CA2256191A1 - Urethane di (meth) acrylate derivatives of 1,3-bis (1-isocyanato-1-methylethyl) benzene - Google Patents
Urethane di (meth) acrylate derivatives of 1,3-bis (1-isocyanato-1-methylethyl) benzene Download PDFInfo
- Publication number
- CA2256191A1 CA2256191A1 CA002256191A CA2256191A CA2256191A1 CA 2256191 A1 CA2256191 A1 CA 2256191A1 CA 002256191 A CA002256191 A CA 002256191A CA 2256191 A CA2256191 A CA 2256191A CA 2256191 A1 CA2256191 A1 CA 2256191A1
- Authority
- CA
- Canada
- Prior art keywords
- meth
- radical
- hydrogen
- urethane
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims abstract description 33
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- -1 C1-C8 alkyl radical Chemical class 0.000 claims abstract description 23
- 239000005548 dental material Substances 0.000 claims abstract description 15
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005864 Sulphur Substances 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 3
- YMEHWISYYMKMFO-WOMRJYOTSA-N methyl N-[(12E,15S)-15-[(4S)-4-(3-chlorophenyl)-2-oxopiperidin-1-yl]-9-oxo-8,17,19-triazatricyclo[14.2.1.02,7]nonadeca-1(18),2(7),3,5,12,16-hexaen-5-yl]carbamate Chemical compound COC(=O)Nc1ccc2-c3cnc([nH]3)[C@H](C\C=C\CCC(=O)Nc2c1)N1CC[C@@H](CC1=O)c1cccc(Cl)c1 YMEHWISYYMKMFO-WOMRJYOTSA-N 0.000 claims abstract 2
- 239000000945 filler Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004568 cement Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 claims description 3
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- XASAPYQVQBKMIN-UHFFFAOYSA-K ytterbium(iii) fluoride Chemical compound F[Yb](F)F XASAPYQVQBKMIN-UHFFFAOYSA-K 0.000 claims description 3
- XMAWUPHYEABFDR-UHFFFAOYSA-N 1,2-bis(4-chlorophenyl)ethane-1,2-dione Chemical compound C1=CC(Cl)=CC=C1C(=O)C(=O)C1=CC=C(Cl)C=C1 XMAWUPHYEABFDR-UHFFFAOYSA-N 0.000 claims description 2
- YNANGXWUZWWFKX-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethane-1,2-dione Chemical compound C1=CC(OC)=CC=C1C(=O)C(=O)C1=CC=C(OC)C=C1 YNANGXWUZWWFKX-UHFFFAOYSA-N 0.000 claims description 2
- PTZRYAAOQPNAKU-UHFFFAOYSA-N 2-[(1-carboxy-3-cyanobutyl)diazenyl]-4-cyanopentanoic acid Chemical compound N#CC(C)CC(C(O)=O)N=NC(C(O)=O)CC(C)C#N PTZRYAAOQPNAKU-UHFFFAOYSA-N 0.000 claims description 2
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 2
- UVEIBTOHNNCCPH-UHFFFAOYSA-N 5-[[6-(4-carboxypent-3-enoxycarbonylamino)-3,5,5-trimethylhexyl]carbamoyloxy]-2-methylpent-2-enoic acid Chemical compound CC(CCNC(=O)OCCC=C(C)C(=O)O)CC(C)(C)CNC(=O)OCCC=C(C)C(=O)O UVEIBTOHNNCCPH-UHFFFAOYSA-N 0.000 claims description 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002639 bone cement Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 239000002241 glass-ceramic Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000004922 lacquer Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- SXPUVBFQXJHYNS-UHFFFAOYSA-N α-furil Chemical compound C=1C=COC=1C(=O)C(=O)C1=CC=CO1 SXPUVBFQXJHYNS-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 claims 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 2
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 claims 1
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 claims 1
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- ZPSNFVVCGMSWID-UHFFFAOYSA-N 2-isocyanatopropan-2-ylbenzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1 ZPSNFVVCGMSWID-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 125000006519 CCH3 Chemical group 0.000 description 2
- 101150041968 CDC13 gene Proteins 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229960004337 hydroquinone Drugs 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000003847 radiation curing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PJMXUSNWBKGQEZ-UHFFFAOYSA-N (4-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(O)C=C1 PJMXUSNWBKGQEZ-UHFFFAOYSA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000005712 Baylis-Hillman reaction Methods 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- WCAXGMYIFWHRDA-UHFFFAOYSA-N [2-hydroxy-1-(2-phenylacetyl)oxypropyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C(O)C)OC(=O)CC1=CC=CC=C1 WCAXGMYIFWHRDA-UHFFFAOYSA-N 0.000 description 1
- UKMBKKFLJMFCSA-UHFFFAOYSA-N [3-hydroxy-2-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)OC(=O)C(C)=C UKMBKKFLJMFCSA-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- SVRKWNZMRCEGIX-UHFFFAOYSA-N benzyl 2-(hydroxymethyl)prop-2-enoate Chemical compound OCC(=C)C(=O)OCC1=CC=CC=C1 SVRKWNZMRCEGIX-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003479 dental cement Substances 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001076 estrogenic effect Effects 0.000 description 1
- MKVYSRNJLWTVIK-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical class CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O MKVYSRNJLWTVIK-UHFFFAOYSA-N 0.000 description 1
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- IPZIVCLZBFDXTA-UHFFFAOYSA-N ethyl n-prop-2-enoylcarbamate Chemical class CCOC(=O)NC(=O)C=C IPZIVCLZBFDXTA-UHFFFAOYSA-N 0.000 description 1
- 229960004279 formaldehyde Drugs 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- A61K6/893—Polyurethanes
Landscapes
- Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Veterinary Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Organic Chemistry (AREA)
- Epidemiology (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Dental Preparations (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Eyeglasses (AREA)
Abstract
The invention relates to urethane di(meth)acrylate derivatives of 1-3-bis(1-isocyanato-1-methylethyl)benzene according to Formula (I) in which R is hydrogen or a straight-chained C1-C8 alkyl radical;
X and Y independently of each other stand for
X and Y independently of each other stand for
Description
Urethane di{meth ~acrylate derivatives of 1,3-bis(1-isocyanato-1-methylethyl)benzene The present invention relates to urethane di(meth)acrylate derivatives of 1,3-bis(1-isocyanato-1-methylethyl)benzene and to dental materials on the basis of these substances.
Urethane (meth)acrylates find practical applications inter alia as a constituent of adhesives, coatings and dental materials (R.
Holman ( Pub . ) , U . V , and EB . Curing Formulation for Printing Inks , Coatings and Paints, SITA-Technology, London I984, 27; J.P.
rFOUSSier, J.F. Rabek (Pub.), Radiation Curing in Polymer Science and Technology, Vol. IV, Elsevier 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-diazahexadecan-1,16-diyldimethacrylate (UDMA) which is accessible by reaction of one mole of 2,2,4-trimethylhexa-methylene diisocyanate with two moles of 2-hydroxyethyl methacrylate (HEMA) {cf. e.g. DE 195 44 671).
However, the refractive index of UDMA, at no = 1.483, is clearly different from the refractive index of customary dental filling materials (ca. 1.52 to 1.55), so that UDMA and other aliphatic urethane dimethacrylates are frequently combined with bis-GMA, the addition product of methacrylic acid and bisphenol-A-diglycidyl ether (refractive index no - 1.549) to match the refractive index to the filler (cf. e.g. DE OS 24 11 760). The mechanical properties of the materials can also be improved by the addition of bis-BMA.
Through the matching of the refractive indices, a greater through-curing depth of the dental materials upon photopoly-merization is achieved, but, because of the hydroxyl groups present, bis-GMA encourages the water absorption of the materials, which leads to a reduced durability under moist conditions. Moreover, bis-GMA .frequently contains impurities, which are hard to remove, of bisphenol-A which has a pronounced oestrogenic action.
