WO2000005325A1 - Photochromic compounds, process for their preparation and their use in polymeric materials - Google Patents
Photochromic compounds, process for their preparation and their use in polymeric materials Download PDFInfo
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- WO2000005325A1 WO2000005325A1 PCT/EP1999/004873 EP9904873W WO0005325A1 WO 2000005325 A1 WO2000005325 A1 WO 2000005325A1 EP 9904873 W EP9904873 W EP 9904873W WO 0005325 A1 WO0005325 A1 WO 0005325A1
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 title claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 75
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 48
- 229910052801 chlorine Inorganic materials 0.000 claims description 48
- 229910052731 fluorine Inorganic materials 0.000 claims description 46
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 42
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 42
- 229910052794 bromium Inorganic materials 0.000 claims description 42
- 239000000460 chlorine Substances 0.000 claims description 42
- 235000019000 fluorine Nutrition 0.000 claims description 42
- 239000011737 fluorine Substances 0.000 claims description 42
- 229940060037 fluorine Drugs 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 38
- -1 phenoxyl group Chemical group 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 34
- 125000003545 alkoxy group Chemical group 0.000 claims description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 32
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 28
- 125000003277 amino group Chemical group 0.000 claims description 26
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 26
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 24
- 125000005843 halogen group Chemical group 0.000 claims description 24
- 125000001153 fluoro group Chemical group F* 0.000 claims description 22
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 19
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical group CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 8
- 125000005394 methallyl group Chemical group 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000004922 lacquer Substances 0.000 claims description 7
- 239000003973 paint Substances 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 239000008199 coating composition Substances 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims description 5
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 4
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000620 organic polymer Polymers 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
- 125000000204 (C2-C4) acyl group Chemical group 0.000 claims description 2
- YFKBXYGUSOXJGS-UHFFFAOYSA-N 1,3-Diphenyl-2-propanone Chemical compound C=1C=CC=CC=1CC(=O)CC1=CC=CC=C1 YFKBXYGUSOXJGS-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- VWTUFJAPYGLYBO-UHFFFAOYSA-N 2,4-dinitro-3-oxopentanedinitrile Chemical compound [O-][N+](=O)C(C#N)C(=O)C(C#N)[N+]([O-])=O VWTUFJAPYGLYBO-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002614 Polyether block amide Polymers 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- 125000005019 carboxyalkenyl group Chemical group 0.000 claims description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000120 polyethyl acrylate Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 239000003963 antioxidant agent Substances 0.000 claims 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229920001684 low density polyethylene Polymers 0.000 claims 1
- 229920000728 polyester Polymers 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000047 product Substances 0.000 description 28
- 229940074995 bromine Drugs 0.000 description 21
- 229940060038 chlorine Drugs 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 0 CC(*1*2CC2)(C(*)(*)c2c1cccc2)Oc1c(*=C)c(cc(cc2)O[N+](**)[O-])c2cc1 Chemical compound CC(*1*2CC2)(C(*)(*)c2c1cccc2)Oc1c(*=C)c(cc(cc2)O[N+](**)[O-])c2cc1 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 150000002476 indolines Chemical class 0.000 description 4
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical class C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 3
- 150000002832 nitroso derivatives Chemical class 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- FBSPVPGRNVGTBQ-UHFFFAOYSA-N 1-nitrosonaphthalene-2,7-diol Chemical compound C1=CC(O)=C(N=O)C2=CC(O)=CC=C21 FBSPVPGRNVGTBQ-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000012458 free base Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 125000005027 hydroxyaryl group Chemical group 0.000 description 2
- 229940099514 low-density polyethylene Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- TWXDDNPPQUTEOV-FVGYRXGTSA-N methamphetamine hydrochloride Chemical compound Cl.CN[C@@H](C)CC1=CC=CC=C1 TWXDDNPPQUTEOV-FVGYRXGTSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000011649 selenium Nutrition 0.000 description 2
- 229940091258 selenium supplement Drugs 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- BHMMCMPHVDFHNG-UHFFFAOYSA-N 1,3-dinitropropan-2-one Chemical compound [O-][N+](=O)CC(=O)C[N+]([O-])=O BHMMCMPHVDFHNG-UHFFFAOYSA-N 0.000 description 1
- IVWSGOOPQGMALJ-UHFFFAOYSA-N 2,3,3-trimethyl-1,2-dihydroindole Chemical compound C1=CC=C2C(C)(C)C(C)NC2=C1 IVWSGOOPQGMALJ-UHFFFAOYSA-N 0.000 description 1
- FLHJIAFUWHPJRT-UHFFFAOYSA-N 2,3,3-trimethylindole Chemical class C1=CC=C2C(C)(C)C(C)=NC2=C1 FLHJIAFUWHPJRT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- WCONMBCADXJZEF-UHFFFAOYSA-N 3,3,4,7-tetramethyl-1,2-dihydroisoindole Chemical compound CC1=CC=C(C)C2=C1CNC2(C)C WCONMBCADXJZEF-UHFFFAOYSA-N 0.000 description 1
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 description 1
- MOMKCIUAVFQUIF-UHFFFAOYSA-N CC(C)(c1c2c(C)ccc1C)N(C)C21Oc(ccc2c3c4ccccc4[o]2)c3N=C1 Chemical compound CC(C)(c1c2c(C)ccc1C)N(C)C21Oc(ccc2c3c4ccccc4[o]2)c3N=C1 MOMKCIUAVFQUIF-UHFFFAOYSA-N 0.000 description 1
- ABWBBFOKHUVLFI-ZOEDNYEGSA-N CC/C(/N(C)C(C)=C)=C\C=C/C Chemical compound CC/C(/N(C)C(C)=C)=C\C=C/C ABWBBFOKHUVLFI-ZOEDNYEGSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000008371 chromenes Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 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 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229960002358 iodine Drugs 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SFDZETWZUCDYMD-UHFFFAOYSA-N monosodium acetylide Chemical compound [Na+].[C-]#C SFDZETWZUCDYMD-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- MLGWTHRHHANFCC-UHFFFAOYSA-N prop-2-en-1-amine;hydrochloride Chemical compound Cl.NCC=C MLGWTHRHHANFCC-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
- G03C1/733—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds with macromolecular compounds as photosensitive substances, e.g. photochromic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/008—Dyes containing a substituent, which contains a silicium atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances
Definitions
- the present invention relates to photochromatic com- pounds.
- the present invention relates to silylated photochromatic compounds, a process for their preparation and their use in polymeric materials.
- a furtner object of the present invention relates to polymeric compositions containing said photochromatic compounds ana the photochromatic articles obtained from their processing.
- Photochromatic compounds are substances which have the characteristic of reversibly changing colour and/or degree of light transmission when exposed to solar or artificial light in the band ranging from UV to visible, or to some types of electromagnetic radiation, returning to their original state of colour and transmission when the initial light source is removed.
- photochromatic char- acte ⁇ stics which belong to various groups of both organic and inorganic compounds such as, for example, those described m the texts "Photochromism”, by G.H. Brown (Ed.), Vol. Ill of the Weissberger series “Techniques of Organic Chemistry", Wiley Interscience, New York (1971) and m “Photochromism: Molecules and Systems", by H. Durr and H. Bouas- Laurent (Ed.), Vol. 40 of the series “Studies m Organic Chemistry” Elsevier (1990) .
- organic photochromatic compounds those belonging to the groups of spiro-indolmo-oxazmes, spiro-pyrans and chromenes, are particularly known and used.
- the above compounds are capable of giving photochromatic characteristics to polymerized organic materials used, for example, m the production of photochromatic lenses for eye-glasses, special inks, toys, and in many other applications.
- the Applicant has now found silylated photochromatic compounds which have good photochromatic characteristics, good fatigue resistance and good colourability characte ⁇ s- tics.
