WO2013078086A1 - Photochromic compounds having at least two photochromic moieties - Google Patents

Photochromic compounds having at least two photochromic moieties Download PDF

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Publication number
WO2013078086A1
WO2013078086A1 PCT/US2012/065494 US2012065494W WO2013078086A1 WO 2013078086 A1 WO2013078086 A1 WO 2013078086A1 US 2012065494 W US2012065494 W US 2012065494W WO 2013078086 A1 WO2013078086 A1 WO 2013078086A1
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Prior art keywords
photochromic
divalent
bond
branched
optionally substituted
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PCT/US2012/065494
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French (fr)
Inventor
Yunyi Lu
Wenjing Xiao
Robert W. Walters
Feng Wang
M. Frank Haley
Jason R. Lewis
Anu Chopra
Beon-Kyu Kim
Huayun Yu
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Transitions Optical, Inc.
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Publication of WO2013078086A1 publication Critical patent/WO2013078086A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • 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
    • C09B57/02—Coumarine dyes
    • 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
    • G03C1/72—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
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1022—Heterocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]

Definitions

  • the present invention relates to photochromic compounds that have at least two photochromic moieties, in which the photochromic moieties are linked together by a multivalent linking group that can, with some embodiments, be flexible and/or substantially prevent electronic interaction between the photochromic moieties through the multivalent linking group,
  • photochromic compounds such as indenofused naphthopyrans
  • actinic radiation In response to certain wavelengths of electromagnetic radiation (or “actinic radiation"), photochromic compounds, such as indenofused naphthopyrans, typically undergo a transformation from one form or state to another form, with each form having a characteristic or distinguishable absorption spectrum associated therewith.
  • photochromic compounds upon exposure to actinic radiation, many photochromic compounds are transformed from a closed-form, which corresponds to an unactivated (or bleached, e.g., substantially colorless) state of the photochromic compound, to an open-form, which corresponds to an activated (or colored) state of the photochromic compound, in the absence of exposure to actinic radiation, such photochromic compounds are reversibly transformed from th activated (or colored) state, back to the unactivated (or bleached) state.
  • compositions and articles such as eyewear lenses, that contain photochromic compounds or have photochromic compounds applied thereto (e.g., in form of a photochromic coating composition) typically display colorless (e.g., clear) and colored states that correspond to the colorless and colored states of the photochromic compounds contained therein or applied thereto.
  • the photochromic compound Upon exposure to actinic radiation (e.g., sunlight), the photochromic compound typically is transformed from the unactivated (or bleached) state to the activated (or colored) state over a period of time that is referred to as an activation time.
  • actinic radiation e.g., sunlight
  • the photochrome compound typscaily is transformed from the activated (or colored) state to the unactivated (or bleached) state over a period of time that is referred to as a fade time
  • ft is generally desirable that the activation time and the fade time associated with a phoiochromic material in each case be minimized.
  • the fade rate associated with a photochromic compound be substantially linear.
  • photochromic eyewear such as photochromic lenses
  • a linear fade rate allows the wearer's eyes to adjust more smoothly and less noticeably to the wearer as the lenses transform from a colored to a bleached state.
  • phoiochromic compounds can be expensive, it is typically desirable to minimize the amount of phoiochromic compound or compounds used without compromising the photochromic properties, such as optical density, of the photochromic article with which the phoiochromic compounds are associated.
  • the photochromic compounds are present in a layer, such as a coating, thai is applied over an underlying article, such as an optical !ens, and/or the photochromic compound is present within the article itself, which can be achieved by methods such as Imbibition and/or cast-in-piace methods.
  • Photochromic compounds can be subject to migration within the matrix, such as an organic matrix, in which they reside, With, for example, a photochromic layer or coating, the photochromic compounds can migrate out of the layer, which can result in an undesirable decrease in the photochromic properties of the photochromic layer.
  • a photochromic compound can migrate from a relatively soft coating layer in which the phoiochromic compound has favorable properties, such as good fade kinetics, into an abutting coating layer that is relatively hard and in which ihe phoiochromic compound has less favorable properties, such as undesirable fade kinetics.
  • the overall effect, in such cases, can be a photochromic article having undesirable photochromic properties, such as undesirable fade kinetics.