In addition to UDMA, the use of other di(meth)acrylate urethanes has been described. M.G. Buonocore and C.A. Casciani, New York State Dental Journal 35 ( 1969 ) 135, describe for example addition products of two moles of HEMA and one mole each of 2,4-toluylene diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate or hexanemethylene diisocyanate. These are a11 crystalline compounds which can be processed to dental materials only together with liquid monomers.
US-A-4,400,159 discloses urethane diacrylates which are obtained by reaction of aliphatic and aromatic diisocyanates with 3-methacrylol-2-hydroxypropyl esters. However, the substances tend to become discoloured, and the aromatic derivatives are crystal-line compounds . These monomers are preferably combined with bis-GMA.
DE 195 44 671 A1 discloses urethane (meth)acrylates with cyclic carbonate groups which are said to show an increased speed of polymerization and a lower sensitivity to polymerization inhibition by oxygen.
Urethane (meth)acrylates find practical applications inter alia as a constituent of adhesives, coatings and dental materials (R.
Holman ( Pub . ) , U . V , and EB . Curing Formulation for Printing Inks , Coatings and Paints, SITA-Technology, London I984, 27; J.P.
rFOUSSier, J.F. Rabek (Pub.), Radiation Curing in Polymer Science and Technology, Vol. IV, Elsevier 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-diazahexadecan-1,16-diyldimethacrylate (UDMA) which is accessible by reaction of one mole of 2,2,4-trimethylhexa-methylene diisocyanate with two moles of 2-hydroxyethyl methacrylate (HEMA) {cf. e.g. DE 195 44 671).
However, the refractive index of UDMA, at no = 1.483, is clearly different from the refractive index of customary dental filling materials (ca. 1.52 to 1.55), so that UDMA and other aliphatic urethane dimethacrylates are frequently combined with bis-GMA, the addition product of methacrylic acid and bisphenol-A-diglycidyl ether (refractive index no - 1.549) to match the refractive index to the filler (cf. e.g. DE OS 24 11 760). The mechanical properties of the materials can also be improved by the addition of bis-BMA.
Through the matching of the refractive indices, a greater through-curing depth of the dental materials upon photopoly-merization is achieved, but, because of the hydroxyl groups present, bis-GMA encourages the water absorption of the materials, which leads to a reduced durability under moist conditions. Moreover, bis-GMA .frequently contains impurities, which are hard to remove, of bisphenol-A which has a pronounced oestrogenic action.
In addition to UDMA, the use of other di(meth)acrylate urethanes has been described. M.G. Buonocore and C.A. Casciani, New York State Dental Journal 35 ( 1969 ) 135, describe for example addition products of two moles of HEMA and one mole each of 2,4-toluylene diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate or hexanemethylene diisocyanate. These are a11 crystalline compounds which can be processed to dental materials only together with liquid monomers.
US-A-4,400,159 discloses urethane diacrylates which are obtained by reaction of aliphatic and aromatic diisocyanates with 3-methacrylol-2-hydroxypropyl esters. However, the substances tend to become discoloured, and the aromatic derivatives are crystal-line compounds . These monomers are preferably combined with bis-GMA.
DE 195 44 671 A1 discloses urethane (meth)acrylates with cyclic carbonate groups which are said to show an increased speed of polymerization and a lower sensitivity to polymerization inhibition by oxygen.
US-A-4,952,241, EP O 254 185 B1, US-A-4,904,750 and EP 0 658 582 A1 disclose prepolymeric (meth)acryl urethane 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 on the basis of tetrafunctional urethane acrylate monomers, which can be prepared by reaction of glycerol dimethacrylate with aromatic or aliphatic diisocyanates. Aliphatic diisocyanates are preferred as regards the coloration of the cured product.
B. Nabeth, J.F. Gerard, J.P. Pascault, J. Appl. Polym. Sci. 60 (1996) 2113, describe the synthesis of polyurethane (meth)-acrylates on the basis of polycaprolactone macrodiols using 1,3-bis(1-isocyanato-1-methylethyl)benzene (TMXDI). Low-molecular-weight urethane di(methacrylate) derivatives on the basis of TMXDI are not known at present.
The object of the invention is to prepare urethane di(meth)-acrylate derivatives capable of flowing and capable of poly-merization, whose refractive index is compatible with that of customary dental filling materials, which do not to tend towards discolorations and which can replace bis-GMA in dental materials without impairing the mechanical properties of the materials.
This object is achieved by urethane di(meth)acrylate derivatives of 1,3-bis(1-isocyanato-1-methylethyl)benzene according to Formula (I), R R
N N~O~X
O ' ' ~ '~O
in which R is hydrogen or a straight-chained C1-C8 alkyl radical, preferably hydrogen, methyl, ethyl, propyl, butyl or hexyl, quite particularly preferably hydrogen or methyl and X and Y independently of each other stand for -HC~R -R4 O-OC
~r g ~ RO-OC R
E R-Z-W-C H2- i H-C H2-O-OC
~r SR
preferably -HC~R or -R4 0-OC
RO-OC . R
in which R1 is a substituted or unsubstituted C6- to C12- aryl or C~-to C16- alkyl aryl or C~- to C1z- aryl alkyl radical and RZ is hydrogen, a C1- to CS- alkyl or a substituted or unsub-stituted C6- to C12- aryl radical;
R3 is hydrogen or a methyl radical and R4 is a C1- to C8- alkylene radical which can be interrupted by oxygen atoms, or is a phenylene radical;
RS is hydrogen or a methyl radical, R6 is a substituted or unsubstituted C6- to C12- aryl or C~-to C16- alkyl aryl or C~- to C1z- aryl alkyl radical, Z is -CO- or a chemical bond and W stands for oxygen, sulphur or NR', whereby R' is hydrogen or a straight-chained C1- to C6- alkyl rad-ical.
US-A-4,386,912 relates to dental filling materials on the basis of tetrafunctional urethane acrylate monomers, which can be prepared by reaction of glycerol dimethacrylate with aromatic or aliphatic diisocyanates. Aliphatic diisocyanates are preferred as regards the coloration of the cured product.
B. Nabeth, J.F. Gerard, J.P. Pascault, J. Appl. Polym. Sci. 60 (1996) 2113, describe the synthesis of polyurethane (meth)-acrylates on the basis of polycaprolactone macrodiols using 1,3-bis(1-isocyanato-1-methylethyl)benzene (TMXDI). Low-molecular-weight urethane di(methacrylate) derivatives on the basis of TMXDI are not known at present.
The object of the invention is to prepare urethane di(meth)-acrylate derivatives capable of flowing and capable of poly-merization, whose refractive index is compatible with that of customary dental filling materials, which do not to tend towards discolorations and which can replace bis-GMA in dental materials without impairing the mechanical properties of the materials.
This object is achieved by urethane di(meth)acrylate derivatives of 1,3-bis(1-isocyanato-1-methylethyl)benzene according to Formula (I), R R
N N~O~X
O ' ' ~ '~O
in which R is hydrogen or a straight-chained C1-C8 alkyl radical, preferably hydrogen, methyl, ethyl, propyl, butyl or hexyl, quite particularly preferably hydrogen or methyl and X and Y independently of each other stand for -HC~R -R4 O-OC
~r g ~ RO-OC R
E R-Z-W-C H2- i H-C H2-O-OC
~r SR
preferably -HC~R or -R4 0-OC
RO-OC . R
in which R1 is a substituted or unsubstituted C6- to C12- aryl or C~-to C16- alkyl aryl or C~- to C1z- aryl alkyl radical and RZ is hydrogen, a C1- to CS- alkyl or a substituted or unsub-stituted C6- to C12- aryl radical;
R3 is hydrogen or a methyl radical and R4 is a C1- to C8- alkylene radical which can be interrupted by oxygen atoms, or is a phenylene radical;
RS is hydrogen or a methyl radical, R6 is a substituted or unsubstituted C6- to C12- aryl or C~-to C16- alkyl aryl or C~- to C1z- aryl alkyl radical, Z is -CO- or a chemical bond and W stands for oxygen, sulphur or NR', whereby R' is hydrogen or a straight-chained C1- to C6- alkyl rad-ical.
