 2H, arom. ) , 7.05 (d, 4H, arom.) , 6.70 (d, 4h, arom.) , 6.37 (d, 2H, acryl . ) , 6.08 (dd, 2H, acrylic . ) , 5.78 (d, 2H, acrylic . ) , 4.26 (br, 12H) , 4.02-3.84 (m, 4H) , 3.09-2.77 (br, 8H) , 1, 63-0.81 (br, 28H)

[0230] GPC: 1080 g / mol

[0231] (Formula 29) Example 7

[0232] Synthesis of radically polymerizable compounds of a

[0233] Structure of Formula 30

[0234] Analogously to Example 6, 3.95 g of HQBIS (2HE)E were initially charged in 30 ml of THE, and 14.4 g of vestanate in 30 ml of THE and 10 μl of catalyst solution were added. The reaction was carried out for 5 h at 40 °C and 19 h at room temperature. To convert any remaining isocyanate groups, an additional 0.17 g of HQBIS (2HE)E and 2 x 10 μl of catalyst solution were added in two steps. The reaction was carried out for a further 4 h at 40 °C and 18 hours at room temperature. Subsequently, isocyanate groups were no longer detectable by FT-IR spectroscopy.

[0235] For workup, 5 mg of BHT was added to the mixture, and THF was largely removed using a rotary evaporator at 25 mbar and a water bath temperature of 40°C. Further removal of volatile components was carried out under a fine vacuum.

[0236] Yield: 20 g Loss on drying (2 hours, 110°C): 0.58% Using HPLC-MS (Method 2) a compound of formula 30 (M+Na += 873).

[0237] NMR: 6.78 (s, 4H, arom. ) , 6.38 (d, 2H, acryl . ) , 6.08 (dd, 2H, acryl . ) , 5.80 (d, 2H, acryl.) , 4.32-4.24 (br, 12H) , 4.04 (br s, 4H) , 3.10-2.80 (br, 8H) , 1.65-0.83 (br, 28H) GPC: 1270 g / mol

[0238] (Formula 30) It is understood that, starting from the isomers or isomer mixtures of the starting materials used, various isomeric structures are formed during the syntheses of the radically polymerizable compounds. However, the compounds obtained by the syntheses are generally not only the monomers with n = 1, but also the corresponding oligomeric compounds with n = 2-9, preferably 2-6.

[0239] 4 . Preparation and properties of polymerizable composition

[0240] Initiated monomer mixtures were prepared from the radically polymerizable compounds of Examples 1-2 and 5-7 by dilution with TCDDA and the addition of an initiator system based on camphorquinone (CQ) and 2-ethylhexyl p-(dimethylamino) benzoate (EHA) and characterized (Table 2). In Examples 3 and 4, the TCDDA used for dilution had already been added during preparation at a proportion of 50 wt. %. Otherwise, the initiated resins were prepared analogously. To prepare the radically polymerizable compositions, the individual components were mixed using a magnetic stirrer until a homogeneous composition was obtained.

[0241] Table 2: Composition in wt . -% , viscosity ( g ), flexural strength (BF) , elastic modulus (EM) , conversion (U) , volume shrinkage (VS) , refractive index uncured (n D VA) , refractive index cured (n DNA) of compositions according to the invention (Ex. AG) ​​containing the radically polymerizable compounds synthesized in Examples 1-7 and of a comparison composition (VB A).

[0242] Table 2: Continued.

[0243] The examples containing the radically polymerizable compounds from Examples 1 and 2 already show a significantly lower volume shrinkage than the BPA-containing comparative example. The difference in the refractive indices of the cured inventive examples AE and G compared to the dental glass used (n D = 1.53 ) is comparable to the difference between Comparative Example A and the same dental glass . Thus , similarly low levels of turbidity in the dental composites are obtained for Examples AE and G according to the invention , which lead to very good aesthetic product properties .

[0244] 5 . Production and properties of dental composites

[0245] Dental composites were produced using the compositions from Table 2, containing the radically polymerizable compounds from Examples 1 and 3-7, by adding 75 wt.% silanized dental glass (G018-053, d50=0.7pm; SCHOTT). The properties of the dental composites are shown in Table 3 below. Table 3: Composition in wt.%, turbidity, flexural strength (BF), Young's modulus (EM), conversion (U) and volume shrinkage (VS) of dental composites (Ex. HM) containing the radically polymerizable compounds synthesized in Examples 1 and 3-7 and the comparison composition B (VB B).

