DE29825066U1 - New urethane di(meth)acrylates of 1,3-bis(1-isocyanato-1-methylethyl)benzene useful as crosslinking agent - Google Patents

Abstract

Urethane di(meth)acrylate derivatives (I) of 1,3-bis(1-isocyanato-1-methylethyl)benzene are new. Urethane di(meth)acrylate derivatives of 1,3-bis(1-isocyanato-1-methylethyl)benzene of formula (I) are new. R : H or linear 1-8 C alkyl; X, Y : a group of formula (IIA), (IIB) or (IIC); R 1>, R 6>(un)substituted 6-12 C aryl, 7-16 C alkylaryl or 7-12 C arylalkyl; R 2>H, 1-5 C alkyl or (un)substituted 6-12 C aryl; R 3>, R 5>H or methyl; R 4>1-8 C alkylene, optionally with oxygen (-O-) atom(s) in the chain, or phenylene; T : carbonyl (-CO-) or a chemical bond; W : -O-, sulfur (-S-) or imino (-NR 7>-); R 7>H or linear 1-6 C alkyl; R 3> not : methyl if R : H and R 4>dimethylene. Independent claims are also included for compositions containing (I); and the preparation of (I).

Description

The present invention relates to Urethane di (meth) acrylate derivatives of 1,3-bis (1-isocyanato-1-methylethyl) benzene and dental materials based on these substances.

Urethane (meth) acrylates are used, among other things, as a component of adhesives, coatings and dental materials (R. Holman (ed.), UV and EB. Curing Formulation for Printing Inks, Coatings and Paints, SITA-Technology, London 1984, 27; JP Foussier, JF Rabek (ed.), Radiation curing in Polymer Science and Technology, vol. IV, Elsvier Applied Science, London and New York 1993, 387). A monomer which is used particularly frequently in the dental field is 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyldimethacrylate (UDMA) which is obtained by reacting one mole 2 , 2,4-Trimethylhexamethylene diisocyanate with two moles of 2-hydroxyethyl methacrylate (HEMA) is accessible (cf. e.g. DE 195 44 671 ).

However, the refractive index of UDMA with n _D = 1.483 differs significantly from the refractive index of conventional dental filler materials (approx. 1.52 to 1.55), so that UDMA and other aliphatic urethane dimethacrylates often adapt with Bis-GMA to adjust the refractive index to the filler , the addition product of methacrylic acid and bisphenol A diglycidyl ether (refractive index n _D = 1.549) can be combined (cf., for example, DE OS 24 11 760). The addition of Bis-BMA also improves the mechanical properties of the materials.

By aligning the refractive indices becomes a greater depth of hardening dental materials achieved in photopolymerization, however favored Bis-GMA due to the hydroxyl groups present the water absorption of the materials, resulting in decreased durability under moist Conditions. About that also contains Up to GMA often difficult to remove contaminants on bisphenol-A, the one pronounced estrogens Shows effect.

In addition to UDMA, the use of others Di (meth) acrylaturethane described. M. G. Buonocore and C.A. Casciani, New York State Dental Journal 35 (1969) 135, for example Addition products of two moles of HEMA and one mole of 2,4-tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, Naphthalene diisocyanate, diphenylmethane diisocyanate or hexane methylene diisocyanate. In all cases, these are crystalline compounds, which only work together with liquid Have monomers processed into dental materials.

US-A-4,400,159 discloses urethane diacrylates, by the implementation of aliphatic and aromatic diisocyanates can be obtained with 3-methacryloyl-2-hydroxypropyl esters. The substances but tend to discolor, and the aromatic derivatives are crystalline Links. These monomers are preferably combined with Bis-GMA.

The DE 195 44 671 A1 discloses urethane (meth) acrylates with cyclic carbonate groups, which are said to be distinguished by an increased rate of polymerization and a lower sensitivity to the inhibition of polymerization by oxygen.