R and R' preferably have the same meaning.
The aromatic groups both of the aryl and of the alkyl aryl radicals can be singly or repeatedly, preferably singly, substituted. Preferred substituents are halogen, in particular bromine, -OCH3, -OH, -CN, -CH3, -C2H5, -N02, -COOH and -COOCH3.
Preferred C~- to C12- aryl alkyl radicals are benzyl, oc methyl benzyl, ~,cx-dimethylbenzyl and ~c,oc-diethylbenzyl, in particular benzyl.
Preferred definitions which can be chosen independently of one another are:
R1 hydrogen or -CH3, R2 -CH3, -C2H5, a benzyl or phenyl radical, R3 hydrogen or a methyl radical, R4 an ethylene, propylene, triethylene, butylene or phenylene radical, RS a methyl radical, R6 a benzyl, phenyl or substituted phenyl radical, W oxygen, sulphur or NH, Z -CO- or a chemical bond and/or R' hydrogen.
Quite particularly preferred definitions which can be chosen independently of each other are:
R1 hydrogen, R2 hydrogen, a benzyl or phenyl radical, R3 a methyl radical, R4 an ethylene, triethylene or propylene radical, RS a methyl radical, R6 a benzyl radical, W oxygen, Z -CO- and/or R' hydrogen.
_ Furthermore, urethane di(meth)acrylate derivatives in which X and Y have the same meaning are preferred.
Particularly preferred urethane di(meth)acrylate derivatives are:
10 /O O HN ~ NH O O
O ~ . ~ O
~O O HN ~ NH O O~
O ~ O
O O HN ~ NH O O
O ~ ~ O O
O H ~ NH O
a O ~ ~ O
I
O O HN ~ NH O
O
O O
O HN ~ NH O
O
O
O O HN ~ NH
.o ~~~~N~
Br . Br II n II
O HN%~NH 0~~
is ~~ ~~' Y Y
o i n i o N/~\ / \N1i 0~
20 ~ o 0' 'HN /~~NH' /0\ ~Q
zs O
p I ~ O
O N O N
O~ ~ O
O O
O
O
HN NH O O
_ $ _ o ~ O
O\ /HN NH\ 'O
O
O O
co-o o-oc HC-0 HN ~ NH O-CH
CH2 ~ ~ Cf-;2 O O O O
C O-O . o--OC
Hz C H2 HC-0 H ~ NH O-CH
C H2 ~ ~ ~ C HZ
H-N O ~ N-H
co-o a-oc ~H2 CH2 HC-O HN ~ NH ~O-CH
a CH2 ~ ~ ~ CH2 S S
- 9 _ H2 C Hz HC-0 HN ~ NH O-CH
v CH2 ~ ~ ~ CH2 D O O
C 0-0 . 0-OC
Hz C H2 HC-0 HN ~ NH O-CH
CHz ~ ~ ~ ~ CHZ
O O
i i o c=0 0=c C 0-0 Q-.OC
~H2 ~ CH2 02N CH2 ~ ~ ,~ ~ CH2 N02 ~ O O
2 5 ~ ~=0 O=C
c o-0 o-oc ~Hz ~ CH2 w/
C H2 ~ ~~ ~ C H2 D O O
C H2--C=O O=C-C HZ
Furthermore, compounds according to Formula I in which R and R3, independently of each other, are hydrogen or methyl and R4 is ethylene or propylene are particularly preferred.
The urethane di(meth)acrylate derivatives according to the invention of formula (I) can be prepared by reaction of com mercial 1,3-bis(1-isocyanato-1-methylethyl)benzene (TMXDI) with corresponding hydroxy(meth)acrylates X-OH or Y-OH and optionally subsequent alkylation of the formed adducts for example with a dialkyl sulphate.
1.) X-OH O N ~ N O, O=C= N=C=O ~~' \ 2.} Y-OH
TMXDI - H2S04 ' (RO)S02 r R
~O~N . N~O~X
IO I IO
The preparation of the hydroxy(meth)acrylates X-OH and Y-OH can take place in a manner known per se (cf. e.g. C. Ferri, Reaktionen der organischen Synthese (Organic Synthesis Reac-tions], G. Thieme Verlag, Stuttgart 1978). The Baylis-Hillman reaction, catalysed by tertiary amines, of acrylates with aldehydes according to the reaction equation ~ + 2R-C ~O ~ OH-HC~
'Rp-OC ~H
~ R O-OC
in which Rl and RZ have the meaning given above, is preferred.
For example, 2-hydroxymethyl acrylic acid benzyl ester can be prepared by reaction of acrylic acid benzyl ester with formal-dehyde:
Concrete example:
C H2-O-OC~ O C H2-O-OC
Further preferred is the unstoichiometric esterification of dihydroxy compounds with (meth)acrylic acid or (meth)acrylic acid chloride according to the reaction equation - U H H O-R4 o-oc HO-R-OH +
sR sR
(U: CI or OH) in which R3 and R4 have the meaning given above and U = C1 or is OH. For example, 4-hydroxyphenyl methacrylate is accessible by reaction of hydroquinone with methacrylic acid chloride:
Concrete example:
O H + C F-OC _~ H 0-OC
Moreover, the synthesis of suitable hydroxy(meth)acrylates can take place by reaction of glycidyl {meth)acrylate with O-nucleophilic reagents, such as alcohols, phenols or carboxylic acids according to the reaction equation 6 R-Z-O-H + C \2 C H-C H2-O-OC
O
R
. O.H
R
in which R5 and R6 have the meaning given above. For example, 1-benzylcarbonyloxy-2-hydroxypropyl methacrylate can be obtained by reaction of phenylacetic acid with glycidyl methacrylate:
Concrete example:
2 0 O C HZ-C O-OH + C \2 C H-C H2-O-OC
O
r OH
HsC
The urethane di(meth)acrylate derivatives according to the invention are suitable in particular for the production of polymers, adhesives and dental materials, such as filling composites, dental adhesives and fixing cements, with the urethane di(meth)acrylates acting as crosslinkers.
Derivatives with a refractive index of no - 1.50 to 1.60, in particular 1.50 to 1.55, are preferred for the production of dental materials.
For the polymerization, the compounds according to the invention are mixed with initiators for radical polymerization and optionally additional radically polymerizable monomers and fillers plus other auxiliaries.
Suitable initiators are described for example in the Encyclopedia of Polymer Science and Technology, Vol . 13, Wiley-Intersci . Pub . , New York etc. 1988, p. 754 et seq. Preferred initiators for cold polymerization are azo compounds such as azobis(isobutyronitrile) (AIBN) or azobis(4-cyanovaleric acid) or peroxides, such as dibenzoyl peroxide, dilauroyl peroxide, tert.-butyl peroctoate, tert.-butyl perbenzoate or di-(tert.-butyl) peroxide.
Benzpinacol and 2,2'-Di(C1-C8-alkyl)benzpinacols in particular are suitable as initiators for hot curing.
Suitable photoinitiators for the UV or visible range are described by J.P. Foussier, J.F. Rabek (Pub.), 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, acylphosphinic oxides, oc-diketones, such as 10-phenanthrenequinone, diacetyl, furil, anisil, 4,4'-dichlorobenzil and 4,4'-dialkoxybenzil and camphor quinone.
Dibenzoyl peroxide, camphor quinone or acylphosphinic oxides are particularly suitable for the production of dental materials.