- the present invention therefore relates to photochro- matic compounds having general formula (i;
- X represents an oxygen atom; a sulfur atom; a selenium atom; an NH group; or an NR a group wherein R a represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group optionally substituted with 1- 5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched C ⁇ -C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; R'x represents a linear or branched Ci-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluo-
- R' represents a linear or branched Ci-Cio alkyl group; a linear or branched C 2 -C ⁇ 0 acyl group; a linear or branched C 2 -C ⁇ o heteroalkyl group in which the heteroa- tom is selected from nitrogen, oxygen, sulfur and sele- nium;
- R' ' represents a hydrogen atom; a halogen atom selected from fluorine, chlorine and bromine; a linear or branched Ci-C ⁇ alkyl group; a linear or branched C ⁇ -C 6 alkoxyl group; a phenyl group; a phenoxyl group; P' represents one of the following groups having general formula (III), (IV) or (V):
- R and R represent a linear or branched Ci-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-C ⁇ alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a vinyl group; an allyl or methallyl group; a linear or branched C 2 -C6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with linear or branched C ⁇ -C 6 alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (C ⁇ -C 6 ) amine groups; a C00R' a ester group wherein R
- R 3 , R 4 , R 5 andR 6 represent a hydrogen atom; a halogen atom selected from fluorine, chlorine, bromine and iodine; a linear or branched Ci- C 6 alkyl group, said alkyl group optionally substituted with 1-6 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched C ⁇ -C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X') 3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups
- P represents a monocyclic or polycyclic aromatic nucleus, belonging to one of the following types: ben- zenic represented by general formula (VI); naphthalenic represented by general formula (VII); quinolinic repre- sented by general formula (VIII); isoquinolinic repre- ' sented by general formula (IX); cumarinic represented by general formula (X) ; quinazolinic represented by general formula (XI); phenanthrenic represented by general formula (XII); anthracenic represented by general formula (XIII); dibenzofuran represented by general formula (XIV) :
- Y represents CH or a nitrogen atom.
- Preferred photochromatic compounds having general formula (I) for the purposes of the present invention are those wherein:
- X represents an oxygen atom
- R' ⁇ represents a methyl
- R' 2 represents an OH group; or a photochromatic com- pound having general formula (II);
- R' represents a linear or branched C 1 -C 4 alkyl group; a linear or branched C 2 -C 4 acyl group; a linear or branched C 2 -C 4 heteroalkyl group in which the heteroa- torn is selected from nitrogen, oxygen, sulfur and selenium;
- R' ' represents a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, or a phenyl group
- Y represents N or CH
- P' represents one of the groups having general formula (III), (IV) or (V) wherein:
- R and R 7 represent one of the following groups: methyl, ethyl, isopropyl, 2- allyl, 2-methallyl, 2-hydroxyethyl, 2-carbo- xymethyl, phenyl, 4-N,N-dimethylaminoaniline, 4- methoxybenzene, 4-cyanobenzene;
- Ri and R 2 represent a methyl or phenyl group; or considered jointly with the carbon atom to which they are bound, represent a cyclohexyl group;
- R 3 , R 4 , R 5 and R 6 represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, N,N-di- methylamine, piperidine, morpholine, carboxyl, carboxymethyl, N,N-dimethylcarboxy-amide, cyano, ' nitro, methylketone, phenylketone, phenyl; P represents one of the groups having general formula from (VI) to (XIV), wherein: (a) two consecutive substituents between R 8 and R i3 , R ⁇ 4 and R 2 ⁇ , R 22 and R 28 , R 30 and R 35 , R 3 ⁇ and R 4i , R 42 and R 47 , R 4 s and R 57 , R58 and R 6 , R ⁇ s and R 75 , independently represent the condensation points with the oxa
- a further object of the present invention relates to a process for the preparation of photochromatic compounds having general formula (I) .
- the photochromatic compounds having general formula (I) can be prepared by the condensation of photochromatic compounds having general formula (II)
- substituents R' ⁇ and X have the same meanings described above, in the presence of an inert organic solvent such as, for example, acetone, ethyl alcohol, isopropanol, toluene, dioxane, or a mixture of these solvents, at a temperature ranging from 50°C to 100°C, preferably from 60°C to 80°C, for a time ranging from 1 hour to 10 hours, preferably from 2 hours to 5 hours.
- an inert organic solvent such as, for example, acetone, ethyl alcohol, isopropanol, toluene, dioxane, or a mixture of these solvents
- the reaction product thus obtained is generally purified on a silica column, with subsequent crystallization from a solvent such as, for example, ace- • tone, toluene, pentane, heptane, diethyl ether, or by repeated precipitations with methanol and dried with toluene.
- a solvent such as, for example, ace- • tone, toluene, pentane, heptane, diethyl ether, or by repeated precipitations with methanol and dried with toluene.
- the photochromatic compounds having general formula (II) are obtained by the condensation of isoindoline compounds having general formula (XVI), or of indoline compounds having general formula (XVII), or of compounds deriving from propargyl alcohol having general formula (XVIII), or of compounds deriving from , ⁇ -unsaturated aldehydes hav- ing general formula (XIX) , with nitroso compounds or aldehyde compounds having general formula (XX) , or with hydroxy- aryl compounds having general formula (XXI), to give the respective photochromatic compounds having general formula (XVIa), (XVIIa) and (XVIIIa) , indicated in Schemes 1-4: Scheme 1
- the condensation reaction is carried out in the presence of an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, or a mixture of these sol- vents, and in the presence of an amine such as, for example, triethylamine, morphoiine, piperidine, or of an acid such as, for example, paratoluenesulfonic acid, sulfuric acid, acid alumina, or of a metal complex such as, for example, titanium (IV) tetraethoxide, at a temperature ranging from 50°C to 100°C, preferably from 60°C to 75°C, for a time ranging from 1 hour to 10 hours, preferably from 2 hours to 3 hours.
- an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, or a mixture of these sol- vents
- an amine such as, for example, triethylamine, morphoi
- the reaction product thus obtained is generally purified by elution on a silica column with subsequent crystallization from a solvent such as, for example, acetone, toluene, heptane, pentane, diethyl ether.
- a solvent such as, for example, acetone, toluene, heptane, pentane, diethyl ether.
- the isoindoline compounds having general formula (XVI) can be prepared according to processes known in the art and described, for example, in: “Tetrahedron” (1966), Vol. 22, page 2481; “Journal of Organic Chemistry” (1979), Vol. 44, page 1519; “Angewandte Chemie International (1968), Vol. 7, page 373.
- the indoline compounds having general formula (XVII) can be prepared by the reaction of 2, 3, 3-trimethylindolenine compounds with an alkyl or (meth) allyl halide as described, for example, in Japanese patent application JP 03/176467.
- the isoindoline compounds having general formula (XVI) and the indoline compounds having general formula (XVII) are usually kept in the form of salts such as, for example, iodides, bromides, chlorides, as the free base is very oxidable in air.
- the compounds deriving from propargyl alcohol having general formula (XVIII) can be prepared by the reaction of ketone compounds with sodium acetylide in xylene or with a lithium/ethylenediamine acetylide complex as described, for example, in U.S. patents 5,585,042 and 5,238,981.
- the compounds deriving from ⁇ , ⁇ -unsaturated aldehydes having general formula (XIX) can be prepared according to the processes known in the art as described, for example, in Japanese patent application JP 48/016481; or in "Organic Synthesis” (1970), Vol. 50, page 66.
- the nitroso compounds having general formula (XX) can be prepared by the reaction of phenol compounds with nitrous acid or butyl nitrite, as described, for example, in Italian patent 1,176,858.
- the aldehyde compounds having general formula (XX) can be prepared by the reaction of phenol compounds with para- formaldehyde, hexamethylenetetramine, or acetic acid, followed by the addition of an aqueous solution of sulfuric acid at 60%-70%, as described, for example, in German patent DE 2,425,430.
- the hydroxy-aryl compounds having general formula (XXI) are normally products which are commercially available such as, for example, ⁇ -naphthol or phenol.
- isoindoline compounds having general formula (XVI), or indoline compounds having general formula (XVII), are the following:
- nitroso compounds having general formula (XX) are the following:
- the photochromatic compounds having general formula (I) of the present invention are brightly yellow or dark yellow- coloured, oily or crystalline products.
- photochromatic compounds having general formula (I) can be applied to the surface or incorporated in mass into the desired articles, using techniques already known in the art and described hereunder. Some polymeric photochromatic end-articles can be obtained with moulding techniques such as, for example, injection or compression moulding, starting from polymers in which one or more of the photochromatic compounds having formula (I) are homogeneously dispersed in mass.
- the photochromatic compounds having general formula (I) can be dissolved in a solvent, together with the polymeric material such as, for example, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate or epoxy, polysiloxane, urethane resin.
- a solvent such as, for example, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate or epoxy, polysiloxane, urethane resin.
