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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
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  • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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  • C03—GLASS; MINERAL OR SLAG WOOL
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  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
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  • 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
• • 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
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  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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  • C09K2211/1003—Carbocyclic compounds
  • C09K2211/1011—Condensed systems
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/14—Macromolecular compounds
  • C09K2211/1441—Heterocyclic
  • C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
• • 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

Definitions

• the present invention relates to photochromic molecules, in particular bi-photochromic molecules comprising a polydialkylsiloxane oligomer linker, and to products comprising them.
• Photochromism is a well known physical phenomenon, which is defined as "a reversible transformation of a single chemical species being induced in one or both directions by electromagnetic radiation between two states having different distinguishable absorption spectra".
• a detailed discussion of this phenomenon can be found in "Photochromism : Molecules and Systems", revised edition, edited by H. Durr and H. Bouas-Laurent, Elsevier, 2003.
• a review of the major classes of organic photochromic molecules can be found in Organic Photochromic and Thermochromic Compounds, Volume 1 , Main Photochromic Families", edited by J. Crano and R. Guglielmetti, Plenum Press, 1999.
• a detailed review of photochromic naphthopyrans can be found in "Functional Dyes", edited by Sung-Hoon Kim, pages 85-137, Elsevier, Amsterdam, 2006.
• Polymerisable groups have been attached to oxazines (US 5821287, National Science Council Taiwan). Polymerisable polyalkoxylated pyrans have been claimed by PPG (WO 00/15629) and Transitions (WO 03/56390).
• Rodenstock (EP 0686685) have linked pyrans by means of a -CH 2 CH 2 - bridge which, it is taught, does not affect the photochromic properties of the photochromic moieties: it is therefore clear that this bridge does not give any advantages in terms of improved properties such as fade rate or colour intensity.
• Zhao and Carreira JACS 2002, 124, 8, p1582 have prepared bis-naphthopyrans linked by a bis-thiophene, by phenyl groups (Organic Letters, 2006, VoI 8 No. 1 , p99) and by oligothiophenes (Chenn. Eur. J.
• Coelho et al (Tetrahedron, 2005, 61 , p11730) have linked pyrans by means of phenyl, phenyl-O- phenyl, and phenyl-CH 2 CH 2 -phenyl bridges.
• Great Lakes (WO 00/39245) claim a trimeric species where three oxazines are attached to a central triazine.
• Great Lakes (WO 00/05325 and WO 00/21968) also claim compounds where two, three or four oxazines are linked to a central tetramethylcyclotetrasiloxane ring.
• a bi- photochromic molecule comprising two photochromic moieties linked via a polydialkylsiloxane oligomer.
• bi-photochromic molecule having the structure set out in claim 4.
• an ophthalmic lens comprising a bi-photochromic molecule according to the invention.
• the invention provides a polymeric host material comprising a bi- photochromic molecule according to the invention.
• the molecules exhibit a considerable improvement in the rate of fade in polymer matrices compared to the parent photochromic molecules.
• the compounds of the invention often exhibit increased strength of photochromic colour compared to the parent photochromic molecule, allowing for molecular weight and the number of photochromic units present.
• the compounds of the invention are particularly useful for use in photochromic ophthalmic lenses. It has also unexpectedly been found that these molecules have improved heat stability when incorporated into polymers, compared to the individual photochromic molecules which are not linked by the bridging group. This allows the molecules of the invention to be incorporated into polymers which require higher processing temperatures than are compatible with the unlinked photochromic molecules.
• the molecules of this invention also have the beneficial property of a lower yellowness index compared to the individual photochromic molecules which are not linked via a polydialkylsiloxane oligomer when processed at the same temperature in the same polymer.
• the compounds of the invention have advantages of improved fade rate, improved photochromic colour strength, increased heat stability and reduced yellowness index when compared to the known bi-photochromic compounds comprising bridging groups.
• two photochromic molecules are linked by means of a bridge which comprises a linking group at each end of a central polydialkylsiloxane (PDAS) chain to provide novel polydialkylsiloxane bridged bi- photochromic molecules.
• PDAS polydialkylsiloxane
• the bridge consists of a linking group at each end of a central PDAS chain.
• the photochromic units may be the same or different, allowing for the possibility of different chromophores with different fade rates to be present in the same molecule.
• the molecules of the invention comprise two photochromic moieties or molecules linked via a polydialkylsiloxane chain.
• the polydialkylsiloxane bridge, or linker comprises a linking group at each end.
• the bridge, or linker consists of a linking group at each end of a central polydialkylsiloxane chain. Any suitable polydialkylsiloxane chain and linking groups may be employed.