Difunctional crosslinker monomers are preferred as additional radically polymerizable monomers, with crosslinking bi- or higher-functional acrylates and methacrylates, such as for example UDMA, di- or triethylene glycol di(meth)acrylate (TEGDMA), decanediol di(meth)acrylate, trimethylol propane tri(meth)-acrylate, pentaerythritol tetra(meth)acrylate, butanediol (di)-methacrylate, 1,10-decanediol di(meth)acrylate diol di(meth)acrylate above a11 being suitable for producing adhesives or dental materials. These monomers are accessible by esterification of (meth)acrylic acid with suitable diols.
Organic as well as inorganic particles and fibres are suitable as fillers. Preferred inorganic fillers for producing dental materials are amorphous, spherical materials on the basis of mixed oxides from Si02, Zr02 and/or TiOz with an average particle size of 0.005 to 2.0 um, preferably of 0.1 to 1 Vim, as are disclosed for example in DE-PS 32 47 800, microfine fillers, such as pyrogenic silica or precipitation silica, as well as macro-or mini-fillers, such as quartz, glass ceramic or glass powder with an average particle size of 0.5 to 20 um, as well as X-ray-opaque fillers, such as ytterbium trifluoride. The term mini-fillers is taken to mean fillers with a particle size of 0.5 to 1.5 Vim, and the term macro-fillers to mean fillers with a particle size of 10 to 20 um.
Glass, polyamide or carbon fibres can also be used as fillers.
Suitable reinforcing fibres are described for example in the "Taschenbuch der Kunststoff-Additive", R. Gachter, H. Miiller, Carl Hanser Verlag, Munich and Vienna 1990, pages 617 to 662.
The compositions according to the invention can also if needed contain other auxiliaries such as solvents, in particular water, ethyl acetate or ethanol, stabilizers, W absorbers, dyestuffs, pigments and/or slip agents. The term stabilizers is taken to mean substances which prevent premature polymerization and thus above a11 increase the storage stability of monomer mixtures and composites without however impairing 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 wt.-~, preferably 10 to 80 wt.-~ and particularly preferably 20 to 70 wt.-~s of one or more urethane di(meth)acrylates, 0 to 80 wt.-$, preferably 0 to 60 wt.-~ and particularly preferably 0 to 50 wt.-~ of one or more other radically polymerizable monomers, 0 to 90 wt.-$ fillers and 0.01 to 5 wt.-$, preferably 0.01 to 2 wt.-$ of an initiator fox radical polymerization.
The filler content is crucially determined by the intended use and is preferably 0 to 20 wt.-$ in the case of adhesives, preferably 20 to 60 wt.-~ in the case of cements and 50 to 85 wt.-~ in the case of filling composites.
The proportion of the other auxiliaries usually lies in the range from 100 ppm to 1.0 wt.-~ in each case, and in the case of dyestuffs and pigments, depending on colouring capacity, also in the range from 10 ppm up to 1.0 wt.-~.
The dental materials according to the invention preferably contain no bis-GMA, but have mechanical properties which correspond in every respect to those of materials containing bis-GMA. Under moist conditions, the materials according to the invention display clearly better mechanical properties than the materials containing bis-GMA.
The urethane di(meth)acrylate derivatives according to the invention are moreover also suitable for the production of other medical or technical, radically curing adhesives, cements and composites, such as for example surgical bone cements, contact lenses, adhesives for optical parts, UV-curable lacquers, coatings and covering materials and also matrix resins for composite materials.
The invention is explained in more detail in the following with reference to embodiments.
Example 1 Synthesis of TMXUDEMA
1,3-bis-(2-aza-1,1,9-trimethyl-3;8-dioxo-4,7-dioxa-9-decen-1-yl)-benzene O O
o~o~rrH ~ rrH~o~o w I
o ~ ~ o TMXUDEMA
90.7 g (371 mmol) of TMXDI were added dropwise within 30 minutes to 101.1 g (742 mmol) of HEMA and 0.19 g of dibutyltin dilaurate (Metatin 812, Acima). After 36 hours' stirring at 70~C the iso-cyanate had completely reacted off (reaction monitoring by means of IR spectroscopy) . 300 ml of methylene chloride were added and the reaction mixture washed twice with 200 ml of NaOH each time and three times with l00 ml of water each time. The methylene chloride phase was dried with sodium sulphate and the solvent evaporated off, after the addition of 80 mg of hydro-quinone monomethyl ether (MEHQ), at the rotation evaporator at ca. 250 mbar. 169 g (88o yield) of a colourless, highly viscous liquid (nozs - 1.5120) with a shearing 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.
1H-NMR ( 400 MHz, CDC13 ) : 7 . 43 and 7 . 27 (m, 4H, aromatic ) ; 6 . 13 and 5.77 (2 s, 4 H, =CHZ); 5.29 (br, 2 H, NH); 4.24-4.40 (br, 8 H, OCHZCH20 ) ; 1. 9 5 ( s , 6H =C-CH3 ) and 1 . 6 6 ( s , 12 H, CH3 ) ppm .
Example 2 Synthesis of TMXUDPMA
1,3-bis-(2-aza-1,1,5,9-tetramethyl-3,8-dioxo-4,7-dioxa-9-decen-1-yl)-benzene O
O ~ ~O \
O NH ~ ~ ,~NH O
O \ O
TMXUDPMA
55.0 g (225 mmol) of TMXDI were added dropwise within 10 minutes to 68.3 g (450 mmol) of 95% hydroxypropyl methacrylate and 0.1 g of Metatin 812. After 3 days' stirring at 60~C the isocyanate had completely reacted off (reaction monitoring by means of IR
spectroscopy). The reaction mixture was reacted with 200 ml of methylene chloride and washed twice with 100 ml of NaOH each time and three times with 100 ml of water each time. The methylene chloride phase was dried with sodium sulphate and the solvent evaporated off, after the addition of 80 mg of MEHQ, at the rotation evaporator at ca. 250 mbar. 106 g (88% yield) of a colourless, highly viscous liquid (no25 = 1.50l8) with a shearing 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.
1H-NMR (400 MHz, CDC13): 10.86 (br, 2 H, NH); 7.26 and 7.22 (m, 4H, aromatic); 6.22 and 5.69 (2 s, 4 H, =CH2); 5.00 (m, ', OCH);
4.09 - 4.29 (m, ', OCHZ); 1.93 (s, 6 H =C-CH3); 1.62 (s, 12 H, CH3) and 1.32 (d, ', CHC~) ppm (with E' 0 12 H) .
Example 3 Composites on the basis. of TMKUDEMA and TMXUDPMA
Three composite pastes K-1 to K-3 with the compositions shown in Table I (all figures in wt.-$) were prepared in a planetary kneader (type LPM 2SP, Linde) and deaerated at 200 mbar for ten minutes.
Composition K-3 contains bis-GMT instead of the urethane di(meth)acrylate derivatives according to the invention and serves as a comparative example.
To determine the mechanical properties, testpieces (2 mm x 2 mm x 20 mm) were formed from the pastes and cured by 6 minutes' exposure to light with a dental radiation source (Spektramat, Vivadent, ~, = 400 to 500 nm). The polymerization shrinkage (AV) was calculated from the difference between the paste and composite densities determined by gas pyknometry, and the bending strength (BS), the bending E-modulus (BEM) were determined according to ISO standard 4049 (1988). For this, the testpieces were stored dry at 37~C for 24 hours or for 24 hours or 7 days in water (WS) or boiled for 24 hours in deionized water (B). The results of the studies are listed in Table II.