[0246] Table 3 : Continued

[0247] Examples H to M, in which the radically polymerizable compounds from Examples 1-7 were used, show a significantly lower volume shrinkage than Comparative Example B, in which a BPA-containing monomer mixture from the prior art was used. The flexural strengths of these dental composites are also comparatively higher. The turbidities, with the exception of Example L, the conversions and the E-modules of the examples according to the invention are comparable to those of Comparative Example B. The increased turbidity in Example L is explained by the significantly higher refractive index of the cured resin compared to glass. With the resin system used in this example, highly transparent composites can be produced in the cured state using dental fillers with even higher refractive index and more X-ray opaque.

[0248] 7 . Comparison with commercially available dental composites

[0249] For comparison, the properties of commercially available BPA-containing dental composites with a higher filler content, which are known in the prior art, are shown in Table 4. Despite the higher filler content, the shrinkage data for these composites are comparable to those of the inventive examples.

[0250] Table 4: Properties of commercially available dental composites known in the state of the art containing BPA-containing polymerizable compositions and 78.5 to 83 wt.% filler.

Claims

Patent claims 1 . A radically polymerizable compound represented by a structure of formula 1 : PG 1 -Sp 1 - [OC (O) NH-K-NHC (O) O-Ar ] n -OC (O) NH-K-NHC (O) O-Sp 2 -PG 2 ( Formula 1 ) , where PG 1 , PG 2 = each independently selected from a radically polymerizable group, preferably selected from (NR 1 ) OC-CR 2 =CH2 and OOC- CR 2 =CH2, more preferably selected from OOC-CR 2 =CH2, R 1 = selected from hydrogen, a Cl-C8 alkyl group, an aryl group and an araliphatic group with C6-C8 carbon atoms, preferably selected from a Cl-C8 alkyl group and a benzyl group, R 2 = selected from hydrogen, a Cl-C4 alkyl group, preferably selected from hydrogen and methyl; Sp 1 , Sp 2= each independently of one another a spacer group selected from unbranched and branched alkylene with Cl-Cl 9 carbon atoms, which may additionally contain oxygen, sulfur and / or -OOC- in the carbon chain; 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, wherein the moiety may be substituted with one or more aliphatic C1-C3 carbon substituents; Ar = -R 3 -BG-R 4 - , where BG = selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, 2,3-naphthylene, 2,6-naphthylene, 1,8-naphthylene, 9,1O-anthracenylene, 1,8-anthracenylene, 9,9-fluorenylene, 9,9-bis(phenyl-4-yl)fluorene and 4,4'-biphenylene, and R 3 , R 4 = each independently a spacer group selected from unbranched and branched alkylene with Cl-C6 carbon atoms, where the carbon atoms in the chain may be replaced by O, S or 0C (O); and n = 1 to 9, preferably 1 to 6. 2 . Radically polymerizable compound according to claim 1 , characterized in that the radically polymerizable compound is represented by a structure of formula 2 : CH2=CR 5 -COO-Sp 1 - [OC (O) NH-K-NHC (O) O-Ar ] n -OC (O) NH-K-NHC (O) O- Sp 2 -OOC-CR 6 =CH2 ( Formula 2 ) , where R5 , R 6 = each independently selected from hydrogen, a Cl-C4 alkyl group, preferably selected from hydrogen and methyl; Sp 1 , Sp 2 = each independently a spacer group selected from unbranched and branched alkylene with Cl-Cl 9 carbon atoms, which may additionally contain oxygen, sulfur and / or -OOC- in the carbon chain; 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, wherein the unit may be substituted with one or more aliphatic C1-C3 carbon substituents, or an aromatic or araliphatic unit having C6-C14 carbon atoms, preferably C6-C13 carbon atoms, wherein the unit may be substituted with one or more aliphatic C1-C3 carbon substituents; Ar = -R 3 -BG-R 4 -, where BG = selected from 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, 2,3-naphthylene, 2,6-naphthylene, 1,8-naphthylene, 9,1O-anthracenylene, 1,8-anthracenylene, 9,9-fluorenylene, 9,9-bis(phenyl-4-yl)fluorene and 4,4'-biphenylene, and R 3 , R 4= each independently of one another a spacer group selected from unbranched and branched alkylene having C1-C6 carbon atoms, where the carbon atoms in the chain may be replaced by O, S or OC(O); and n = 1 to 9, preferably 1 to 6.