- the mixture thus obtained is deposited on a transparent carrier to form, after evaporation of the solvent, a photochromatic coating.
- the photochromatic compounds having general formula (I) can also be added to a polymerizable monomer such as, for example, a meth (acrylic) or allyl carbonate monomer, so that, after polymerization carried out in the presence of a suitable initiator such as, for example, azo-bis (isobutyro- nitrile) in the case of the meth (acrylic) monomer or a per- oxyketal in the case of the allyl carbonate monomer, they are uniformly incorporated in the resin formed.
- a suitable initiator such as, for example, azo-bis (isobutyro- nitrile) in the case of the meth (acrylic) monomer or a per- oxyketal in the case of the allyl carbonate monomer, they are uniformly incorporated in the resin formed.
- the photochromatic compounds having general ' formula (I) can be applied to a transparent substrate such as, for example, polycarbonate, polymethyl methacrylate or polydiethyleneglycol bis (allyl carbonate), by surface im- pregnation obtained by putting the substrate in contact, at a suitable temperature, with a solution or dispersion containing one or more of the photochromatic compounds having general formula (I), operating according to the method described, for example, in U.S. patent 5,130,353.
- a transparent substrate such as, for example, polycarbonate, polymethyl methacrylate or polydiethyleneglycol bis (allyl carbonate
- the photochromatic compounds having general formula (I) of the present invention have the characteristic of being able to be incorporated in mass or using one of the techniques described above, into various organic polymers such as, for example, high density polyethylene (HDPE), low density poly- ethylene (LDPE) , ethylene-vinylacetate copolymer, polyether amides, polypropylene, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate, ep- oxy, polysiloxane or urethane resins, polycarbonate, polydi- ethylene glycol bis (allyl carbonate), polyamides, polyes- ters, polystyrene, polyvinylchloride, polyethylacrylate, siliconic polymers.
- HDPE high density polyethylene
- LDPE low density poly- ethylene
- ethylene-vinylacetate copolymer polyether amides
- polypropylene polymethyl methacrylate
- a further object of the present invention therefore relates to polymeric compositions comprising the above polymeric materials and the above photochromatic compounds hav- ing general formula (I) and the photochromatic articles ob- tained from their processing.
- the photochromatic compounds having general formula (I) of the present invention are added to the above polymeric compositions in a quantity ranging from 0.01% to 5% by weight, preferably between 0.1% and 2% by weight, with respect to the weight of said polymeric compositions.
- the photochromatic compounds having general formula (I) of the present invention can also be added to coating compositions, such as for example, paints, lacquers, paints or lacquers based on hybrid polysiloxanes and/or silica gel, compositions based on plastic materials.
- a further object of the present invention consequently relates to coating compositions, such as for example, paints, lacquers, paints or lacquers based on hybrid polysiloxanes and/or silica gel, compositions based on plastic materials, comprising said photochromatic compounds.
- the photochromatic compounds having general formula (I) of the present invention are added to the above coating compositions in a quantity ranging from 0.01% to 5% by weight, preferably between 0.1% and 2% by weight, with respect to the weight of said coating compositions.
- Paints or lacquers based on hybrid polysiloxanes and/or silica gel are obtained by means of the "sol-gel" process described, for example, by M. Nogami, Y. Abe in: “Journal of Materials Science” (1995), Vol. 3C, pages 5789-5792.
- the above coating compositions can be applied to the substrate (metal, plastic, wood, etc.) using the conventional methods such as, for example, brushing, spraying, pouring, dipping or electrophoresis.
- the photochromatic compounds having general formula (I) of the present invention can optionally be used in the presence of usual additives for organic polymers such as, for example, phenolic antioxidants, sterically hindered amines, benzotriazoles, benzophenones, phosphites or phosphonites .
- organic polymers such as, for example, phenolic antioxidants, sterically hindered amines, benzotriazoles, benzophenones, phosphites or phosphonites .
- the photochromatic compounds having general formula (I) of the present invention which, as already mentioned above, have a brightly yellow or dark yellow colouring, can be used as such, mixed with each other, or combined with other suitable organic photochromatic compounds in order to obtain, after activation, the formation of other colourings such as brown and grey.
- the above mixture is heated to 80°C, under a nitrogen atmosphere, for 24 hours. At the end, the mixture is cooled and subsequently extracted with 30 ml of hexane.
- the aqueous phase obtained is treated with aqueous sodium hydroxide (solution at 30%) until pH 14 is reached: a yellow-white precipitate is thus formed which is rapidly filtered and washed with 30 ml of water and 10 ml of hexane.
- the product is dried under vacuum and conserved in a nitrogen atmosphere: the yield is 31.5 g.
- a quantity equal to 31.5 g of the above product is placed in a 100 ml inox steel autoclave together with 20 ml of toluene and 23.8 g of methyliodide.
- the autoclave is heated to 85°C and is maintained at this temperature, under a nitrogen atmosphere, for 6 hours.
- the autoclave is cooled to room temperature and the raw product is filtered obtaining a crystalline precipitate which is washed with 20 ml of ethyl acetate and finally with 20 ml of hexane.
- the above mixture is heated to 70 °C and maintained at this temperature, under stirring, under a nitrogen atmosphere, for 1 hour.
- the reaction raw product obtained is filtered and subsequently purified by passage on a neutral col- umn of active aluminum oxide 90 (activity degree I), eluting with a mixture of heptane/ethyl acetate in a ratio of 1/1.
- the aqueous phase is further washed with toluene, treated with aqueous sodium hydroxide (solution at 30%) until reaching pH 14 and with toluene.
- the organic phases obtained are concentrated and dried.
- the above mixture is heated to 90 °C and maintained at this temperature, under stirring, under a nitrogen atmosphere, for 6 hours.
- the raw reaction product obtained is dried and repeatedly extracted with boiling heptane to which 1 g of activated carbon has been added.
- the heptane extracts are concentrated and boiled with an additional 0.6 g of activated carbon.
- reaction raw product obtained is filtered and subsequently purified by passage on a silica column eluting with a mixture of toluene/hexane in a ratio of 1/1.
- An almost pure photochromatic product (yellow-white solid) is obtained, which is further purified by crystallization from toluene.
- the solvent is eliminated by distillation under vacuum and 40 ml of toluene and 2.0 g of activated carbon are subsequently added. This mixture is heated to 7C°C for 15 minutes: the reaction raw product is filtered, concentrated and cooled.
- the precipitated raw product is filtered obtaining 6.3 g of a solid white product corresponding to the Compound having formula (XVIIa) -3 which is identified by gas-mass
- the reaction raw product obtained is purified by passage on a silica column, eluating with ethyl acetate and then with acetone.
- reaction raw product obtained is purified by repeated precipitations with methanol and dried with toluene.
- EXAMPLE 10 Evaluation of the photochromatic activity.
- the photochromatic activity is evaluated in ethanol, at 10°C, of Compounds (Ia)-(Ic) obtained as described in Examples 7-9.
- Solutions are prepared at a concentration equal to 10 ⁇ 4 M of the various Compounds (Ia)-(Ic) in ethanol and subse- quently 2 ml of each solution i? placed in a 1 cm quartz cell.
- the quartz cell containing the solution is introduced into a temperature control system, equipped with a magnetic stirrer (the solution is maintained under stirring during the measurement) .
- the spectrum of the activated and deactivated forms and the decolouring kinetics are registered with a UV/visible spectrophotometer with a photodiode detector (HP 8453) equipped with perpendicular optical fibres which give a continuous monochromatic irradiation.
- the light source is a high pressure Hg lamp and the irradiation wave length is determined by monochromatic filters. This system allows the absorbance to be contemporaneously monitored at all wave-lengths. The following parameters are determined using the measurements obtained as described above and with a calculation effected with the GRAFit program of Erithaeus Software Ltd.
- t ⁇ /2 (s) time in which the absorbance of the merocya- nine open form is equal to half of the initial absorbance value
- k ⁇ (s _1 ) constant of the oxazine ring closing thermal reaction rate
- ⁇ PMC (nm) wave-length of the maximum absorbance of the merocyanine open form
- colourability difference between the final absorbance and initial absorbance of the merocyanine open form.
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Abstract
Photochromatic compounds having general formula (I). The above photochromatic compounds can be used in polymeric materials, obtaining photochromatic articles.