Table I
Composition of the composite pastes (wt.-%) Com onent K-1 K-2 K-3a~
TMXUDEMA 7.59 - -TMXUDPMA - 7.59 -bis-GMA - - 7.59 UDMA 6.72 6.72 6.72 TEGDMA 3.64 3.64 3.64 Ytterbium fluoride 14.89 14.89 14.89 Rhone-Poulenc Barium glass b' 51.61 51.61 51.61 Spharosil ~ c 14.39 14.39 l4.39 AEROSIL ~ OX-50 d~ 1.00 1.00 1.00 Hydroquinone meth 1 ether 0.02 0.02 0.02 Camphor uinone 0.05 0.05 0.05 N-(2-cyanoethyl-N-methyl- 0.09 0.09 0.09 aniline a) comparative example b) silanized barium aluminium silicate glass powder (Schott), proportion with a grain size < 7 Vim: 99%
c) Si02-Zr02 mixed oxide (Tokoyama Soda), secondary grain size < 7~m d) silanized pyrolysis silica (Degussa) Table II
Mechanical properties of the cured composite materials Pro ert K-1 K-2 K-3a~
~V vol.-~ -2.9 -2.8 -2.8 BS, d MPa 141 120 116 BS, 24 h WS MPa 153 145 140 BS, 7 d WS MPa 147 144 121 BS, 24 h B MPa 143 129 l23 I BEM, dr GPa 13.14 13.62 12.13 BEM, 24 h WS GPa 12.40 12.56 l1.44 BEM, 7 d WS GPa 12.58 11.66 11.63 BEM, 24 h B GPa 12.92 1l.52 10.56 a) Comparative example
The aromatic groups both of the aryl and of the alkyl aryl radicals can be singly or repeatedly, preferably singly, substituted. Preferred substituents are halogen, in particular bromine, -OCH3, -OH, -CN, -CH3, -C2H5, -N02, -COOH and -COOCH3.
Preferred C~- to C12- aryl alkyl radicals are benzyl, oc methyl benzyl, ~,cx-dimethylbenzyl and ~c,oc-diethylbenzyl, in particular benzyl.
Preferred definitions which can be chosen independently of one another are:
R1 hydrogen or -CH3, R2 -CH3, -C2H5, a benzyl or phenyl radical, R3 hydrogen or a methyl radical, R4 an ethylene, propylene, triethylene, butylene or phenylene radical, RS a methyl radical, R6 a benzyl, phenyl or substituted phenyl radical, W oxygen, sulphur or NH, Z -CO- or a chemical bond and/or R' hydrogen.
Quite particularly preferred definitions which can be chosen independently of each other are:
R1 hydrogen, R2 hydrogen, a benzyl or phenyl radical, R3 a methyl radical, R4 an ethylene, triethylene or propylene radical, RS a methyl radical, R6 a benzyl radical, W oxygen, Z -CO- and/or R' hydrogen.
_ Furthermore, urethane di(meth)acrylate derivatives in which X and Y have the same meaning are preferred.
Particularly preferred urethane di(meth)acrylate derivatives are:
10 /O O HN ~ NH O O
O ~ . ~ O
~O O HN ~ NH O O~
O ~ O
O O HN ~ NH O O
O ~ ~ O O
O H ~ NH O
a O ~ ~ O
I
O O HN ~ NH O
O
O O
O HN ~ NH O
O
O
O O HN ~ NH
.o ~~~~N~
Br . Br II n II
O HN%~NH 0~~
is ~~ ~~' Y Y
o i n i o N/~\ / \N1i 0~
20 ~ o 0' 'HN /~~NH' /0\ ~Q
zs O
p I ~ O
O N O N
O~ ~ O
O O
O
O
HN NH O O
_ $ _ o ~ O
O\ /HN NH\ 'O
O
O O
co-o o-oc HC-0 HN ~ NH O-CH
CH2 ~ ~ Cf-;2 O O O O
C O-O . o--OC
Hz C H2 HC-0 H ~ NH O-CH
C H2 ~ ~ ~ C HZ
H-N O ~ N-H
co-o a-oc ~H2 CH2 HC-O HN ~ NH ~O-CH
a CH2 ~ ~ ~ CH2 S S
- 9 _ H2 C Hz HC-0 HN ~ NH O-CH
v CH2 ~ ~ ~ CH2 D O O
C 0-0 . 0-OC
Hz C H2 HC-0 HN ~ NH O-CH
CHz ~ ~ ~ ~ CHZ
O O
i i o c=0 0=c C 0-0 Q-.OC
~H2 ~ CH2 02N CH2 ~ ~ ,~ ~ CH2 N02 ~ O O
2 5 ~ ~=0 O=C
c o-0 o-oc ~Hz ~ CH2 w/
C H2 ~ ~~ ~ C H2 D O O
C H2--C=O O=C-C HZ
Furthermore, compounds according to Formula I in which R and R3, independently of each other, are hydrogen or methyl and R4 is ethylene or propylene are particularly preferred.
The urethane di(meth)acrylate derivatives according to the invention of formula (I) can be prepared by reaction of com mercial 1,3-bis(1-isocyanato-1-methylethyl)benzene (TMXDI) with corresponding hydroxy(meth)acrylates X-OH or Y-OH and optionally subsequent alkylation of the formed adducts for example with a dialkyl sulphate.
1.) X-OH O N ~ N O, O=C= N=C=O ~~' \ 2.} Y-OH
TMXDI - H2S04 ' (RO)S02 r R
~O~N . N~O~X
IO I IO
The preparation of the hydroxy(meth)acrylates X-OH and Y-OH can take place in a manner known per se (cf. e.g. C. Ferri, Reaktionen der organischen Synthese (Organic Synthesis Reac-tions], G. Thieme Verlag, Stuttgart 1978). The Baylis-Hillman reaction, catalysed by tertiary amines, of acrylates with aldehydes according to the reaction equation ~ + 2R-C ~O ~ OH-HC~
'Rp-OC ~H
~ R O-OC
in which Rl and RZ have the meaning given above, is preferred.
For example, 2-hydroxymethyl acrylic acid benzyl ester can be prepared by reaction of acrylic acid benzyl ester with formal-dehyde:
Concrete example:
C H2-O-OC~ O C H2-O-OC
Further preferred is the unstoichiometric esterification of dihydroxy compounds with (meth)acrylic acid or (meth)acrylic acid chloride according to the reaction equation - U H H O-R4 o-oc HO-R-OH +
sR sR
(U: CI or OH) in which R3 and R4 have the meaning given above and U = C1 or is OH. For example, 4-hydroxyphenyl methacrylate is accessible by reaction of hydroquinone with methacrylic acid chloride:
Concrete example:
O H + C F-OC _~ H 0-OC
Moreover, the synthesis of suitable hydroxy(meth)acrylates can take place by reaction of glycidyl {meth)acrylate with O-nucleophilic reagents, such as alcohols, phenols or carboxylic acids according to the reaction equation 6 R-Z-O-H + C \2 C H-C H2-O-OC
O
R
. O.H
R
in which R5 and R6 have the meaning given above. For example, 1-benzylcarbonyloxy-2-hydroxypropyl methacrylate can be obtained by reaction of phenylacetic acid with glycidyl methacrylate:
Concrete example:
2 0 O C HZ-C O-OH + C \2 C H-C H2-O-OC
O
r OH
HsC
The urethane di(meth)acrylate derivatives according to the invention are suitable in particular for the production of polymers, adhesives and dental materials, such as filling composites, dental adhesives and fixing cements, with the urethane di(meth)acrylates acting as crosslinkers.
Derivatives with a refractive index of no - 1.50 to 1.60, in particular 1.50 to 1.55, are preferred for the production of dental materials.
For the polymerization, the compounds according to the invention are mixed with initiators for radical polymerization and optionally additional radically polymerizable monomers and fillers plus other auxiliaries.
Suitable initiators are described for example in the Encyclopedia of Polymer Science and Technology, Vol . 13, Wiley-Intersci . Pub . , New York etc. 1988, p. 754 et seq. Preferred initiators for cold polymerization are azo compounds such as azobis(isobutyronitrile) (AIBN) or azobis(4-cyanovaleric acid) or peroxides, such as dibenzoyl peroxide, dilauroyl peroxide, tert.-butyl peroctoate, tert.-butyl perbenzoate or di-(tert.-butyl) peroxide.
Benzpinacol and 2,2'-Di(C1-C8-alkyl)benzpinacols in particular are suitable as initiators for hot curing.