• the compounds are of the general formula: PC-L-PDAS-U-PC wherein PC and PC represent a photochromic moiety; PDAS represents a polydialkylsiloxane chain; and L and L' represent linking groups.
• PC and PC may be the same or different. It is particularly preferred that PC and PC independently represent photochromic moieties of general structure I to IV:
• R1 and R2 independently represent hydrogen, linear or branched C 1-10 alkyl, linear or branched Ci- I0 alkoxy, C 1 . 10 hydroxyalkoxy, C-MO alkoxy(Ci_io)alkoxy, phenyl, Ci-io alkoxyphenyl, halogen, C 1 . 5 haloalkyl, C 1 - 5 alkylamino, Ci -5 dialkylamino, arylamino, diarylamino, aryl C 1 . 5 alkylamino, or a cyclic amino group;
• R3 represents hydrogen, linear or branched C 1-10 alkyl, C 3 -C20 cycloalkyl, C 6 -C 2 O bicycloalkyl, linear or branched C 2- io alkenyl, linear or branched C 1-10 alkoxy, C 1-10 hydroxyalkyl, C 1-10 aminoalkyl, linear or branched Ci -20 alkoxycarbonyl, carboxyl, halogen, aryloxycarbonyl, formyl, acetyl or aroyl;
• R4 represents phenyl, C 1- - I0 alkoxyphenyl, Ci- 10 dialkoxyphenyl, C 1 - I0 alkylphenyl, Ci- 10 dialkylphenyl, in addition to those groups specified for R3;
• R5, R6, R7, R8, R9, R10, R14, R15, R16 are as defined above for R1 and R2;
• R11 represents linear or branched Ci_ 2 o alkyl, C3-C2 0 cycloalkyl, C 6 -C2o bicycloalkyl, (Ci -5 alkyl)aryl, (Ci -5 alkyl)cycloalkyl, (Ci -5 alkyl) bicycloalkyl, Ci -5 haloalkyl, Ci -5 dihaloalkyl or Ci -5 trihaloalkyl;
• R12 and R13 represent C-M O alkyl, Ci -5 alkyl alkoxycarbonyl, or together form a C 5-7 ring;
• R17 and R18 represent linear or branched C-MO alkyl, Ci_i 0 hydroxyalkyl, or together form a C 5-7 ring.
• L and L' which may be the same or different, represent a linking group. Any suitable linking group may be used. It is preferred that L and L' represent a linking group of the form
• Y is independently oxygen or sulphur
• R19 is hydrogen or C-i-io linear or branched alkyl
• R20 is Ci-i 0 linear or branched alkyl
• p is an integer from 1 to 15
• r is an integer from 0 to 10
• Q is linear or branched Ci-i 0 alkyl, C-M O alkenyl or 1 ,2-, 1 ,3, or 1 ,4-substituted aryl, or substituted heteroaryl.
• Y is oxygen.
• Particularly preferred linker groups L and L' are:
• PDAS represents a polydialkylsiloxane chain.
• PDAS represents an oligomer of the form
• R19 is C-i.-to alkyl, and n is an integer of from 4 to 75.
• Polydialkylsiloxane oligomers are commercially available, for example from Gelest Inc, Shin-Etsu Chemical Co. Ltd; Chisso Corp; Toshiba Silicone Co. Ltd; and Toray-Dow Corning Co. Ltd.
• Suitable polydialkylsiloxane oligomers include, but are not limited to, polydimethylsiloxane oligomers, such that R19 is preferably methyl.
• n is between 6 and 30 inclusively.
• R19 is methyl and n is an integer of from 6 to 30.
• Preferred polydimethylsiloxane oligomers include the oligomers DMS-B12, DMS-C15, DMS-C16, DMS-C21, DMS-A11, DMS-A12, DMS-A15, DMS-A21 , DMS-A211 and DMS-A214 available from Gelest Inc; KF-6001, KF-6002, KF-6003, KF-8010, X-22- 160AS, X-22-162A, X-22-161A, X-22-161B and X-22-162C from Shin-Etsu; and Silaplane FM-44 from Chisso.
• oligomers DMS-B 12, DMS- C15, DMS-C16, DMS-C21, DMS-A11, DMS-A12, DMS-A15, DMS-A21 , DMS-A211 and DMS-A214 from Gelest are quoted as having the following structures and approximate molecular weight or molecular weight ranges.
• the Gelest nomenclature is used to name the following polydimethylsiloxane oligomers, rather than the cumbersome (and not strictly accurate, as the oligomers are mixtures) systematic names.