Description
PHOTOCHROMIC COMPOUNDS, PROCESS FOR THEIR PREPARATION AND THEIR USE IN POLYMERIC MATERIALS
The present invention relates to photochromatic com- pounds.
More specifically, the present invention relates to silylated photochromatic compounds, a process for their preparation and their use in polymeric materials.
A furtner object of the present invention relates to polymeric compositions containing said photochromatic compounds ana the photochromatic articles obtained from their processing.
Photochromatic compounds are substances which have the characteristic of reversibly changing colour and/or degree of light transmission when exposed to solar or artificial light in the band ranging from UV to visible, or to some types of electromagnetic radiation, returning to their original state of colour and transmission when the initial light source is removed. There are numerous substances with photochromatic char-
acteπstics, which belong to various groups of both organic and inorganic compounds such as, for example, those described m the texts "Photochromism", by G.H. Brown (Ed.), Vol. Ill of the Weissberger series "Techniques of Organic Chemistry", Wiley Interscience, New York (1971) and m "Photochromism: Molecules and Systems", by H. Durr and H. Bouas- Laurent (Ed.), Vol. 40 of the series "Studies m Organic Chemistry" Elsevier (1990) .
Among organic photochromatic compounds, those belonging to the groups of spiro-indolmo-oxazmes, spiro-pyrans and chromenes, are particularly known and used.
The above compounds are capable of giving photochromatic characteristics to polymerized organic materials used, for example, m the production of photochromatic lenses for eye-glasses, special inks, toys, and in many other applications.
As an example, tne following patents can be mentioned: USA 3,562,172, USA 3,578,602, USA 4,215,010, USA 4,342,668, USA 5,055,576, USA 5,110,922, USA 5,186,867, EP 146,135, EP 134,633, EP 141,407, EP 245,020, IT 1,233,348 and IT 1,238,694.
The Applicant has now found silylated photochromatic compounds which have good photochromatic characteristics, good fatigue resistance and good colourability characteπs- tics. The present invention therefore relates to photochro-
matic compounds having general formula (i;
wherein:
X represents an oxygen atom; a sulfur atom; a selenium atom; an NH group; or an NRa group wherein Ra represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group optionally substituted with 1- 5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched Cι-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; R'x represents a linear or branched Ci-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluo-
rine, chlorine and bromine, hydroxyl groups, linear or ' branched Cι-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a vinyl group; an allyl or methallyl group; a linear or branched C2-C6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with linear or branched Ci-Cβ alkoxyl groups, carboxyl groups, amine groups, N,N- dialkyl (Cι-C6 amine groups; a COOR'a ester group wherein R'a represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bro- mine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear cr branched Cι-Cδ alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; R'2 represents an OH group; or a photochromatic com- pound having general formula (II).
R' ' represents a hydrogen atom; a halogen atom selected from fluorine, chlorine and bromine; a linear or branched Ci-Cβ alkyl group; a linear or branched Cι-C6 alkoxyl group; a phenyl group; a phenoxyl group; P' represents one of the following groups having general formula (III), (IV) or (V):
( V ) ;
R and R, the same or different, represent a linear or branched Ci-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cβ alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a vinyl group; an allyl or methallyl group; a linear or branched C2-C6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with linear or branched Cι-C6 alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (Cι-C6) amine groups; a C00R'a ester group wherein R'a represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group optionally substituted with 1- 5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched Ci-Cε alkoxyl groups, carboxyl groups, cyano
groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; Ri and R2, the same or different, represent a linear or branched Ci-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluo- rine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Cι-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a vinyl group; an allyl or methallyl group; an acrylic or methacrylic group; a heteroallyl group; a linear or branched C2-Cι0 alkenyl group; a C00R'a ester group wherein R'a represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group optionally substituted with 1- 5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched C-i-Cio alkyl groups, linear or branched Cι-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a linear or branched Cι-C6 alkoxyl group; an N-alkyl (Cι-C6) amine group; an N,N-dialkyl (Cι-C6) amine group; or Ri and R2, considered jointly with the carbon atom to which they are bound, represent a C4-C10 cycloalkyl group, said cycloalkyl group optionally substituted
with halogen atoms selected from fluorine, chlorine and ' bromine, or with hydroxyl groups, linear or branched Ci-Cβ alkoxyl groups, carboxyl groups, cyano groups, amine groups, N-alkyl (Cι-C6) amine groups, N,N-dialkyl (Ci-Cβ) amine groups; an N,N-dialkyl (Ci-Cβ) amide group; an aryl group selected from phenyl and biphenyl; a cyano group;
R3, R4, R5 andR6, the same or different, represent a hydrogen atom; a halogen atom selected from fluorine, chlorine, bromine and iodine; a linear or branched Ci- C6 alkyl group, said alkyl group optionally substituted with 1-6 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Cι-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched Cι-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a hydroxyl group; a linear or branched Cι-C6 alkoxyl group; an
amine group; an N-alkyl (Ci-Cβ) amine group; an N,N- ' dialkyl (Cι-Ce) amine group; a piperidine, piperazine or morpholine group; a Cι-C6 carboxyalkyl group; a C2-C6 carboxyalkenyl group; a carboxyamide group; an N-alkyl (Ci-Ce) carboxyamide group; an N,N-dialkyl (Cι-C6) carboxyamide group; a cyano group; a nitro group; a sul- fonic group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with N,N-dialkyl (Ci-Ce) amine groups, linear or branched Cι-C6 alkoxyl groups, hydroxyl groups, linear or branched Cι~C6 alkyl groups; an acyl group of the alkyl ketone, aryl ketone or benzyl ketone type; a vinyl group; an allyl or methallyl group; an acrylic or methacrylic group; a heteroallyl group; a linear or branched C2-C6 alkenyl group, said alkenyl group optionally substituted with one or two N,N-dialkyl- (Ci- Cβ) -4-aniline groups; an N-2, 3-dihydroindoline group; a linear or branched Cι-C6 thioether group; two consecutive substituents between R3 and R6 can rep- resent the condensation points with other aromatic, heterocyclic or quinonic rings;
P represents a monocyclic or polycyclic aromatic nucleus, belonging to one of the following types: ben- zenic represented by general formula (VI); naphthalenic represented by general formula (VII); quinolinic repre-
sented by general formula (VIII); isoquinolinic repre-' sented by general formula (IX); cumarinic represented by general formula (X) ; quinazolinic represented by general formula (XI); phenanthrenic represented by general formula (XII); anthracenic represented by general formula (XIII); dibenzofuran represented by general formula (XIV) :
wherein: - at least two consecutive substituents between R8 and Ri3, Ri4 and R2ι, R22 and R28, R3o and R35, R36 and R41, R42 and R47, R48 and R57, Rss and R67, Rββ and R75, represent the condensation points with the oxazine or pyran ring, the other substituents having the meaning described for substituents R3, R4, R5 and Re;
Y represents CH or a nitrogen atom.
Preferred photochromatic compounds having general formula (I) for the purposes of the present invention, are those wherein:
X represents an oxygen atom;
R'ι represents a methyl;
R'2 represents an OH group; or a photochromatic com-
pound having general formula (II);
R' represents a linear or branched C1-C4 alkyl group; a linear or branched C2-C4 acyl group; a linear or branched C2-C4 heteroalkyl group in which the heteroa- torn is selected from nitrogen, oxygen, sulfur and selenium;
R' ' represents a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, or a phenyl group; Y represents N or CH; P' represents one of the groups having general formula (III), (IV) or (V) wherein:
R and R7, the same or different, represent one of the following groups: methyl, ethyl, isopropyl, 2- allyl, 2-methallyl, 2-hydroxyethyl, 2-carbo- xymethyl, phenyl, 4-N,N-dimethylaminoaniline, 4- methoxybenzene, 4-cyanobenzene;
Ri and R2, the same or different, represent a methyl or phenyl group; or considered jointly with the carbon atom to which they are bound, represent a cyclohexyl group;
R3, R4, R5 and R6, the same or different, represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, N,N-di- methylamine, piperidine, morpholine, carboxyl,
carboxymethyl, N,N-dimethylcarboxy-amide, cyano, ' nitro, methylketone, phenylketone, phenyl; P represents one of the groups having general formula from (VI) to (XIV), wherein: (a) two consecutive substituents between R8 and Ri3, Rι4 and R2ι, R22 and R28, R30 and R35, R3β and R4i, R42 and R47, R4s and R57, R58 and R6 , Rεs and R75, independently represent the condensation points with the oxazine or pyran ring; and the other substituents each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, 2-hydrcxyethyl, 2-allyl, piperidine, morpholine, N,N-dimethylamine, carboxyl, carboxymethyl, N,N-dimethylcarboxyamide, cyano, nitro, methylketone, ethylketone, phenylketone, methylthiol;
(b) two consecutive substituents between R8 and R13, Ri4 and R2ι, R22 and R28, R30 and R35, R30 and R4i, R42 and R47, R48 and R57, R58 and R67, Res and R75, different from those indicated under point (a) , represent the condensation points with the benzenic or qui- nonic ring.