Suitable photoinitiators for the UV or visible range are described by J.P. Foussier, J.F. Rabek (Pub.), 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, acylphosphinic oxides, oc-diketones, such as 10-phenanthrenequinone, diacetyl, furil, anisil, 4,4'-dichlorobenzil and 4,4'-dialkoxybenzil and camphor quinone.
Dibenzoyl peroxide, camphor quinone or acylphosphinic oxides are particularly suitable for the production of dental materials.
Difunctional crosslinker monomers are preferred as additional radically polymerizable monomers, with crosslinking bi- or higher-functional acrylates and methacrylates, such as for example UDMA, di- or triethylene glycol di(meth)acrylate (TEGDMA), decanediol di(meth)acrylate, trimethylol propane tri(meth)-acrylate, pentaerythritol tetra(meth)acrylate, butanediol (di)-methacrylate, 1,10-decanediol di(meth)acrylate diol di(meth)acrylate above a11 being suitable for producing adhesives or dental materials. These monomers are accessible by esterification of (meth)acrylic acid with suitable diols.
Organic as well as inorganic particles and fibres are suitable as fillers. Preferred inorganic fillers for producing dental materials are amorphous, spherical materials on the basis of mixed oxides from Si02, Zr02 and/or TiOz with an average particle size of 0.005 to 2.0 um, preferably of 0.1 to 1 Vim, as are disclosed for example in DE-PS 32 47 800, microfine fillers, such as pyrogenic silica or precipitation silica, as well as macro-or mini-fillers, such as quartz, glass ceramic or glass powder with an average particle size of 0.5 to 20 um, as well as X-ray-opaque fillers, such as ytterbium trifluoride. The term mini-fillers is taken to mean fillers with a particle size of 0.5 to 1.5 Vim, and the term macro-fillers to mean fillers with a particle size of 10 to 20 um.
Glass, polyamide or carbon fibres can also be used as fillers.
Suitable reinforcing fibres are described for example in the "Taschenbuch der Kunststoff-Additive", R. Gachter, H. Miiller, Carl Hanser Verlag, Munich and Vienna 1990, pages 617 to 662.
The compositions according to the invention can also if needed contain other auxiliaries such as solvents, in particular water, ethyl acetate or ethanol, stabilizers, W absorbers, dyestuffs, pigments and/or slip agents. The term stabilizers is taken to mean substances which prevent premature polymerization and thus above a11 increase the storage stability of monomer mixtures and composites without however impairing 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 wt.-~, preferably 10 to 80 wt.-~ and particularly preferably 20 to 70 wt.-~s of one or more urethane di(meth)acrylates, 0 to 80 wt.-$, preferably 0 to 60 wt.-~ and particularly preferably 0 to 50 wt.-~ of one or more other radically polymerizable monomers, 0 to 90 wt.-$ fillers and 0.01 to 5 wt.-$, preferably 0.01 to 2 wt.-$ of an initiator fox radical polymerization.
The filler content is crucially determined by the intended use and is preferably 0 to 20 wt.-$ in the case of adhesives, preferably 20 to 60 wt.-~ in the case of cements and 50 to 85 wt.-~ in the case of filling composites.
The proportion of the other auxiliaries usually lies in the range from 100 ppm to 1.0 wt.-~ in each case, and in the case of dyestuffs and pigments, depending on colouring capacity, also in the range from 10 ppm up to 1.0 wt.-~.
The dental materials according to the invention preferably contain no bis-GMA, but have mechanical properties which correspond in every respect to those of materials containing bis-GMA. Under moist conditions, the materials according to the invention display clearly better mechanical properties than the materials containing bis-GMA.
The urethane di(meth)acrylate derivatives according to the invention are moreover also suitable for the production of other medical or technical, radically curing adhesives, cements and composites, such as for example surgical bone cements, contact lenses, adhesives for optical parts, UV-curable lacquers, coatings and covering materials and also matrix resins for composite materials.
The invention is explained in more detail in the following with reference to embodiments.
Example 1 Synthesis of TMXUDEMA
1,3-bis-(2-aza-1,1,9-trimethyl-3;8-dioxo-4,7-dioxa-9-decen-1-yl)-benzene O O
o~o~rrH ~ rrH~o~o w I
o ~ ~ o TMXUDEMA
90.7 g (371 mmol) of TMXDI were added dropwise within 30 minutes to 101.1 g (742 mmol) of HEMA and 0.19 g of dibutyltin dilaurate (Metatin 812, Acima). After 36 hours' stirring at 70~C the iso-cyanate had completely reacted off (reaction monitoring by means of IR spectroscopy) . 300 ml of methylene chloride were added and the reaction mixture washed twice with 200 ml of NaOH each time and three times with l00 ml of water each time. The methylene chloride phase was dried with sodium sulphate and the solvent evaporated off, after the addition of 80 mg of hydro-quinone monomethyl ether (MEHQ), at the rotation evaporator at ca. 250 mbar. 169 g (88o yield) of a colourless, highly viscous liquid (nozs - 1.5120) with a shearing 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.
1H-NMR ( 400 MHz, CDC13 ) : 7 . 43 and 7 . 27 (m, 4H, aromatic ) ; 6 . 13 and 5.77 (2 s, 4 H, =CHZ); 5.29 (br, 2 H, NH); 4.24-4.40 (br, 8 H, OCHZCH20 ) ; 1. 9 5 ( s , 6H =C-CH3 ) and 1 . 6 6 ( s , 12 H, CH3 ) ppm .
Example 2 Synthesis of TMXUDPMA
1,3-bis-(2-aza-1,1,5,9-tetramethyl-3,8-dioxo-4,7-dioxa-9-decen-1-yl)-benzene O
O ~ ~O \
O NH ~ ~ ,~NH O
O \ O
TMXUDPMA
55.0 g (225 mmol) of TMXDI were added dropwise within 10 minutes to 68.3 g (450 mmol) of 95% hydroxypropyl methacrylate and 0.1 g of Metatin 812. After 3 days' stirring at 60~C the isocyanate had completely reacted off (reaction monitoring by means of IR
spectroscopy). The reaction mixture was reacted with 200 ml of methylene chloride and washed twice with 100 ml of NaOH each time and three times with 100 ml of water each time. The methylene chloride phase was dried with sodium sulphate and the solvent evaporated off, after the addition of 80 mg of MEHQ, at the rotation evaporator at ca. 250 mbar. 106 g (88% yield) of a colourless, highly viscous liquid (no25 = 1.50l8) with a shearing 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.
1H-NMR (400 MHz, CDC13): 10.86 (br, 2 H, NH); 7.26 and 7.22 (m, 4H, aromatic); 6.22 and 5.69 (2 s, 4 H, =CH2); 5.00 (m, ', OCH);
4.09 - 4.29 (m, ', OCHZ); 1.93 (s, 6 H =C-CH3); 1.62 (s, 12 H, CH3) and 1.32 (d, ', CHC~) ppm (with E' 0 12 H) .
Example 3 Composites on the basis. of TMKUDEMA and TMXUDPMA
Three composite pastes K-1 to K-3 with the compositions shown in Table I (all figures in wt.-$) were prepared in a planetary kneader (type LPM 2SP, Linde) and deaerated at 200 mbar for ten minutes.
Composition K-3 contains bis-GMT instead of the urethane di(meth)acrylate derivatives according to the invention and serves as a comparative example.
To determine the mechanical properties, testpieces (2 mm x 2 mm x 20 mm) were formed from the pastes and cured by 6 minutes' exposure to light with a dental radiation source (Spektramat, Vivadent, ~, = 400 to 500 nm). The polymerization shrinkage (AV) was calculated from the difference between the paste and composite densities determined by gas pyknometry, and the bending strength (BS), the bending E-modulus (BEM) were determined according to ISO standard 4049 (1988). For this, the testpieces were stored dry at 37~C for 24 hours or for 24 hours or 7 days in water (WS) or boiled for 24 hours in deionized water (B). The results of the studies are listed in Table II.