US-A-4,952,241, EP 0 254 185 B1 , US-A-4,904,750 and EP 0 658 582 A1 disclose prepolymer (meth) acrylate derivatives which can be used above all as flexibilizing monomers or dilution monomers in combination with bis-GMA.

US-A-4,386,912 relates to dental filling materials based on tetrafunctional urethane acrylate monomers by reacting glycerol dimethacrylate with aromatic or Have aliphatic diisocyanates prepared. Aliphatic diisocyanates are in terms of coloring of the hardened Product preferred.

B. Nabeth, J.F. Gerard, J.P. Pascault, J. Appl. Polym. Sci. 60 (1996) 2113, describe the synthesis of Polyurethane (meth) acrylates based on polycaprolactone macrodiols using 1,3-bis (1-isocyanato-l-methylethyl) benzene (TMXDI). Low molecular weight urethane di (meth) acrylate derivatives based on TMXDI are not yet known.

The invention is based on the object flowable, polymerizable urethane di (meth) acrylate derivatives to provide their refractive index with the usual dental filling materials compatible, which do not tend to discoloration and the Bis-GMA can substitute in dental materials without the mechanical Deteriorate properties of materials.

in der R Wasserstoff oder ein geradkettiger C₁-C₈-Alkylrest, vorzugsweise Wasserstoff, Methyl, Ethyl, Propyl, Butyl oder Hexyl, ganz besonders bevorzugt Wasserstoff oder Methyl ist und X und Y unabhängig voneinanderThis object is achieved by urethane di (meth) acrylate derivatives of 1,3-bis (1-isocyanato-l-methylethyl) benzene according to formula (I)

in which R is hydrogen or a straight-chain C ₁ -C ₈ -alkyl radical, preferably hydrogen, methyl, ethyl, propyl, butyl or hexyl, very particularly preferably hydrogen or methyl and X and Y independently of one another

• R ^{1 is} a substituted or unsubstituted C ₆ to C ₁₂ aryl or C ₇ to C ₁₆ alkylaryl or C ₇ to C ₁₂ arylalkyl radical and R ^{2 is} hydrogen, a C ₁ to C ₅ alkyl or is a substituted or unsubstituted C 6 to C ₁₂ aryl; R ^{3 is} hydrogen or a methyl radical and R ^{4 is} a C ₁ to C ₈ alkylene radical which can be interrupted by oxygen atoms or is a phenylene radical; R ^{5 is} hydrogen or a methyl radical, R ^{6 is} a substituted or unsubstituted C ₆ to C ₁₂ aryl or C ₇ to C ₁₆ alkylaryl or C ₇ to C ₁₂ arylalkyl radical, Z -CO or a chemical bond and W is oxygen, sulfur or NR ', where R ^{7 is} hydrogen or a straight-chain C ₁ - to C ₆ -alkyl radical.

R and R ⁷ preferably have the same meaning.

The aromatic groups of both the aryl and the alkylaryl radicals can be substituted one or more times, preferably once. Preferred substituents are halogen, in particular bromine, -OCH ₃ , -OH, -CN, -CH ₃ , -C ₂ H ₅ , -NO ₂ , -COOH and - COOCH ₃ .

Preferred C ₇ to C ₁₂ arylalkyl radicals are benzyl, α-methylbenzyl, α, α-dimethylbenzyl and α, α-diethylbenzyl, in particular benzyl.

Independently selectable preferred Definitions are:

• R ^{1 is} hydrogen or -CH ₃ , R ² -CH ₃ , -C ₂ H ₅ , a benzyl or phenyl radical, R ^{3 is} hydrogen or a methyl radical, R ^{4 is} an ethylene, propylene, triethylene, butylene or phenylene radical, R ^{5 is} a methyl radical, R ^{6 is} a benzyl, phenyl or substituted phenyl radical, W is oxygen, sulfur or NH, Z -CO- or a chemical bond and / or R ^{7 is} hydrogen.