Specific examples of preferred compounds according to the present invention are:
Compound having formula (la):
Compound having formula (lb):
A further object of the present invention relates to a process for the preparation of photochromatic compounds having general formula (I) .
The photochromatic compounds having general formula (I) can be prepared by the condensation of photochromatic
compounds having general formula (II)
wherein the substituents R', R'', P, P' and Y have the same meanings described above, with silylated tetramers having general formula (XV) :
wherein the substituents R'ι and X have the same meanings described above, in the presence of an inert organic solvent such as, for example, acetone, ethyl alcohol, isopropanol, toluene, dioxane, or a mixture of these solvents, at a temperature ranging from 50°C to 100°C, preferably from 60°C to 80°C, for a time ranging from 1 hour to 10 hours, preferably from 2 hours to 5 hours. The reaction product thus obtained is generally purified on a silica column, with subsequent
crystallization from a solvent such as, for example, ace- • tone, toluene, pentane, heptane, diethyl ether, or by repeated precipitations with methanol and dried with toluene. The photochromatic compounds having general formula (II) are obtained by the condensation of isoindoline compounds having general formula (XVI), or of indoline compounds having general formula (XVII), or of compounds deriving from propargyl alcohol having general formula (XVIII), or of compounds deriving from , β-unsaturated aldehydes hav- ing general formula (XIX) , with nitroso compounds or aldehyde compounds having general formula (XX) , or with hydroxy- aryl compounds having general formula (XXI), to give the respective photochromatic compounds having general formula (XVIa), (XVIIa) and (XVIIIa) , indicated in Schemes 1-4: Scheme 1
- 11
Scheme 2
Scheme 3
(XXI)
(XVIII) (XVIIIa)
Scheme 4
wherein the substituents R, from Rx to R7, R'', Y and P have the same meanings described above and Y' represents an NO or
CHO group.
The condensation reaction is carried out in the presence of an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, or a mixture of these sol- vents, and in the presence of an amine such as, for example, triethylamine, morphoiine, piperidine, or of an acid such as, for example, paratoluenesulfonic acid, sulfuric acid, acid alumina, or of a metal complex such as, for example, titanium (IV) tetraethoxide, at a temperature ranging from 50°C to 100°C, preferably from 60°C to 75°C, for a time ranging from 1 hour to 10 hours, preferably from 2 hours to 3 hours. The reaction product thus obtained is generally purified by elution on a silica column with subsequent crystallization from a solvent such as, for example, acetone, toluene, heptane, pentane, diethyl ether.
The isoindoline compounds having general formula (XVI) can be prepared according to processes known in the art and described, for example, in: "Tetrahedron" (1966), Vol. 22, page 2481; "Journal of Organic Chemistry" (1979), Vol. 44, page 1519; "Angewandte Chemie International (1968), Vol. 7, page 373.
The indoline compounds having general formula (XVII) can be prepared by the reaction of 2, 3, 3-trimethylindolenine compounds with an alkyl or (meth) allyl halide as described, for example, in Japanese patent application JP 03/176467.
The isoindoline compounds having general formula (XVI) and the indoline compounds having general formula (XVII), are usually kept in the form of salts such as, for example, iodides, bromides, chlorides, as the free base is very oxidable in air.
The compounds deriving from propargyl alcohol having general formula (XVIII) can be prepared by the reaction of ketone compounds with sodium acetylide in xylene or with a lithium/ethylenediamine acetylide complex as described, for example, in U.S. patents 5,585,042 and 5,238,981.
The compounds deriving from α, β-unsaturated aldehydes having general formula (XIX) can be prepared according to the processes known in the art as described, for example, in Japanese patent application JP 48/016481; or in "Organic Synthesis" (1970), Vol. 50, page 66.
The nitroso compounds having general formula (XX) can be prepared by the reaction of phenol compounds with nitrous acid or butyl nitrite, as described, for example, in Italian patent 1,176,858. The aldehyde compounds having general formula (XX) can be prepared by the reaction of phenol compounds with para- formaldehyde, hexamethylenetetramine, or acetic acid, followed by the addition of an aqueous solution of sulfuric acid at 60%-70%, as described, for example, in German patent DE 2,425,430.
The hydroxy-aryl compounds having general formula (XXI) are normally products which are commercially available such as, for example, β-naphthol or phenol.
Specific examples of isoindoline compounds having general formula (XVI), or indoline compounds having general formula (XVII), are the following:
CH-
Specific examples of nitroso compounds having general
formula (XX) are the following:
NO
NO
The photochromatic compounds having general formula (I) of the present invention are brightly yellow or dark yellow- coloured, oily or crystalline products.
Their solutions in common organic solvents such as, for example, benzene, toluene, methanol, ethanol, when exposed to light sources, are brightly yellow or dark yellow- coloured. These solutions, if exposed to a light source, either visible or ultraviolet, become blue or green. The colouring quickly decays when the light source is removed.
The photochromatic compounds having general formula (I) can be applied to the surface or incorporated in mass into the desired articles, using techniques already known in the art and described hereunder. Some polymeric photochromatic end-articles can be obtained with moulding techniques such as, for example, injection or compression moulding, starting from polymers in which one or more of the photochromatic compounds having formula (I) are homogeneously dispersed in mass. Alternatively, the photochromatic compounds having general formula (I) can be dissolved in a solvent, together with the polymeric material such as, for example, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate or epoxy, polysiloxane, urethane resin. The mixture thus obtained is deposited on a transparent carrier to form, after evaporation of the solvent, a photochromatic coating.
The photochromatic compounds having general formula (I) can also be added to a polymerizable monomer such as, for example, a meth (acrylic) or allyl carbonate monomer, so that, after polymerization carried out in the presence of a suitable initiator such as, for example, azo-bis (isobutyro- nitrile) in the case of the meth (acrylic) monomer or a per- oxyketal in the case of the allyl carbonate monomer, they are uniformly incorporated in the resin formed.
Finally, the photochromatic compounds having general ' formula (I) can be applied to a transparent substrate such as, for example, polycarbonate, polymethyl methacrylate or polydiethyleneglycol bis (allyl carbonate), by surface im- pregnation obtained by putting the substrate in contact, at a suitable temperature, with a solution or dispersion containing one or more of the photochromatic compounds having general formula (I), operating according to the method described, for example, in U.S. patent 5,130,353. The photochromatic compounds having general formula (I) of the present invention have the characteristic of being able to be incorporated in mass or using one of the techniques described above, into various organic polymers such as, for example, high density polyethylene (HDPE), low density poly- ethylene (LDPE) , ethylene-vinylacetate copolymer, polyether amides, polypropylene, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate, ep- oxy, polysiloxane or urethane resins, polycarbonate, polydi- ethylene glycol bis (allyl carbonate), polyamides, polyes- ters, polystyrene, polyvinylchloride, polyethylacrylate, siliconic polymers.
A further object of the present invention therefore relates to polymeric compositions comprising the above polymeric materials and the above photochromatic compounds hav- ing general formula (I) and the photochromatic articles ob-
tained from their processing.
The photochromatic compounds having general formula (I) of the present invention, are added to the above polymeric compositions in a quantity ranging from 0.01% to 5% by weight, preferably between 0.1% and 2% by weight, with respect to the weight of said polymeric compositions.
The photochromatic compounds having general formula (I) of the present invention can also be added to coating compositions, such as for example, paints, lacquers, paints or lacquers based on hybrid polysiloxanes and/or silica gel, compositions based on plastic materials. A further object of the present invention consequently relates to coating compositions, such as for example, paints, lacquers, paints or lacquers based on hybrid polysiloxanes and/or silica gel, compositions based on plastic materials, comprising said photochromatic compounds.