  • Si would be desirable to develop phoiochromic compounds that are subject to reduced migration or substantially no migration within a matrix, such as an organic matrix, in which they reside, it would also be desirable thai such newly developed photochromic compounds provide a desirable level of photochromic properties.
  • L 1 is a muftivafeni linking group selected from multivalent amine, multivalent linear or branched C r C 2 c a!kyl, multivalent optionally substituted C 3 -C 12 cycioalkyi, multivalent optionally substituted C3-C12 heterocycloalkyi, multivalent optionally substituted aryl, multivalent optionally substituted heteroaryi.
  • ⁇ (R ⁇ 0) q - where R 4 for each q is independently selected from divalent linear or branched C C 12 aikyl and q is from 1 to 50, and combinations of two or more thereof.
  • Subscript n of Formula (!) is at least 2.
  • R 1 for each n is independently selected from a bond, divalent linear or branched C -C 2 o aikyl, divalent optionally substituted C3-C12 cycioalkyi, divalent optionally substituted C 3 ⁇ C 12 heterocycloalkyi, divalent optionally substituted aryl, divalent optionall substituted heteroaryi, and combinations of two or more thereof
  • X 1 for each n and X 2 for each n are each independently selected from O, NH, and a bond, provided that when R 1 is a bond and X 1 is a bond, R 1 and X 1 together define a bond.
  • L 2 for each n is independently selected from a group represented by the following Formula (II),
  • the R 2 group of Formula (II), for each t, is independently selected from a bond, divending linear or branched C C 2 o alkyl, divalent optionally substituted C 3 -C 2 cycioalkyi, divalent optionally substituted aryl, divalent optionally substituted heteroaryi, and combinations of two or more thereof.
  • the R 3 group of Formula (II), for each p, is independently selected from divalent linear or branched C C 2 o alkyi, divalent optionally substituted C3-C12 cycloaky!, divalent optionally substituted ary!, divalent optionally substituted heieroaryi, and combinations of two or more thereof.
  • X 3 for each t and X 4 for each t are each independently selected from O, NH, and a bond.
  • X 2 , R 2 and X 3 of Formula ⁇ il) there are the fo!iowing provisos: provided that when R 2 is a bond and X 3 is a bond, R 2 and X 3 together define a bond; and provided that when X 2 is a bond, R 2 is a bond, X 3 is a bond, and t is greater than 0, X 2 , R 2 and X 3 together define a bond.
  • Subscript t of Formula (li) for each n, Is 0 to 100
  • Subscript p, for each n is 0 to 20.
  • ail ranges or ratios disclosed herein are to be understood to encompass any and ail subranges or subratios subsumed therein.
  • a stated range or ratio of "1 to 10" should be considered to include any and all subranges between (and inciusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges or subratios beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, such as but not limited to, 1 to 6.1 , 3.5 to 7.8, and 5.5 to 10.
  • left-to-right representations of linking groups are inciusive of other appropriate orientations, such as, but not limited to, right-to-ieft orientations.
  • the left-to-right representation of the divalent linking group o
  • photochrome compounds of the present invention as described herein, including photochromie compounds represented by Formula (I) and Formula (M), and related photochromie compounds, in each case optionally further include one or more coproducts, such as, but not limited to oligomers, resulting from the synthesis of such photochromie compounds.
  • multivalent linking groups means a group that has at least two covalent bonds that serve to link the linking group to two or more photochromie moieties.
  • divalent with regard to divalent linking groups, means a group that has two covalent bonds that serve to link the linking group to two substituertts or portions of the photochromie compound.
  • actinic radiation means electromagnetic radiation that is capable of causing a response in a material, such as, but not limited to, transforming a photochromie material from one form or state to another as will be discussed in further detail herein,
  • photochromie and similar terms, such as “photochromie compound” means having an absorption spectrum for at least visible radiation that varies in response to absorption of at least actinic radiation.
  • photochromie material means any substance that is adapted to display photochromie properties (i.e. adapted to have an absorption spectrum for at least visible radiation thai varies in response to absorption of at least actinic radiation) and which includes at least one photochromie compound.
  • photochromie compound includes thermally reversible photochromie compounds and non-thermally reversible photochromie compounds.