Very particularly preferred, independently of each other selectable Definitions are:

• R ^{1 is} hydrogen, R ^{2 is} hydrogen, a benzyl or phenyl radical, R ^{3 is} a methyl radical, R ^{4 is} an ethylene, triethylene or propylene radical, R ^{5 is} a methyl radical, R ^{6 is} a benzyl radical, W is oxygen, Z -CO- and / or R ^{7 is} hydrogen.

Such urethane di (meth) acrylate derivatives are also preferred, in which X and Y have the same meaning.

Particularly preferred urethane di (meth) acrylate derivatives are:

Furthermore, compounds according to formula I are particularly preferred in which R and R ^{3 are} independently hydrogen or methyl and R ^{4 is} ethylene or propylene.

The urethane di (meth) acrylate derivatives according to the invention of the formula (I) can be obtained by reacting commercially available 1,3-bis (1-isocyanate-1-methylethyl) benzene (TMXDI) with corresponding hydroxy (meth) acrylates X-OH or Y-OH and optionally subsequent alkylation of the adducts formed for example with a dialkyl sulfate.

in der R¹ und R² die oben angegebene Bedeutung haben. Beispielsweise läßt sich 2-Hydroxymethylacrylsäurebenzylester durch Umsetzung von Acrylsäurebenzylester mit Formaldehyd herstellen:The hydroxy (meth) acrylates X-OH and Y-OH can be prepared in a manner known per se (see, for example, C. Ferri, Reactions in Organic Synthesis, G. Thieme Verlag, Stuttgart 1978). The Baylis-Hillman reaction of acrylates with aldehydes catalyzed by tertiary amines is preferred according to the reaction equation

in which R ¹ and R ^{2 have} the meaning given above. For example, benzyl 2-hydroxymethylacrylate can be prepared by reacting benzyl acrylate with formaldehyde:

in der R³ und R⁴ die oben angegebene Bedeutung haben und U = Cl oder OH ist. Beispielsweise ist 4-Hydroxyphenylmethacrylat durch Umsetzung von Hydrochinon mit Methacrylsäurechlorid zugänglich:The non-stoichiometric esterification of dihydroxy compounds with (meth) acrylic acid or (meth) acrylic acid chloride according to the reaction equation is further preferred

in which R ³ and R ^{4 have} the meaning given above and U = Cl or OH. For example, 4-hydroxyphenyl methacrylate can be obtained by reacting hydroquinone with methacrylic acid chloride:

erfolgen, in der R⁵ und R⁶ die oben angegebene Bedeutung haben. Beispielsweise kann 1-Benzylcarbonyloxy-2-hydroxypropylmethacrylat durch Umsetzung von Phenylessigsäure mit Glycidylmethacrylat erhalten werden:In addition, the synthesis of suitable hydroxy (meth) acrylates by reacting glycidyl (meth) acrylate with O-nucleophilic reagents such as alcohols, phenols or carboxylic acids according to the reaction equation

take place in which R ⁵ and R ^{6 have} the meaning given above. For example, 1-benzylcarbonyloxy-2-hydroxypropyl methacrylate can be obtained by reacting phenylacetic acid with glycidyl methacrylate:

The urethane di (meth) acrylate derivatives according to the invention are particularly suitable for the production of polymers, adhesives and Dental materials, such as filling composites, dental adhesives and fastening cements, wherein the urethane di (meth) acrylates as Crosslinkers act.

Derivatives with a refractive index of n _D = 1.50 to 1.60, in particular 1.50 to 1.55, are preferred for producing dental materials.

The compounds of the invention are used for the polymerization with initiators for radical polymerization and, if necessary, additional ones radically polymerizable monomers and fillers and other auxiliaries mixed.

Suitable initiators are, for example in the Encyclopedia of Polymer Science and Engineering, Vol. 13, Wiley-Intersci. Pub., New York etc. 1988, pp. 754 ff. Preferred initiators for cold polymerization are azo compounds such as azo bis (isobutyronitrile) (AIBN) or azobis (4-cyanvaleric acid) or peroxides, such as dibenzoyl peroxide, Dilauroyl peroxide, tert-butyl peroctate, tert-butyl perbenzoate or di (tert-butyl) peroxide.