The photochromatic compounds having general formula (I) of the present invention are added to the above coating compositions in a quantity ranging from 0.01% to 5% by weight, preferably between 0.1% and 2% by weight, with respect to the weight of said coating compositions.
Paints or lacquers based on hybrid polysiloxanes and/or silica gel are obtained by means of the "sol-gel" process described, for example, by M. Nogami, Y. Abe in: "Journal of Materials Science" (1995), Vol. 3C, pages 5789-5792.
The above coating compositions can be applied to the substrate (metal, plastic, wood, etc.) using the conventional methods such as, for example, brushing, spraying, pouring, dipping or electrophoresis. The photochromatic compounds having general formula (I) of the present invention can optionally be used in the presence of usual additives for organic polymers such as, for example, phenolic antioxidants, sterically hindered amines, benzotriazoles, benzophenones, phosphites or phosphonites . The photochromatic compounds having general formula (I) of the present invention which, as already mentioned above, have a brightly yellow or dark yellow colouring, can be used as such, mixed with each other, or combined with other suitable organic photochromatic compounds in order to obtain, after activation, the formation of other colourings such as brown and grey. For this purpose, photochromatic compounds belonging to the group of spiro-indolino-oxazines or spiro- pyrans described in the art such as, for example, in U.S. patent 5,066,818, are particularly useful for the purpose. Some illustrative examples are provided hereunder for a better understanding of the present invention and for its embodiment but in no way limit the scope of the invention itself. EXAMPLE 1 Preparation of 1 , l,4,7-tetramethyl-N-allyl~3-methylene-
isoindoline iodide having formula (XV ')~A:
CH2 (XVI')-A CH
CH2
40 g of acetonylacetone, 16 g of allylylamine hydrochloride, 20 ml of water and 12 ml of ethyl alcohol are charged into a 100 ml flask, equipped with a reflux cooler and mechanical stirrer.
The above mixture is heated to 80°C, under a nitrogen atmosphere, for 24 hours. At the end, the mixture is cooled and subsequently extracted with 30 ml of hexane. The aqueous phase obtained is treated with aqueous sodium hydroxide (solution at 30%) until pH 14 is reached: a yellow-white precipitate is thus formed which is rapidly filtered and washed with 30 ml of water and 10 ml of hexane.
The product is dried under vacuum and conserved in a nitrogen atmosphere: the yield is 31.5 g. This product is identified as 1, 1, 4,7-tetramethyl-isoindoline, by gas-mass (molecular weight = 227) .
A quantity equal to 31.5 g of the above product is placed in a 100 ml inox steel autoclave together with 20 ml of toluene and 23.8 g of methyliodide. The autoclave is heated to 85°C and is maintained at this temperature, under a nitrogen atmosphere, for 6 hours. At the end, the autoclave is cooled to room temperature and the raw product is filtered obtaining a crystalline precipitate which is washed with 20 ml of ethyl acetate and finally with 20 ml of hexane.
43.6 g of product are obtained, corresponding to 1,1,4, 7-tetramethyl-N-allyl-3-methylene-isoindoline iodide having formula (XVI') -A. The free base, corresponding to Compound (XVI'), is identified by gas-mass (molecular weight = 241) and the salt by NMR. EXAMPLE 2 Preparation of the compound having formula (XVTa) -1 :
The above mixture is heated to 70 °C and maintained at this temperature, under stirring, under a nitrogen atmosphere, for 1 hour. The reaction raw product obtained is filtered and subsequently purified by passage on a neutral col- umn of active aluminum oxide 90 (activity degree I), eluting with a mixture of heptane/ethyl acetate in a ratio of 1/1.
An almost pure photochromatic product (yellow solid) is obtained which is further purified by crystallization from pentane. After crystallization, 2 g of a solid, white product are obtained, corresponding to the compound having formula (XVIa)-l which is identified by gas-mass (molecular weight = 422) . EXAMPLE 3 Preparation of l,l-dimethyl-N-methyl-allyl-2-methylene- indoline iodide having formula (XVII') -A:
7,2 g of 2, 3, 3-trimethylindoline, 8.1 g of potassium iodide, 5.4 g of allylamine hydrochloride, 20 ml of water and 12 ml of acetonitrile are charged into a 100 ml closed test-tube.
The above mixture is heated to 90 °C for 8 hours. At the end, the raw product obtained is washed with water, with toluene and with hydrochloric acid until pH 7.
The aqueous phase is further washed with toluene, treated with aqueous sodium hydroxide (solution at 30%) until reaching pH 14 and with toluene. The organic phases obtained are concentrated and dried.
A pinkish-brown oil is obtained: the yield is 8.3 g. This product is identified as 1, l-dimethyl-N-methylallyl-2- methylene-indoline iodide by gas-mass (molecular weight = 213) . EXAMPLE 4 Preparation of the compound having formula (XVIIa) -1 :
(XVIIa)-l
1.7 g of 1, l-dimethyl-N-methyl-allyl-2-methylene- indoline iodide obtained as described in Example 3, 1.73 g of the sodium salt of l-nitroso-2-naphthol and 8 ml of toluene, are charged into a 250 ml flask equipped with a reflux cooler and mechanical stirrer.
The above mixture is heated to 90 °C and maintained at this temperature, under stirring, under a nitrogen atmosphere, for 6 hours. The raw reaction product obtained, is dried and repeatedly extracted with boiling heptane to which 1 g of activated carbon has been added. The heptane extracts are concentrated and boiled with an additional 0.6 g of activated carbon.
The reaction raw product obtained is filtered and subsequently purified by passage on a silica column eluting with a mixture of toluene/hexane in a ratio of 1/1.
An almost pure photochromatic product (yellow-white solid) is obtained, which is further purified by crystallization from toluene.
After crystallization, 1.2 g of a solid white product are obtained, corresponding to the compound having formula (XVIIa)-l which is identified by gas-mass (molecular weight = 368) . EXAMPLE 5 Preparation of the compound having formula (XVIIa) -2
(XVIIa)-2
16 g of 2, 7-dihydroxynaphthalene, 7.0 g of sodium nitrate, 100 ml of water and 4.0 g of sodium hydroxide are charged into a 250 ml flask, equipped with a reflux cooler and mechanical stirrer.
The above mixture is stirred, under a nitrogen atmos- ' phere, until dissolution. 10.7 g of sulfuric acid diluted in 30 ml of water are subsequently added dropwise and the reaction temperature is maintained at 0°C to 5°C. After 30 min- utes at this temperature, the reaction raw product is filtered, washed with water and dried in air. 18.6 g of a dark brown powder corresponding to 2, 7-dihydroxy-l-nitroso- naphthalene, are obtained.
18.6 g of 2, 7-dihydroxy-l-nitroso-naphthalene are mixed with 17 g of indoline and 30 ml of isopropyl alcohol: the mixture obtained is maintained for 3 hours at reflux temperature.
At the end of the reaction, the solvent is eliminated by distillation under vacuum and 40 ml of toluene and 2.0 g of activated carbon are subsequently added. This mixture is heated to 7C°C for 15 minutes: the reaction raw product is filtered, concentrated and cooled.
The precipitated raw product is filtered obtaining 7.0 g of a solid white product corresponding to the Compound having formula (XVIIa) -2 which is identified by gas-mass (molecular weight = 344. EXAMPLE 6 Preparation of the compound having formula (XVIIa) -3 :
6.9 g of Compound (XVIIa) -2 obtained in Example 5, 25 ml of toluene, 25 ml of acetonitrile and 4 ml of triethylamine are charged into a 250 ml flask, equipped with a reflux cooler and mechanical stirrer, obtaining a solution which is not completely homogeneous. This solution is maintained under a stream of nitrogen to prevent the product from oxidation. The above mixture is heated to 20 °C and a solution of 1.8 g of acryloyl chloride in 10 ml of toluene are added dropwise, obtaining a crystalline precipitate. After 10 minutes 50 ml of water and 5.0 g of sodium carbonate are added; the mixture is stirred and the two phases are separated. The organic phase is concentrated under vacuum obtaining a dark oil which is cooled.
The precipitated raw product is filtered obtaining 6.3 g of a solid white product corresponding to the Compound
having formula (XVIIa) -3 which is identified by gas-mass
(molecular weight = 398) .