  • thermally reversible photochromie compounds/materials as used herein means compounds/materials capable of converting from a first state, for example a "clear state,” to a second state, for example a "colored state,” in response to actinic radiation, and reverting back to the first state in response to thermal energy.
  • non-thermally reversible photochromie compounds/materials means compounds/materials capable of converting from a first state, for example a "clear state,” to a second state, for example a "colored state,” in response to actinic radiation, and reverting back to the first state in response to actinic radiation of substantially the same wavelength(s) as the absorption(s) of the colored state (e.g., discontinuing exposure to such actinic radiation).
  • the terms “first” and “second” are not intended to refer to any particular order or chronology, but instead refer to two different conditions or properties.
  • the first state and the second state of a photochrornic compound can differ with respect to at least one optical property, such as but not limited to the absorption of visible and/or UV radiation.
  • the photochrornic compounds of the present invention can have a different absorption spectrum in each of the first and second state.
  • a photochrornic compound of the present invention can be clear in the first state and colored in the second state.
  • a photochrornic compound of the present invention can have a first color in the first state and a second color in the second state.
  • optical article or element or device means pertaining to or associated with light and/or vision.
  • the optical article or element or device can be chosen from ophthalmic articles, elements and devices, display articles, elements and devices, windows, mirrors, and active and passive liquid crystal cell articles, elements and devices.
  • ophthalmic means pertaining to or associated with the eye and vision.
  • ophthalmic articles or elements include corrective and non-corrective lenses, including single vision or multi-vision lenses, which can be either segmented or non-segmented mufti-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetically or otherwise) vision, Including without limitation, contact lenses, intra-ocu!ar lenses, magnifying lenses, and protective lenses or visors.
  • ophthalmic substrate means lenses, partially formed lenses, and lens blanks.
  • display means the visible o machine-readable representation of information in words, numbers, symbols, designs or drawings.
  • Non-limiting examples of display articles, elements and devices include screens, monitors, and security elements, such as security marks.
  • window means an aperture adapted to permit the transmission of radiation therethrough.
  • windows include automotive and aircraft transparencies, filters, shutters, and optical switches.
  • mirror means a surface that specularly reflects a large or substantial fraction of incident light.
  • liquid crystal cell refers to a structure containing a liquid crystal material that is capable of being ordered.
  • Active liquid crystal ceils are cells in which the liquid crystal material is capable of being reversibly and controilabiy switched or converted between ordered and disordered states, or between two ordered states by the application of an external force, such as electric or magnetic fields.
  • Passive liquid crystal cells are cells in which the liquid crystal material maintains an ordered state.
  • a non-limiting example of an active liquid crystal cell element or device is a liquid crystal display,
  • coating means a supported film derived from a flowabfe composition, which can or can not have a uniform thickness, and specifically excludes polymeric sheets.
  • a layer that includes one or more photochromic compounds of the present invention can, with some embodiments, be a photochromic coating.
  • sheet means a pre-forrned film having a generally uniform thickness and capable of self-support.
  • a coating containing one or more photochromic compounds of the present invention can be In direct contact (e.g., abutting contact) with at least a portion of a substrate, such as an optical article, or it can be In indirect contact with at least a portion of the substrate through one or more other interposed structures or materials, such as a monomoiecuiar layer of a coupling or adhesive agent.
  • a coating containing one or more photochromic compounds of the present invention can be in contact with one or more other interposed coatings, polymer sheets or combinations thereof, at least one of which is in direct contact with at least a portion of the substrate.
  • photosensitive material means materials that physically or chemically respond to electromagnetic radiation, including, but not limited to, phosphorescent materials and fluorescent materials.
  • non-photosensitive materials means materials that do not physically or chemically respond to electromagnetic radiation, including, but not limited to, static dyes.
  • moiecular weight values of polymers such as weight average molecular weights ( w) and number average molecular weights (Mn) are determined by gel permeation chromatography using appropriate standards, such as polystyrene standards.
  • polydi ' spersity index (PDf) values represent a ratio of the weight average moiecular weight ⁇ Mw) to the number average molecular weight (Mn) of the polymer (i.e., Mw/ n).
  • polymer means homopoiymers (e.g., prepared from a single monomer species), copolymers (e.g., prepared from at least two monomer species), and graft polymers.