Particularly suitable initiators for hot curing are benzpinacol and 2,2'-di (C ₁ -C ₈ alkyl) benzpinacols.

Suitable photoiniators for the UV or visible area are described by J.P. Fouassier, J.F. Rabek (ed.), Radiation Curing in Polymer Science and Technology, Vol. II, Elsevier Applied Science, London and New York 1993, pages 155 to 237. Preferred photoinitiators are benzoin ethers, dialkyl benzil ketals, Dialkoxyacetophenones, acylphosphine oxides, α-diketones, such as 10-phenanthrenequinone, Diacetyl, furil, anisil, 4,4'-dichlorobenzil and 4,4'-dialkoxybenzil and camphor quinone.

For the production of dental materials dibenzoyl peroxide, camphorquinone or acylphosphine oxides are particularly suitable.

As an additional radically polymerizable Monomers are preferred, bifunctional crosslinking monomers, wherein for the production of adhesives or dental materials, especially cross-linking bifunctional or higher functional Acrylates and methacrylates, such as, for example, UDMA, di- or triethylene glycol di (meth) acrylate (TEGDMA), Decanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Butanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate and 1,12-dodecanediol di (meth) acrylate suitable. These monomers are by esterification of (meth) acrylic acid with corresponding diols accessible.

Organic and inorganic particles and fibers are suitable as fillers. Preferred inorganic fillers for the production of dental materials are amorphous, spherical materials based on mixed oxides of SiO ₂ , ZrO ₂ and / or TiO ₂ with an average average particle size of 0.005 to 2.0 μm, preferably 0.1 to 1 μm, as disclosed, for example, in DE-PS 32 47 800, microfine fillers, such as pyrogenic silica or precipitated silica, and macro or mini-fillers, such as quartz, glass ceramic or glass powder with an average particle size of 0.5 to 20 μm , and X-ray opaque fillers, such as ytterbium trifluoride. Mini-fillers are fillers with a particle size from 0.5 to 1.5 μm and macro fillers are fillers with a particle size of 10 to 20 μm.

In addition, glass, polyamide or Carbon fibers as fillers be used. Suitable reinforcing fibers are, for example in the "Paperback the plastic additives ", R. Gächter, H. Müller, Carl Hanser Verlag, Munich and Wien 1990, pages 617 to 662.

In addition, the compositions according to the invention if necessary, other auxiliaries such as solvents, especially water, Ethyl acetate or ethanol, stabilizers, UV absorbers, dyes, pigments and / or contain lubricants. Stabilizers include such Understand substances that prevent premature polymerization and above all the storage stability of monomer mixtures and Increase composites, without however affecting the properties of the cured materials. Preferred stabilizers are hydroquinone monomethyl ether (MEHQ) and 2,6-di-tert-butyl-4-methylphenol (BHT).

Dental materials preferably have the following composition:

• 1 to 99% by weight, preferably 10 to 80% by weight and particularly preferably 20 to 70% by weight of one or more urethane di (meth) acrylate derivatives, 0 to 80% by weight, preferably 0 to 60% by weight and particularly preferably 0 to 50% by weight of one or more other radically polysable monomers 0 to 90% by weight fillers and 0.01 to 5% by weight, preferably 0.01 to 2% by weight of an initiator for the radical polymerization.

The filler content is decisive determined by the intended use and is preferred in the case of adhesives 0 to 20% by weight, preferably 20 to 60% by weight for cements and filling composites 50 to 85% by weight.

The proportion of the other auxiliaries is usually in the range from 100 ppm to 1.0% by weight in the case of dyes and also pigments depending on the coloring ability in the range of 10 ppm to 1.0% by weight.

The dental materials according to the invention contain preferably no bis-GMA, but show mechanical properties, which correspond to those of bis-GMA-containing materials in every respect. The materials according to the invention exhibit under moist conditions significantly better mechanical properties than materials containing bis-GMA.