EXAMPLE 7
Preparation of the compound having formula (la) :
0.15 g of 2, 4, 6, 8-tetramethylcyclotetrasiloxane of Al-
drich (95%), a catalytic quantity of the complex platinu -
divinyltetramethyl-disiloxane and 10 ml of anhydrous toluene
are charged into a 100 ml flask, equipped with a reflux
cooler and mechanical stirrer. The mixture is maintained at
60°C, under stirring and in a nitrogen atmosphere, for 5
minutes.
1.0 g of the Compound (XVI-a)-l, obtained as described ■ in Example 2, dissolved in 20 ml of anhydrous toluene is then added: this mixture is maintained at 80°C for 3 hours. At the end the solvent is eliminated by evaporation under vacuum.
The reaction raw product obtained is purified by passage on a silica column, eluating with ethyl acetate and then with acetone.
0.28 g of a product (dark yellow oil) are obtained, corresponding to the Compound having formula (la), which is identified by liquid chromatography coupled with a mass spectrometer (molecular weight = 1116.5) . EXAMPLE 8 Preparation of the compound having formula (lb) :
0.10 g of 2, 4, 6, 8-tetramethylcyclotetrasiloxane of Al- drich (95%), a catalytic quantity of the complex platinum- divinyltetramethyl-disiloxane and 5.0 ml of anhydrous toluene are charged into a 100 ml flask, equipped with a reflux cooler and mechanical stirrer. The mixture is maintained at 80°C, under stirring and in a nitrogen atmosphere, for 5 minutes.
0.8 g of the Compound (XVII-a)-l, obtained as described in Example 4, dissolved in 20 ml of anhydrous toluene are then added: this mixture is maintained at 80°C for 4 hours. At the end the solvent is eliminated by evaporation under vacuum.
- 31
The reaction raw product obtained is purified by repeated precipitations with methanol and dried with toluene.
0.25 g of a product (dark yellow oil) are obtained, corresponding to the Compound having formula (lb), which is identified by liquid chromatography coupled with a mass spectrometer (molecular weight = 1360.5). EXAMPLE 9 Preparation of the compound having formula (Ic) :
1.8 g of the Compound (XVII-a)-3, obtained as described in Example 6, dissolved in 40 ml of anhydrous toluene are then added: this mixture is maintained at 70 °C for 8 hours.
At the end the solvent is eliminated by evaporation under vacuum.
The reaction raw product obtained is purified by repeated precipitations with methanol and dried with toluene. 0.85 g of a product (dark yellow oil) are obtained, corresponding to the Compound having formula (Ic) , which is identified by liquid chromatography coupled with a mass spectrometer (molecular weight = 1832.5). EXAMPLE 10 Evaluation of the photochromatic activity.
The photochromatic activity is evaluated in ethanol, at 10°C, of Compounds (Ia)-(Ic) obtained as described in Examples 7-9.
Solutions are prepared at a concentration equal to 10~4 M of the various Compounds (Ia)-(Ic) in ethanol and subse-
quently 2 ml of each solution i? placed in a 1 cm quartz cell.
The quartz cell containing the solution is introduced into a temperature control system, equipped with a magnetic stirrer (the solution is maintained under stirring during the measurement) . The spectrum of the activated and deactivated forms and the decolouring kinetics are registered with a UV/visible spectrophotometer with a photodiode detector (HP 8453) equipped with perpendicular optical fibres which give a continuous monochromatic irradiation. The light source is a high pressure Hg lamp and the irradiation wave length is determined by monochromatic filters. This system allows the absorbance to be contemporaneously monitored at all wave-lengths. The following parameters are determined using the measurements obtained as described above and with a calculation effected with the GRAFit program of Erithaeus Software Ltd. for the mathematical treatment of the graphs: tι/2 (s) : time in which the absorbance of the merocya- nine open form is equal to half of the initial absorbance value; kΔ (s_1) : constant of the oxazine ring closing thermal reaction rate; λPMC (nm) : wave-length of the maximum absorbance of the merocyanine open form;
colourability: difference between the final absorbance and initial absorbance of the merocyanine open form.
The data obtained analyzing Compounds (Ia)-(Ic) are compared with the data obtained using Compounds (XVIa)-l, (XVIIa) -1 and (XVIIa) -3: Compounds (la) - (Ic) show an increase in the value of the kΔ (s_1) constant.
The data obtained are indicated in Table 1.
TABLE 1
*: the samples analyzed have two values of the kΔ
constant .
Claims
1. Photochromatic compounds having general formula (i;
X represents an oxygen atom; a sulfur atom; a selenium atom; an NH group; or an NRa group wherein Ra represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group option- ally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Cχ-Cιo alkyl groups, linear or branched Cι-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2, 6, 6-tetramethylpiperidine group;
R'╬╣ represents a linear or branched C-i-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched C╬╣-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a vinyl group; an allyl or methallyl group; a linear or branched C2-C6 alkenyl group; an aryl group selected from phenyl, diphenyl and naphthyl, said aryl group optionally substituted with linear or branched C╬╣~C6 alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (Ci-C╬▓) amine groups; a COOR'a ester group wherein R'a represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched C╬╣-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6- tetramethylpiperidine group;
R'2 represents an OH group; or a photochromatic compound having general formula (II) : 
R' represents a linear or branched Ci-Cio alkyl group; a linear or branched C2-C╬╣o acyl group; a linear or branched C2-C╬╣0 heteroalkyl group in which the heteroatom is selected from nitrogen, oxygen, sulfur and selenium;
R' ' represents a hydrogen atom; a halogen atom selected from fluorine, chlorine and bromine; a linear or branched Ci-C╬╡ alkyl group; a linear or branched C╬╣~C6 alkoxyl group; a phenyl group; a phenoxyl group;
P' represents one of the following groups having general formula (III), (IV) or (V):
R and R7, the same or different, represent a linear or branched Ci-Cio alkyl group, said alkyl group op- tionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci~C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a vinyl group; an allyl or methallyl group; a linear or branched C2-C╬▓ alkenyl group; an aryl group selected from phenyl, diphenyl and naphthyl, said aryl group optionally substi- tuted with linear or branched C╬╣-C6 alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (C╬╣-C6) amine groups; a COOR'a ester group wherein R'a represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group optionally substi- tuted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched C╬╣-C10 alkyl groups, linear or branched Cj-C╬▓ alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6, 6-tetramethylpiperidine group; Ri and R2, the same or different, represent a linear or branched Ci-Cio alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched C╬╣-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a vinyl group; an allyl or methallyl group; an acrylic or methacrylic group; a heteroallyl group; a linear or branched C2-C╬╣0 alkenyl group; a COOR'a ester group wherein R'a represents a linear or branched Ci-Cio alkyl group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched C╬╣-C6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperidine group; a linear or branched Ci-C╬▓ alkoxyl group; an N-alkyl (C╬╣-C6) amine group; an N,N-dialkyl (Ci-C╬▓) amine group; or
Ri and R2, considered jointly with the carbon atom to which they are bound, represent a C4-C╬╣0 cycloalkyl group, said cycloalkyl group optionally substituted with halogen atoms selected from fluorine, chlorine and bromine, or with hydroxyl groups, linear or branched Cj-C╬▓ alkoxyl groups, carboxyl groups, cyano groups, amine groups, N-alkyl (C╬╣-C6) amine groups, N,N-dialkyl (C╬╣-C6) amine groups; an N,N-dialkyl (C╬╣-C6) amide group; an aryl group se- lected from phenyl and bip enyl; a cyano group;
R3, R4, R5 and R6, the same or different, represent a hydrogen atom; a halogen atom selected from fluorine, chlorine, bromine and iodine; a linear or branched C╬╣-C6 alkyl group, said alkyl group op- tionally substituted with 1-6 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-C╬╡ alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetramethylpiperid- ine group; a benzyl group, said benzyl group optionally substituted with 1-5 halogen atoms selected from fluorine, chlorine and bromine, or with C(X')3 groups wherein X' is selected from fluorine, chlorine and bromine, hydroxyl groups, linear or branched Ci-Cio alkyl groups, linear or branched Ci- Ce alkoxyl groups, carboxyl groups, cyano groups, or with a 2,