Table I
Composition of the composite pastes (wt.-%) Com onent K-1 K-2 K-3a~
TMXUDEMA 7.59 - -TMXUDPMA - 7.59 -bis-GMA - - 7.59 UDMA 6.72 6.72 6.72 TEGDMA 3.64 3.64 3.64 Ytterbium fluoride 14.89 14.89 14.89 Rhone-Poulenc Barium glass b' 51.61 51.61 51.61 Spharosil ~ c 14.39 14.39 l4.39 AEROSIL ~ OX-50 d~ 1.00 1.00 1.00 Hydroquinone meth 1 ether 0.02 0.02 0.02 Camphor uinone 0.05 0.05 0.05 N-(2-cyanoethyl-N-methyl- 0.09 0.09 0.09 aniline a) comparative example b) silanized barium aluminium silicate glass powder (Schott), proportion with a grain size < 7 Vim: 99%
c) Si02-Zr02 mixed oxide (Tokoyama Soda), secondary grain size < 7~m d) silanized pyrolysis silica (Degussa) Table II
Mechanical properties of the cured composite materials Pro ert K-1 K-2 K-3a~
~V vol.-~ -2.9 -2.8 -2.8 BS, d MPa 141 120 116 BS, 24 h WS MPa 153 145 140 BS, 7 d WS MPa 147 144 121 BS, 24 h B MPa 143 129 l23 I BEM, dr GPa 13.14 13.62 12.13 BEM, 24 h WS GPa 12.40 12.56 l1.44 BEM, 7 d WS GPa 12.58 11.66 11.63 BEM, 24 h B GPa 12.92 1l.52 10.56 a) Comparative example
Claims (18)
1. Urethane di(meth)acrylate derivative of 1,3-bis(1-iso -cyanato-1-methylethyl)benzene according to Formula (I), in which R is hydrogen or a straight-chained C1-C8 alkyl radical, X and Y independently of each other stand for in which R1 is a substituted or unsubstituted C6- to C12- aryl, C7-to C16- alkyl aryl or C7- to C12- aryl alkyl radical, R2 is hydrogen, a C1- to C5- alkyl or a substituted or unsubstituted C6- to C12- aryl radical, R3 is hydrogen or a methyl radical, R4 is a C1- to C8- alkylene radical which can be interrupted by oxygen atoms, or a phenylene radical, R5 is hydrogen or a methyl radical, R6 is a substituted or unsubstituted C6- to C12- aryl, C7-to C16- alkyl aryl or C7- to C12- aryl alkyl radical, Z is -CO- or a chemical bond and W stands for oxygen, sulphur or NR7, whereby R7 is hydrogen or a straight-chained C1- to C6- alkyl radical, with the proviso that when R is hydrogen and R4 is dimethylene, R3 is not methyl.
2. Urethane di(meth)acrylate derivative according to Claim 1, characterized in that X and Y independently of each other stand for or~~
3. Urethane di(meth)acrylate derivative according to Claim 1 or 2, characterized in that the aryl groups are singly or repeatedly substituted by halogen, -OCH3, -OH, -CN, -CH3, -C2H5, -NO2, -COOH and/or -COOCH3.
4. Urethane di(meth)acrylate derivative according to one of Claims 1 to 3, characterized in that X and Y are the same.
5. 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, R1 hydrogen or -CH3, R2 -CH3, -C2H5, a benzyl or phenyl radical, R3 hydrogen or a methyl radical, R4 an ethylene, propylene, triethylene, butylene or phenylene radical, R5 a methyl radical, R6 a benzyl, phenyl or substituted phenyl radical, W oxygen, sulphur or NH, Z -CO- or a chemical bond and/or R7 is hydrogen.
6. Urethane di(meth)acrylate derivative according to Claim 5, characterized in that R1 is hydrogen, R2 hydrogen, a benzyl or phenyl radical, R3 a methyl radical, R4 an ethylene, propylene or triethylene radical, R5 a methyl radical, R6 a benzyl radical, W oxygen, Z -CO- and/or R7 is hydrogen.
7. Process for the production of a urethane di(meth)acrylate derivative according to one of Claims 1 to 6, characterized in that 1,3-bis(1-isocyanato-1-methylethyl)benzene is reacted with hydroxy(meth)acrylates according to the formulae X-OH or Y-OH, X and Y having the given meaning, and the reaction product is optionally then alkylated.
8. Composition containing a urethane di(meth)acrylate derivative according to one of Claims 1 to 6.
9. Composition according to Claim 7, characterized in that it contains 1 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 mono mers;
0 to 90 % fillers; and 0.01 to 5 % of an initiator for the radical polymerization plus further auxiliaries where necessary.
0 to 80 % of one or more radically polymerizable mono mers;
0 to 90 % fillers; and 0.01 to 5 % of an initiator for the radical polymerization plus further auxiliaries where necessary.
10. Composition according to Claim 9, characterized in that it contains 20 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 0.01 to 2 % of an initiator for the radical polymerization plus further auxiliaries where necessary.
0 to 80 % of one or more radically polymerizable monomers;
0 to 85 % fillers; and/or 0.01 to 2 % of an initiator for the radical polymerization plus further auxiliaries where necessary.
11. Composition according to Claim 9 or 10, characterized in that it contains, as radically polymerizable monomers, one or more bi- or higher-functional acrylates and/or methacrylates.
12. Composition according to Claim 11, characterized in that it contains 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diaza-hexadecan-1,16-diyldimethacrylate, di-or triethylene glycol di(meth)acrylate (TEGDMA), decanediol di(meth)acrylate, trimethylol propane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,10-decanediol di(meth)acrylate and/or 1,12-dodecanediol di(meth)acrylate.
13. Composition according to one of Claims 9 to 12, characterized in that it contains, as filler, amorphous spherical materials on the basis of mixed oxides from SiO2, ZrO2 and/or TiO2, pyrogenic silica, precipitation silica, quartz, glass ceramic or glass powder and/or ytterbium fluoride.
14. Composition according to one of Claims 9 to 13, characterized in that it contains, as initiator, azobis(isobutyro-nitrile), azobis(4-cyanovaleric acid), dibenzoyl peroxide, dilauroyl peroxide, tert.-butyl peroctoate, tert.-butyl perbenzoate, di-(tert.-butyl)-peroxide, benzpinacol, a 2,2'-di(C1-C$-alkyl)benzpinacol, a benzoin ether, a dialkyl benzil ketal, dialkoxyacetoph-enone, acylphosphinic oxide, 9,10-phenanthrenequinone, diacetyl, furil, anisil, 4,4'-dichlorobenzil, 4,4'-dialkoxybenzil and/or camphor quinone.
15. Composition according to one of Claims 9 to 14 for use as dental material.
16. Use of a urethane di(meth)acrylate derivative according to one of Claims 1 to 6 for the production of radically curable adhesives, cements or composites.