The urethane di (meth) acrylate derivatives according to the invention are suitable about it also for the production of other medical or technical, radically curing Adhesives, cements and composites such as surgical Bone cements, contact lenses, adhesives for optical parts, UV-curable Varnishes, coatings and coating materials as well as matrix resins for Composite materials.

The invention is explained below of embodiments explained further.

example 1

90,7 g (371 mmol) TMXDI wurden innerhalb von 30 Minuten zu 101,1 g (742 mmol) HEMA und 0,19 g Dibutylzinndilaurat (Metatin 812, Fa. Acima) getropft. Nach 36-stündigem Rühren bei 70°C war das Isocyanat vollständig abreagiert (Reaktionskontrolle mittels IR-Spektroskopie). Die Reaktionsmischung wurde mit 300 ml Methylenchlorid versetzt und zweimal mit je 200 ml 2N NaOH und dreimal mit je 100 ml Wasser gewaschen. Die Methylenchloridphase wurde mit Natriumsulfat getrocknet und das Lösungsmittel nach Zugabe von 80 mg Hydrochinonmonomethylether (MeHQ) am Rotationsverdampfer bei ca. 250 mbar abgedampft. Es wurden 169 g (88% Ausbeute) einer farblosen, hochviskosen Flüssigkeit (n_D ²⁵ 1,5120) mit einer Scherviskosität (23°C) von 860 Pa ·s erhalten.Synthesis of TMXUDEMA 1,3-bis (2-aza-1,1,9-trimethyl-3,8-dioxo-4,7-dioxa-9-decen-1-yl) benzene

90.7 g (371 mmol) of TMXDI were added dropwise to 101.1 g (742 mmol) of HEMA and 0.19 g of dibutyltin dilaurate (Metatin 812, Acima) within 30 minutes. After stirring for 36 hours at 70 ° C., the isocyanate had reacted completely (reaction control by means of IR spectroscopy). The reaction mixture was mixed with 300 ml of methylene chloride and washed twice with 200 ml of 2N NaOH and three times with 100 ml of water. The methylene chloride phase was dried with sodium sulfate and the solvent was evaporated off after adding 80 mg of hydroquinone monomethyl ether (MeHQ) on a rotary evaporator at about 250 mbar. 169 g (88% yield) of a colorless, highly viscous liquid (n _D ²⁵ 1.5120) with a shear viscosity (23 ° C.) of 860 Pa · s were obtained.

IR (film): 3361 (s), 2976 (s), 1714 (s), 1637 (m), 1504 (s), 1384 (s), 1174 (s), 1043 (m) and 944 (m) cm ^-1

¹ H NMR (400 MHz, CDCl ₃ ): 7.43 and 7.27 (m, 4 H, aromatic); 6.13 and 5.77 (2 s, 4 H, = CH ₂ ); 5, 29 (br, 2H, NH); 4.24 to 4.40 (br, 8 H, OCH ₂ CH ₂ O); 1.95 (s, 6H, = C-CH3) and 1.66 (s, 12H, CH ₃ ) ppm.

Example 2

55,0 g (225 mmol) TMXDI wurden innerhalb von 10 Minuten zu 68,3 g (450 mmol) 95%-igem Hydroxylpropylmethacrylat und 0,1 g Metatin 812 getropft. Nach 3-tägigem Rühren bei 60°C war das Isocyanat vollständig abreagiert (Reaktionskontrolle mittels IR-Spektroskopie). Die Reaktionsmischung wurde mit 200 ml Methylenchlorid versetzt und zweimal mit je 100 ml 2N NaOH und dreimal mit je 100 ml Wasser gewaschen. Die Methylenchloridphase wurde mit Natriumsulfat getrocknet und das Lösungsmittel nach Zugabe von 80 mg McHQ am Rotationsverdampfer bei ca. 250 mbar entfernt. Es wurden 106 g (88% Ausbeute) einer farblosen, hochviskosen Flüssigkeit (n_D ²⁵ = 1,5018) mit einer Scherviskosität (23°C) von 1665 Pa · s erhalten.Synthesis of TMXUDPMA 1,3-bis- (2-aza-1,1,5,9-tetramethyl-3,8-dioxo-4,7-dio xa-9-decene-1-yl) benzene