  • (meth)acryiate and similar terms, such as “(meth)acryiic acid ester” means methacrylates and/or acrylates.
  • (meth)acrylic acid means methacrylic acid and/or acrylic acid.
  • linear or branched groups such as linear or branched aikyi
  • linear or branched aikyi are herein understood to include; a methylene group or a methyl group; groups that are linear, such as linear C 2 -C w aikyi groups; and groups that are appropriately branched, such as branched C 3 -C 3 ⁇ 4 ) alky! groups.
  • optionally substituted group means a group, including but not limited to, aikyi group, cycloalkyl group, heterocycioalkyl group, ary! group, and/or heteroaryf group, in which at least one hydrogen thereof has been optionally replaced or substituted with a group that is other than hydrogen, such as, but not limited to, bafo groups (e.g., F, Ci, I, and Br), hydroxy!
  • bafo groups e.g., F, Ci, I, and Br
  • amine groups such as -N(R 1 )(R 12 ) where R 11 and R 12 are each independently selected from hydrogen, linear or branched C -C 2 o aikyi. C 3 -Ci 2 cycloaky!, C3-C 12 heterocycioalkyl, aryl, and heteroaryf.
  • aikyi 8 means linear or branched Ci ⁇ C Z0 aikyi, such as, but not limited to linear or branched C Ci 0 aikyi or linear or branched C 2 -CIQ alkyl.
  • a!kyl groups from which the various a!kyl groups of the present invention can be selected from include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, sec-butyl, tert-buty!, pentyl, neopenty!, hexyl, heptyf, octy!, nonyl and decyi.
  • Aikyi groups of the various compounds of the present invention can, with some embodiments, include one or more unsaturated linkages selected from -CH-CH- groups and/or one or more -C ⁇ C- groups, provided the alkyl group is free of two or more conjugated unsaturated linkages.
  • cycioaik means groups that are appropriately cyclic, such as C 3 -C 12 cycloa!kyl (including, but not limited to, cyclic .C 5 ⁇ C ? alkyl) groups.
  • cycloalkyl groups include, but are not limited to, cyclopropyl, cyciobutyi, cyclopentyl, cyciohexyi, and cyclooctyl.
  • cycloalkyl as used herein also includes: polycycloa!kyl groups (or poiycyciic alky!
  • heterocycfoalkyi means groups that are appropriately cyclic, such as C 3 -C 12 heierocycloaikyi groups or C 5 -C 6 heierocycloaikyi groups, and which have at least one hetera atom in the cyclic ring, such as, but not limited to, O, S, N, P, and combinations thereof,
  • heierocycloaikyi groups include, but are not limited to, ietrahydrofuranyi, tetrahydropyranyl and piperidinyl.
  • heterocycioaikyl as used herein also includes: poiycyciic heterocycloalkyi groups, such as but not limited to, 7-oxabicycio[2.2.1]heptanyf; and fused ring poiycyciic heierocycloaikyi groups, such as but not limited to, octahydrocyc!opentaibjpyranyl, and octahydro-1 H-isochromenyi.
  • poiycyciic heterocycloalkyi groups such as but not limited to, 7-oxabicycio[2.2.1]heptanyf
  • fused ring poiycyciic heierocycloaikyi groups such as but not limited to, octahydrocyc!opentaibjpyranyl, and octahydro-1 H-isochromenyi.
  • aryl includes, but is not limited to, C 8 -C 18 ary!, such as but not limited to, C 5 ⁇ C 0 aryl (including poiycyciic fused ring aryl groups).
  • aryl groups include, but are not limited to, phenyl, naphthyi, and anthracenyi.
  • heteroaryl/' includes but is not limited to C-C-,, heteroaryl, such as but not limited to C 5 -C 0 heteroaryl (including poiycyciic fused ring heteroaryl groups) and means an aryf group having at least one hetero atom in the aromatic ring.
  • heteroaryl groups include, but are not limited to, furanyl, pyranyl and pyridinyi.
  • aralkyi includes but is not limited to C 6 -C 2 4.
  • araikyl such as but not limited to C 6 -C 10 aralkyi, means an aryl group substituted with an aikyi group that is bonded (or linked) to another group, hxamp!es of ara!kyl groups include, but are not limited to, benzyl, and phenethyi.