17. Use according to Claim 16 for the production of dental materials.
18. Use according to Claim 16 for the production of surgical bone cements, contact lenses, adhesives for optical parts, UV-curable lacquers, coatings and covering materials, matrix resins and composite materials.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19803979A DE19803979C2 (en) | 1998-01-28 | 1998-01-28 | Compositions containing urethane di (meth) acrylate derivatives of 1,3-bis (1-isocyanato-1-methylethyl) benzene |
DE19803979.4 | 1998-01-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2256191A1 true CA2256191A1 (en) | 1999-07-28 |
Family
ID=7856371
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002256191A Abandoned CA2256191A1 (en) | 1998-01-28 | 1998-12-17 | Urethane di (meth) acrylate derivatives of 1,3-bis (1-isocyanato-1-methylethyl) benzene |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0934926B1 (en) |
JP (1) | JP3182738B2 (en) |
AT (1) | ATE292113T1 (en) |
CA (1) | CA2256191A1 (en) |
DE (2) | DE19803979C2 (en) |
Cited By (2)
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US9782329B2 (en) | 2013-07-08 | 2017-10-10 | 3M Innovative Properties Company | Hardenable dental composition containing a mixture of agglomerated and aggregated nano-particles, kit of parts and use thereof |
US11944692B2 (en) | 2018-06-19 | 2024-04-02 | Voco Gmbh | Thermoactive dental composite composition |
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US6653375B2 (en) | 1998-01-28 | 2003-11-25 | Ivoclar Ag | Urethane di(meth)acrylate derivatives of 1,3-bis(1-isocyanato-1-methylethyl)benzene |
DE19961341C2 (en) * | 1999-12-17 | 2003-09-11 | 3M Espe Ag | Improved dental materials |
DE10339912B4 (en) | 2003-08-29 | 2016-07-21 | Ivoclar Vivadent Ag | Dental coating materials, their use and methods of coating a substrate surface |
US8455566B2 (en) * | 2006-10-18 | 2013-06-04 | E I Du Pont De Nemours And Company | Materials leading to improved dental composites and dental composites made therefrom |
DE102006060983A1 (en) | 2006-12-20 | 2008-06-26 | Heraeus Kulzer Gmbh | Dental composites with tricyclo [5.2.1.02.6] decane derivatives |
EP2008636A1 (en) | 2007-06-29 | 2008-12-31 | 3M Innovative Properties Company | Dental composition containing a polyfunctional (meth)acrylate comprising urethane, urea or amide groups, method of production and use thereof |
WO2011059117A1 (en) * | 2009-11-16 | 2011-05-19 | 株式会社トクヤマ | Urethane (meth) acrylate monomer and manufacturing method for same |
CN102936210A (en) * | 2012-11-15 | 2013-02-20 | 中南林业科技大学 | 2,4-toluene diisocyanate and preparation method and application thereof |
MX354347B (en) * | 2013-06-17 | 2018-02-21 | Univ Mexico Nac Autonoma | Bisgma-free orthodontic adhesives. |
EP2918259B1 (en) * | 2014-03-10 | 2019-01-02 | DENTSPLY DETREY GmbH | Dental composition based on condensed aromatic compounds |
ES2762237T3 (en) * | 2014-03-20 | 2020-05-22 | Ivoclar Vivadent Ag | Monomer mix for dental materials manufacturing |
US10130564B2 (en) | 2014-03-31 | 2018-11-20 | Mitsui Chemicals, Inc. | Dental polymerizable monomers |
DE102015104440A1 (en) * | 2015-03-24 | 2016-09-29 | Heraeus Kulzer Gmbh | Process for producing dental prostheses and ready-to-use dental material and kit containing the dental material |
JP6634071B2 (en) * | 2015-03-31 | 2020-01-22 | 三井化学株式会社 | Polymerizable monomers for dental materials, compositions, adhesive dental materials, and kits |
WO2017155692A1 (en) | 2016-03-07 | 2017-09-14 | 3M Innovative Properties Company | Preformed dental composite crown, process of production and use thereof |
EP3515396B1 (en) | 2016-09-22 | 2022-01-05 | 3M Innovative Properties Company | Cationically and radiation curable composition |
BR112019026532A2 (en) | 2017-06-14 | 2020-06-23 | 3M Innovative Properties Company | CURABLE COMPOSITION FOR THE PRODUCTION OF A DENTAL COMPOUND CROWN AND PRODUCTION PROCESS |
US11597830B2 (en) | 2017-06-20 | 2023-03-07 | 3M Innovative Properties Company | Radiation curable composition for additive manufacturing processes |
JP6941186B2 (en) | 2017-11-28 | 2021-09-29 | 三井化学株式会社 | (Meta) Acrylate and Its Applications |
JP6920463B2 (en) | 2017-11-28 | 2021-08-18 | 三井化学株式会社 | (Meta) acrylate, monomer composition, dental material obtained from the composition, and method for producing the same. |
EP3795597A4 (en) | 2018-08-21 | 2022-02-23 | Mitsui Chemicals, Inc. | (meth)acrylate, monomer composition for dental material, molded body, composition for dental material, dental material, and method for producing (meth)acrylate |
JP7304900B2 (en) | 2019-01-21 | 2023-07-07 | 三井化学株式会社 | Photopolymerization initiator, photocurable composition, cured product, and dental material |
EP3854374A1 (en) | 2020-01-24 | 2021-07-28 | Ivoclar Vivadent AG | Aesthetic dental filling material with high curing depth |
DE102021113777A1 (en) * | 2021-05-27 | 2022-12-01 | Kulzer Gmbh | Polymerizable composition containing thiolurethane groups |
EP4124331A1 (en) | 2021-07-27 | 2023-02-01 | Ivoclar Vivadent AG | Aesthetic dental filling material with high curing depth |
EP4380494A1 (en) | 2021-08-05 | 2024-06-12 | Solventum Intellectual Properties Company | Composition for isolating tissue |
WO2024018305A1 (en) | 2022-07-21 | 2024-01-25 | 3M Innovative Properties Company | Curable composition for producing transparent orthodontic attachments |
WO2024110805A1 (en) | 2022-11-25 | 2024-05-30 | Solventum Intellectual Properties Company | Curable composition for use in a process of treating a dental situation in the mouth of a patient |
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US4400159A (en) * | 1980-06-24 | 1983-08-23 | Scientific Pharmaceuticals, Inc. | Adducts of 3-methacroyl-2-hydroxypropyl esters with diisocyanates |
DE3743782A1 (en) * | 1987-12-23 | 1989-07-13 | Bayer Ag | ESTER URETHANE (METH) ACRYLIC ACID DERIVATIVES |
AU634338B2 (en) * | 1990-02-08 | 1993-02-18 | Mitsubishi Rayon Company Limited | Composition for plastic lenses |
JPH0525240A (en) * | 1991-07-19 | 1993-02-02 | Mitsubishi Rayon Co Ltd | Composition for plastic lens |
DE4343246A1 (en) * | 1993-12-17 | 1995-06-22 | Thera Ges Fuer Patente | Prepolymers, free-radically polymerizable compositions prepared therefrom and their use |
DE19544671A1 (en) * | 1995-11-30 | 1997-06-05 | Bayer Ag | Urethane (meth) acrylates with cyclic carbonate groups |
-
1998
- 1998-01-28 DE DE19803979A patent/DE19803979C2/en not_active Revoked
- 1998-12-17 CA CA002256191A patent/CA2256191A1/en not_active Abandoned
-
1999
- 1999-01-21 DE DE59911817T patent/DE59911817D1/en not_active Expired - Lifetime
- 1999-01-21 AT AT99250022T patent/ATE292113T1/en not_active IP Right Cessation
- 1999-01-21 EP EP99250022A patent/EP0934926B1/en not_active Expired - Lifetime
- 1999-01-26 JP JP01764599A patent/JP3182738B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9782329B2 (en) | 2013-07-08 | 2017-10-10 | 3M Innovative Properties Company | Hardenable dental composition containing a mixture of agglomerated and aggregated nano-particles, kit of parts and use thereof |
US11944692B2 (en) | 2018-06-19 | 2024-04-02 | Voco Gmbh | Thermoactive dental composite composition |
Also Published As
Publication number | Publication date |
---|---|
JP3182738B2 (en) | 2001-07-03 |
EP0934926A1 (en) | 1999-08-11 |
DE19803979C2 (en) | 2001-06-28 |
JPH11315059A (en) | 1999-11-16 |
DE59911817D1 (en) | 2005-05-04 |
DE19803979A1 (en) | 1999-08-05 |
EP0934926B1 (en) | 2005-03-30 |
ATE292113T1 (en) | 2005-04-15 |
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Legal Events
Date | Code | Title | Description |
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EEER | Examination request | ||
FZDE | Discontinued |