55.0 g (225 mmol) of TMXDI were added dropwise to 68.3 g (450 mmol) of 95% hydroxylpropyl methacrylate and 0.1 g of Metatin 812 within 10 minutes. After stirring for 3 days at 60 ° C., the isocyanate had reacted completely (reaction control by means of IR spectroscopy). The reaction mixture was mixed with 200 ml of methylene chloride and washed twice with 100 ml of 2N NaOH and three times with 100 ml of water. The methylene chloride phase was dried with sodium sulfate and the solvent was removed after adding 80 mg of McHQ on a rotary evaporator at about 250 mbar. 106 g (88% yield) of a colorless, highly viscous liquid (n _D ²⁵ = 1.5018) with a shear viscosity (23 ° C.) of 1665 Pa · s were obtained.

IR (film): 3366 (m), 2980 (s), 1719 (s), 1637 (m), 1521 (s), 1458 (s), 1296 (m), 1248 (s), 1172 (s) and 1088 (m) cm ^-1 .

¹ H NMR (400 MHz, CDCl ₃ ): 10.86 (br, 2 H, NH); 7.26 and 7.22 (m, 4 H aromatics); 6.22 and 5.69 (2 s, 4H, = CH ₂ ); 5.00 (m, *, OCH); 4.09 - 4.29 (m, *, OCH ₂ ); 1.93 (s, 6 H, = C-CH _3); 1.62 (s, 12 H, CH ₃ ) and 1.32 (d, *, CHCH ₃ ) ppm (with Σ * 0 12 H).

Example 3

composites based on TMXUDEMA and TMXUDPMA

In a planetary mixer (type LPM 2SP, from Linde), three composite pastes K-1 to K-3 with the in Table I compositions shown (all data in% by weight) and at 200 mbar for vented ten minutes.

The composition contains K-3 instead the urethane di (meth) acrylate derivatives according to the invention bis-GMA and serves as a comparative example.

To determine the mechanical properties test specimens were formed from the pastes (2 mm × 2 mm × 20 mm) and by exposure for 6 minutes with a dental radiation source (spectramat, Vivadent, λ = 400 bis 500 nm) cured. The polymerization shrinkage (ΔV) was determined from the difference of the gas-pynometic paste and Composite density calculated, the bending strength (BF), the bending modulus (BEM) were determined according to ISO standard 4049 (1988). For this, the Test specimen at 37 ° C for 24 hours dry or for Stored in water (WL) for 24 hours or 7 days or for 24 hours boiled in deionized water (K). The results of the investigations are summarized in Table II.

Claims (14)

Urethane di (meth) acrylate derivative of 1,3-bis (1-isocyanato-1-methylethyl) benzene according to formula (I)

in which R is hydrogen or a straight-chain C ₁ -C ₈ alkyl radical, X and Y are independent of one another

mean, where R ^{1 is} a substituted or unsubstituted C ₆ to C ₁₂ aryl, C ₇ to C ₁₆ alkylaryl or C ₇ to C ₁₂ arylalkyl radical, R ^{2 is} hydrogen, a C ₁ to C ₅ Alkyl or a substituted or unsubstituted C ₆ to C ₁₂ aryl radical, R ^{3 is} hydrogen or a methyl radical, R ^{4 is} a C ₁ to C ₈ alkylene radical which can be interrupted by oxygen atoms, or a phenylene radical, R ^{5 is} hydrogen or is a methyl radical, R ^{6 is} a substituted or unsubstituted C ₆ to C ₁₂ aryl, C ₇ to C ₁₆ alkylaryl or C ₇ to C ₁₂ arylalkyl radical, Z is -CO- or a chemical bond and W is oxygen , Sulfur or NR ⁷ , where R ^{7 is} hydrogen or a straight-chain C ₁ - to C ₆ -alkyl radical, with the proviso that R ^{3 is} not a methyl radical, when R is hydrogen and R ^{4 is} a dimethylene group. Urethane di (meth) acrylate derivative according to Claim 1, characterized in that X and Y are independent of one another