  • n-segrnenf means a segment of a photochrome compound according to the present invention that is bonded to the multivalent linking group t ⁇
  • the photochrome compound when n is 3, can be described as having three n- segments that are each bonded to thvalent linking group L 1 ; the three n-segments can be further described as a first n-segment, a second n-segment, and a third n- segment, in which any one such n-segment is the same or different than any other such n-segment.
  • photochromic compounds of the present invention and compositions containing such photochromic compounds, will be described in further detail as follows.
  • subscript n is at least 2. With some embodiments, subscript n can be from 2 to 10, or from 2 to 5, or from 2 to 4, or from 2 to 3.
  • Subscript q of -(R 4 -0) q - of L of Formula (!) can be, with some embodiments, from 1 to 50, or from 1 to 30, or from 1 to 20, or from 1 to 10, or from 1 to 5, or from 1 to 3.
  • subscript t can, with some embodiments, be from 0 to 100, or from 0 to 50, or from 0 to 30, or from 0 to 20, or from 0 to 15, or from 0 to 10, or from 0 to 5, or from 0 to 3,
  • subscript p can be from 0 to 20, or from 0 to 15, or from 0 to 10, or from 0 to 5, or from 0 to 3.
  • the aikyi groups, cycioalkyl groups, heterocycloalky! groups, ary! groups, and heteroary! groups from which the various multivalent and divalent Sinking groups, such as multivalent linking group L 1 , divalent R ⁇ divalent R 2 , divalent R 3 , and divalent R 4 can each be Independently selected include, but are not limited to, those classes and examples of alky! groups, cycioalkyl groups, heterocycioalkyl groups, aryi groups, and heteroary! groups as described previously herein.
  • the photochromic moieties (PC) of the photochromic compounds are linked together by linkages or linking groups that limit, or inhibit, or prevent electronic interaction between any two photochromic moieties through the linking group.
  • An example of electronic interaction includes, but is not limited to, extension of the pi-conjugated system of one photochromic moiety through the linking group with the pi-conjugated system of another photochromic moiety bonded to the same linking group.
  • L 1 , R 1 , X 1 , X 2 and L 2 are each selected so as to substantially prevent electronic interaction between any two photochromic moieties of the photochromic compound through L ⁇ R 1 , X 1 , X 2 and L 2 .
  • L ⁇ R ⁇ X 1 , X 2 and L 2 are each selected so as to substantially prevent extension of the pi-conjugated system of any photochromic moiety through L 1 , R 1 , X 1 , X 2 and L 2 with the pi- conjugated system of any other photochromic moiety of the photochromic compound
  • L 1 , R 1 , X ' , X z and L 2 are each selected so as to be substantially free of conjugated pi-bonds that provide extension of the pi-conjugated system of any photochromic moiety through L 1 , R 1 , X 1 , X 2 and L 2 with the pi-conjugated system of any other photochromic moiety of the photochromic compound.
  • I 1 , R , X 1 , X 2 and L 2 are each selected, with some embodiments, so as to provide a flexible linkage between each photochromic moiety (PC) of the photochromic compounds of the present invention.
  • L ⁇ R , R 2 and R 3 are each independently selected from mu!tivalent divalent linear or branched optionally substituted C C 20 alkyf, mu!tSvalent/divalent optionally substituted C3-C12 cycloalkyi, multivalent/divajent optionally substituted C,r-C1 ⁇ 2 heterocydoalky), and combinations of two or more thereof, and alternatively or additionally, R 1 and R 2 can each be Independently selected from a bond, subject to the provisos as recited previously herein.
  • L 1 , R 1 , R 2 and R 3 are each, independently selected from multivalent/divalent linear or branched optionally substituted C1-C2 0 alkyi, and/or multivalent divalent optionally substituted C3-C12 cycloalkyi, and combinations of two or more thereof, and alternatively or additionally, R 1 and R 2 can each be independently selected from a bond, subject to the provisos as recited previously herein.
  • n is 2;
  • L 1 is a divalent linking group selected from divalent linear or branched optionally substituted Ci-C 2 o, divalent optionally substituted C3-C12 cycioa!kyi, divalent optionally substituted aryl, divalent optionally substituted heieroaryl, and combinations of two or more thereof;
  • R ! is a bond;
  • X 1 is NH; and
  • X 2 is O.