2, 6, 6-tetramethylpiperidine group; a hydroxyl group; a linear or branched Ci-C╬▓ alkoxyl group; an amine group; an N-alkyl (d-C6) amine group; an N,N-dialkyl (Ci-C╬▓) amine group; a piperidine, piperazine or morpholine group; a C╬╣-C6 carboxyalkyl group; a C2-C╬┤ carboxyalkenyl group; a carboxyamide group; an N-alkyl (C╬╣~C6) carboxyamide group; an N,N-dialkyl (Ci-C╬▓) carboxyamide group; a cyano group; a nitro group; a sulfonic group; an aryl group selected from phenyl, biphenyl and naph- thyl, said aryl group optionally substituted with N,N-dialkyl (C╬╣-C6) amine groups, linear or branched C╬╣-C6 alkoxyl groups, hydroxyl groups, linear or branched Ci-C╬▓ alkyl groups; an acyl group of the alkyl ketone, aryl ketone or benzyl ketone type; a vinyl group; an allyl or methallyl group; an acrylic or methacrylic group; a heteroal- lyl group; a linear or branched C2-C6 alkenyl group, said alkenyl group optionally substituted with one or two N,N-dialkyl- (C╬╣-C6) -4-aniline groups; an N-2,
3-dihydroindoline group; a linear or branched Ci-C╬╡ thioether group; two consecutive substituents between R3 and Re can represent the condensation points with other aromatic, heterocyclic or quinonic rings; P represents a monocyclic or polycyclic aromatic nucleus, belonging to one of the following types: benzenic represented by general formula (VI); naph- thalenic represented by general formula (VII) quinolinic represented by general formula (VIII) isoquinolinic represented by general formula (IX) cumarinic represented by general formula (X) quinazolinic represented by general formula (XI) phenanthrenic represented by general formula (XII) anthracenic represented by general formula (XIII) dibenzofuran represented by general formula (XIV) :
wherein: at least two consecutive substituents between R8 and R╬╣3, R14 and R2╬╣, R22 and R28, R30 and R35, 36 and R41, R42 and R47, R4s and R57, Rss and R67/ Res and R75, represent the condensation points with the oxazine or pyran ring, the other substituents having the meaning described for substituents R3, R4, R5 and
Re; Y represents CH or a nitrogen atom. 2. The photochromatic compounds having general formula (I) according to claim 1, wherein:
X represents an oxygen atom; - R'╬╣ represents a methyl;
R'2 represents an OH group; or a photochromatic compound having general formula (II); R' represents a linear or branched C╬╣~C alkyl group; a linear or branched C2-C4 acyl group; a linear or branched C2-C4 heteroalkyl group in which the heteroatom is selected from nitrogen, oxygen, sulfur and selenium;
R' ' represents a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, or a phenyl group; - Y represents N or CH;
P' represents one of the groups having general formula (III), (IV) or (V) wherein:
R and R7, the same or different, represent one of the following groups: methyl, ethyl, isopropyl, 2-allyl, 2-methallyl, 2-hydro- xyethyl, 2-carboxymethyl, phenyl, 4-N,N- dimethylaminoaniline, 4-methoxybenze-ne,
4-cyanobenzene;
Ri and R2, the same or different, represent a methyl or phenyl group; or considered jointly with the carbon atom to which they are bound, represent a cyclohexyl group;
R3, R4, R5 and Re, the same or different, represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, N,N-dimethylamine, piperidine, morpholine, carboxyl, carboxymethyl, N,N-dimethylcarboxyamide, cyano, nitro, meth- ylketone, phenylketone, phenyl;
P represents one of the groups having general formula from (VI) to (XIV), wherein:
(a) two consecutive substituents between R8 and R13, R14 and R2i, R22 and R28, R30 and R35, R36 and R4i, R42 and R4 , R48 and R57, 58 and R╬╡ ,
R68 and R75, independently represent the condensation points with the oxazine or pyran ring; and the other substituents each independently represent a hydrogen atom, a fluo- rine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, 2-hydroxyethyl, 2-allyl, piperidine, morpholine, N,N- dimethylamine, carboxyl, carboxymethyl, N,N- dimethylcarboxyamide, cyano, nitro, methylke- tone, ethylketone, phenylketone, methylthiol; (b) two consecutive substituents between R8 and R13, Ri4 and R21, R22 and R28, R30 and R35, R36 and R41, R42 and R47, R48 and R57, R58 and R6 , R68 and R75, different from those indicated under point (a) , represent the condensation points with the benzenic or quinonic ring. The photochromatic compound having general formula (I) according to claim 1 or 2, consisting of the compound having formula (la) :
The photochromatic compound having general formula (I) according to claim 1 or 2, consisting of the compound having formula (lb) :
5. The photochromatic compound having general formula (I) according to claim 1 or 2, consisting of the compound having formula (Ic) :
A process for the preparation of the photochromatic compounds having general formula (I) according to any of the previous claims, comprising the condensation of photochromatic compounds having general formula (II) :
wherein the substituents R'i and X have the same meanings described above, in the presence of an inert organic solvent, or a mixture of inert organic solvents, at a temperature ranging from 50┬░C to 100┬░C, for a time ranging from 1 hour to 10 hours.
7. The process according to claim 6, wherein the inert organic solvent is selected from: acetone, ethyl alcohol, isopropanol, toluene, dioxane, or from mixtures of these solvents.
8. The process according to claim 6 or 7, wherein the reaction temperature ranges from 60┬░C to 80┬░C.
9. The process according to claim 6, 7 or 8, wherein the reaction time ranges from 2 hours to 5 hours.
10. Polymeric compositions comprising at least one photo-
- 5! chromatic compound according to any of the claims from 1 to 9, and at least one organic polymer selected from high density polyethylene, low density polyethylene, ethylene-vinylacetate copolymer, polyether amides, polypropylene, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate, ep- oxy, polysiloxane or urethane resins, polycarbonate, polydiethylene glycol bis (allyl carbonate), polyamides, polyesters, polystyrene, polyvinyl chloride, polyethyl- acrylate, siliconic polymers.
11. Coating compositions, such as paints, lacquers, paints or lacquers based on hybrid polysiloxanes and/or silica gel, compositions based on plastic materials, comprising one or more of the photochromatic compounds having general formula (I) according to any of the claims from 1 to 9.
12. The compositions according to claim 10 or 11, comprising additives for organic polymers selected from phenol antioxidants, sterically hindered amines, benzotri- azoles, benzophenones, phosphites or phosphonites.
13. Photochromatic articles obtained from the processing of the compositions according to any of claims 10, 11 or 12.
14. Mixtures comprising at least one photochromatic com- pound having general formula (I) according to any of the claims from 1 to 9 and at least one photochromatic compound belonging to the group of spiro-indolino- oxazines or spiro-pyrans.
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| IT98MI001690A ITMI981690A1 (en) | 1998-07-22 | 1998-07-22 | "PHOTOCROMATIC COMPOUNDS PROCEDURE FOR THEIR PREPARATION AND THEIR USE IN POLYMER MATERIALS" |
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| WO2004065464A1 (en) * | 2003-01-24 | 2004-08-05 | Sunbow Co., Ltd. | Process for preparing polypropylene resin containing photochromic compounds and polypropylene yarn produced using polypropylene resin |
| US7465415B2 (en) | 2004-07-30 | 2008-12-16 | Ppg Industries Ohio, Inc. | Photochromic materials derived from ring-opening monomers and photochromic initiators |
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| WO2004052966A1 (en) * | 2002-12-09 | 2004-06-24 | Hetero Drugs Limited | A novel polymorph of clopidogrel hydrogen sulfate |
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| US7465415B2 (en) | 2004-07-30 | 2008-12-16 | Ppg Industries Ohio, Inc. | Photochromic materials derived from ring-opening monomers and photochromic initiators |
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| US9139552B2 (en) | 2005-04-08 | 2015-09-22 | Transitions Optical, Inc. | Indeno-fused naphthopyrans having ethylenically unsaturated groups |
| WO2010020770A1 (en) | 2008-08-18 | 2010-02-25 | James Robinson Limited | Polydialkylsiloxane-bridged bi-photochromic molecules |
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Also Published As
| Publication number | Publication date |
|---|---|
| ITMI981690A1 (en) | 2000-01-22 |
| ITMI981690A0 (en) | 1998-07-22 |
| AU5158599A (en) | 2000-02-14 |
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