mean. Urethane di (meth) acrylate derivative according to claim 1 or 2, characterized in that the aryl groups by halogen, -OCH ₃ , -OH, -CN, -CH ₃ , -C ₂ H ₅ , -NO ₂ , -COOH and / or - COOCH ₃ are substituted one or more times. Urethane di (meth) acrylate derivative according to any one of claims 1 to 3, characterized in that X and Y are the same. Urethane di (meth) acrylate derivative according to one of Claims 1 to 4, characterized in that R is hydrogen, methyl, ethyl, propyl, butyl or hexyl, R ^{1 is} hydrogen or -CH ₃ , R ² -CH ₃ , -C ₂ H ₅ , a benzyl or phenyl radical, R ^{3 is} hydrogen or a methyl radical, R ^{4 is} an ethylene, propylene, triethylene, butylene or phenylene radical, R ^{5 is} a methyl radical, R ^{6 is} a benzyl, phenyl or substituted phenyl radical, W is oxygen, Is sulfur or NH, Z -CO- or a chemical bond and / or R ^{7 is} hydrogen. Urethane di (meth) acrylate derivative according to claim 5, characterized in that R ^{1 is} hydrogen, R ^{2 is} hydrogen, a benzyl or phenyl radical, R ^{3 is} a methyl radical, R ^{4 is} an ethylene, propylene or triethylene radical, R ^{5 is} a methyl radical, R ⁶ a benzyl radical, W is oxygen, Z -CO- and / or R ^{7 is} hydrogen. Composition containing a urethane di (meth) acrylate derivative according to one of claims 1 to 6. Composition according to claim 7, characterized in that she 1 up to 99% of one or more urethane di (meth) acrylate derivatives according to one of claims 1 to 6; 0 to 80% of one or more radically polymerizable monomers; 0 to 90% fillers; and 0.01 to 5% of an initiator for radical polymerization and optionally contains other auxiliary substances. Composition according to claim 8, characterized in that she 20 up to 70% of one or more urethane di (meth) acrylate derivatives according to one of claims 1 to 6; 0 to 80% of one or more radically polymerizable monomers; 0 to 85% fillers; and or 0.1 to 2% of an initiator for radical polymerization and optionally contains other auxiliary substances. Composition according to claim 8 or 9, characterized characterized that they as radically polymerizable monomers one or more bi- or more functional Acrylates and / or Contains methacrylates. Composition according to claim 10, characterized in that she 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyldimethacrylate, Di- or triethylene glycol di (meth) acrylate, decanediol di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,10-decanediol di (meth) acrylate and / or 1,12-dodecanediol di (meth) acrylate contains. Composition according to one of claims 8 to 11, characterized in that it is filled with amorphous spherical materials based on mixed oxides of SiO ₂ , ZrO ₂ and / or TiO ₂ , pyrogenic silica, precipitated silica, quartz, glass ceramic or glass powder and / or contains ytterbium fluoride. Composition according to one of Claims 8 to 12, characterized in that it contains azobis (isobutyronitrile), azobis (4-cyanvalerialic acid), dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroctoate, tert-butyl perbenzoate, di- (tert-butyl) as initiator -peroxide, benzpinacol, a 2, 2'-di (C ₁ -C ₈ -alkyl) benzpinacol, a benzoin ether, a dialkylbenzyl ketal, dialkoxyacetophenone, acylphosphine oxide, 9,10-phenanthrenequinone, diacetyl, furil, anisil, 4,4'- Contains dichlorobenzil, 4,4'-dialkoxybenzil and / or camphorquinone. Composition according to one of claims 8 to 13 for use as a dental material.