3. Radically polymerizable compound according to claim 1 or 2, characterized in that Ar is selected from 9,9-bis-[(4-(ethoxy-2-yl)-phenyl]-fluorene, 1,3-bis(ethoxy-2-yl)benzene, 1,4-bis(ethoxy-2-yl)benzene, bis(ethan-2-yl)terephthalate, 1,2-dimethanediylbenzene, 1,3-dimethanediylbenzene, 1,4-dimethanediylbenzene, 9,10-dimethanediylanthracene, 4,4'-dimethanediylbiphenyl, 1,3- Di(pentane-3,3-diyl)benzene, 1,4-di(propane-2,2-diyl)benzene and 9,9-bis(methylene)fluorene.

4. Radically polymerizable compound according to one of claims 1 to 3, characterized in that Sp 1 and Sp 2are each independently selected from a C2-C6 alkylene group, preferably an unbranched C2-C6 alkylene group.

5. Radically polymerizable compound according to one of claims 1 to 4, characterized in that K is selected from the following structures of formulas 3 to 15: (orme) 6. Radically polymerizable compound according to one of the Claims 1 to 4, characterized in that K is selected from the following structures of formulas 3 to 6, 10 and 12 : (Formula 3) (Formula 4) (Formula 5) (Formula 6) (Formula 10) ( Formula 12 ) .

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 formulas 16 to 22: (Formula 20) ( Formula 22 ) , where n = each independently 1-9, preferably 1-6; and R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 = each independently selected from hydrogen and a methyl group.

8. A radically polymerizable composition comprising: a) a monomer mixture comprising: a1) one or more radically polymerizable compounds according to any one of claims 1 to 7, and a2) optionally one or more further radically polymerizable monomers and / or oligomers which do not fall under the at least one compound of formula 1; b) optionally at least one initiator or initiator system for the polymerization; c) optionally one or more stabilizers; d) optionally one or more fillers; e) optionally additives commonly used in dentistry.

9. Radically polymerizable composition according to claim 8, characterized in that several compounds of formula 1, selected from monomers (n = 1) and / or oligomers (n = 2-9), are present in the radically polymerizable composition.

10. Radically polymerizable composition according to claim 8 or 9, characterized in that the radically polymerizable composition contains one or more radically polymerizable compounds of formula 1 in a mass fraction of 0.1-100 wt.%, preferably 1-98 wt.%, more preferably 2-85 wt.%, even more preferably 2-65 wt.%, most preferably 10-65 wt.%, based on the total mass of all radically polymerizable monomers and oligomers of the polymerizable composition.

11. Radically polymerizable composition according to one of claims 8 to 10, characterized in that the monomer mixture comprises as a further radically polymerizable monomer a2) tricyclodecanedimethanol di(meth)acrylate and / or a compound represented by a structure selected from the formula 23: ( Formula 23 ) , where R 14 , R 15 = are each independently selected from hydrogen and a methyl group, and R 16 , R 17 = are each independently selected from - (OC2H4)pO- and - (OC3H7) pO- .

12. Radically polymerizable composition according to claim 11, characterized in that in the radically polymerizable composition, the compounds selected from tricyclodecanedimethanol di(meth)acrylate and / or compounds represented by a structure of formula 23 are present in a mass fraction of 20-90 wt.%, preferably 20-60 wt.%, more preferably 30-55 wt.%, based on the total mass of all radically polymerizable monomers and oligomers of the polymerizable composition.

13. Radically polymerizable composition according to one of claims 8 to 12, characterized in that the radically polymerizable composition is a radically polymerizable dental material.

14. Use of the radically polymerizable compound according to any one of claims 1 to 7 or the radically polymerizable composition according to one of claims 8 to 13 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, temporary crowns and bridges, crowns, bridges, restorations, orthodontic and / or prosthetic material.

15. Use according to claim 14, 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, gingival masks, tray materials, mouth guards and / or veneers are produced from the polymerizable dental material by means of 3D printing.

16. Cured dental material made from a polymerizable composition according to any one of claims 8 to 13.

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