• DMS-A12 Molecular weight range 900 - 1000 NH 2 - (CH 2 ) 3 —Si- ⁇ -f-Si-o-h ⁇ ii-(CH 2 ) 3 — NH 2
• polydimethylsiloxane oligomers are generally supplied either with an average molecular weight or a molecular weight range, and any number quoted as the number of repeat units of the dimethylsiloxane is to be interpreted as an average value.
• the parent photochromic compounds may be prepared as described in US 5,650,098 (1 ,2-b naphthopyrans), US 5,623,005 (2,1-b naphthopyrans), US 5,446,151 (2,1-b naphthoxazines), and US 6,303,673 (1 ,2-b naphthoxazines).
• linking group is attached to the commercially available oligomer, if required, and this reagent is then reacted with the parent photochromic compound to give the polydialkylsiloxane-bridged bi-photochromic molecule.
• the linking group may also be attached to the parent photochromic compound, which is then reacted with the commercially available oligomer to give the polydialkylsiloxane-bridged bi-photochromic molecule. Suitable reaction conditions will be apparent to the skilled person.
• polydimethylsiloxane oligomers are supplied either with an average molecular weight or a molecular weight range, and any number quoted as the number of repeat units of the dimethylsiloxane is to be interpreted as an average value. Accordingly, any yields quoted in the following Examples are inevitably approximate.
• the oligomers DMS-B12, DMS-C15, DMS-C16 and DMS-A214 are available from Gelest Inc. and are quoted as having the following structures and approximate molecular weight or molecular weight ranges.
• the reagent bis-phthaloyl-DMS-C15 was prepared in analogous fashion to bis-succinyl- DMS-C15 in Example 1 , using an equivalent quantity of phthalic anhydride in place of succinic anhydride.
• Example 5 (1.3-Dihvdro-3,3-dimethyl-1-neopentyl-6'-(4"-N-ethyl, N- (succinvlethvl)anilino)spiror2H-indole-2,3'-3H-naphtho ⁇ ,2-biM ,41oxazine) ? - DMS-C 15
• TLC thin layer chromatography
• Example 7 (1.3-Dihvdro-3,3-dimethyl-1-isobutyl-9'-succinyl-spiror2H-indole-2,3'-3H- naphthor2,1-bi ⁇ ,41oxazine)g-DMS-C16
• Dicyclohexyl carbodiimide (0.90 g) was added, and the mixture stirred for 2 hours at room temperature. TLC (5:1 toluene:EtOAc) indicated that the two starting material photochromies had been consumed. The mixture was filtered to remove dicyclohexyl urea, which was washed with toluene (5 ml). The solution was used for chromatography, eluting with a mixture of toluene and ethyl acetate.
• Example 11 (1 ,3-Dihvdro-3,3-dimethyl-1 -neopentyl-9'-succinyl-spiror2H-indole-2,3'- 3H-naphthor2.1-biri .4loxazine1) ? -DMS-A214
• 2,2-Bis(4'-methoxyphenyl)-5-hydroxymethyl-6-methyl-2H-naphtho[1 ,2-b]pyran was mixed with bis-succinyl-DMS-C15 (2.0 g), toluene (20 ml) and dimethylaminopyridine (0.05 g). This was stirred for 2 minutes, then dicyclohexyl carbodiimide (0.51 g) was added. The mixture was stirred for 45 minutes and TLC (3:1 toluene: EtOAc) indicated a main spot for polydialkylsiloxane-bridged bi-photochromic product, with effectively no starting material remaining. The mixture was cooled in an ice bath for 1 hour, then was filtered and the dicyclohexyl urea washed with toluene (5 ml).
• the parameter "Adjusted Delta Abs” allows for the molecular weight of the polydialkylsiloxane-bridged bi-photochromic compound, the molecular weight of the unbridged comparative compound and the number of photochromic units present. This is calculated as follows:
• Adjusted Delta Abs (Delta Abs Example compound x (MoI Wt example compound)/(Mol Wt comparative compound))/Number of photochromic units present in Example compound
• Example 10 which has a different photochromic unit at each end of the chain, the absorptions from each photochromic unit are treated separately.
• the Ti # values for the tailed dimers are between 29.4% and 65.4% of the T 1/2 values of the corresponding comparative compounds.
• the T 3/ 4 values of the tailed dimers show even greater improvements, being between 13.9% and 40.0% of the T 3/4 values of the corresponding comparative compounds.
• Samples of compounds of Example 7 and Example 12 and the corresponding comparative compounds C4 and C2 were incorporated at 250 ppm into polycarbonate, and polystyrene at different processing temperatures using a Boy 35M injection moulding machine, giving rectangular chips.
• the chips were measured for absorption using the same equipment as was used for measuring lenses.
• the chips were measured for yellowness index (as ASTM D1925) using a Datacolor Spectraflash SF450 colour spectrometer.

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