  • the photochrome compounds of the present invention can, with some embodiments, be prepared from isocyanate functional materials having at least two isocyanate groups.
  • isocyanate functional materials from which the photochrome compounds of the present invention can be prepared include, but are not limited to: aikylene diisocyanates, such as hexamethylene diisocyanate; aromatic isocyanates, such as toluene diisocyanate, methylene diphenyi 4,4 -diisocyanate, meta-tetramethy!xy!ene diisocyanate (also referred to as m-T XDI), triphenyfmethan8-4 > 4 ' ,4' !
  • naphthalene diisocyanate such as naphthalene 1 ,5-dtisocyanate, and pheny!ene diisocyanate, such as p-phenylene diisocyanate
  • cycioa!kyl isocyanates such as, isocyanato-1- (isocyanatomethyl)-1 ,3,3 rimethyl-cyclohexane, for example 5- isocyanato-1- (isocyanafomefhyl)-1 ,3 f 3-tnmethyl-cyclohexane (alos referred to as isophorone diisocyanate or iPDi), and methylene dicyclohexyi diisocyanate, such as methylene dicyclohexyi 4,4'-diisocyanate; and dimmers and trimers of any combination of such isocyanate functional materials (such as diisocyanates) containing Isocyanurate, u
  • PhotochromiG compounds can be described with reference to: Formula (1 ⁇ In which n is 2, L 1 is a divalent linking group selected from divalent linear or branched optionally substituted C r C 3 ⁇ 4 , divalent optionally substituted C 3 -C 12 cycioalkyl, divalent optionally substituted aryi, divalent optionally substituted heieroaryl, and combinations of two or more thereof, R 1 is a bond, X 1 is NH, and X 2 Is O; and Formula (II) in which i is 0, p is from 1 to 5, and R 3 for each p is independently divalent linear or branched C2-C10 aiky!, such as ethan-1,2-diyi or pram-1 ,2-diyi.
  • Photochromic compounds according to such non-!imiting embodiments of the present invention can, with some embodiments, be prepared by reaction of 2 moles of a hydroxyi functional photochromic reactant (or intermediate) with one mole of a difunctionaf isocyanate.
  • the photochromic compounds of the present invention can be described with reference to: Formula (I) in which n is 2, L is a divalent linking group selected from divalent linear or branched optionally substituted C 1 -C 20 .
  • Photochromlc compounds according to such non-iimiting embodiments of the present invention can, with some embodiments, be prepared by reaction of one mole of a hydroxyi functional photochromic reactant with one or more moles of a cyclic carboxylic acid ester, such as a lactone, including but not limited to e-capro!actone, which results in the formation of a hydroxyi functional lactone extended
  • the photochromic compounds of the present invention can be described with reference to Formula (I) in which n is 2, R 1 is a bond, X 1 is NH, X 2 is O, and V is more particularly selected from: divalent linear or branched optionally substituted C C 2 o alkyi, such as divalent linear or branched C r C s alkyl, such as hexamethan-1 ,6-diyi; a structure represented by the following Formula (111),
  • the photochfomic compounds of the present invention can, with some embodiments, be prepared from isocyanate functional materials having at ieasi two isocyanate groups.
  • multivalent linking group V when the multivalent linking group V is selected from divalent linear or branched C1-C20 alky!, multivalent linking group L 1 can be a residue of a diisocyanate, such as, but not limited to, hexamethylene diisocyanate, for example, 1 ,6-hexamethylene diisocyanate.
  • the divalent linking group L' represented by Formula (Ml) is a residue of a diisocyanate, such as tetramethylxy!ene diisocyanate, for example, meta- tetramethyixy!ene diisocyanate.
  • the divalent linking group L represented by Formufa (IV) is a residue of a diisocyanate, such as methylene dicyciohexyi diisocyanate, for example, methylene drcyc!obexyl 4,4' ⁇ diisocyanate.
  • the divalent linking group L 1 represented by Formula (V) is a residue of a diisocyanate, such as isocyanato-1-(!socyanatomethyl)-1 ,3,3-inmethyl-cyc(ohexane, for example, 5- isocyanato-1-(isocyanatomethyl)-1 ,3,3--trimetnyi-cyclohexane (also called isophorone diisocyanate).
  • Photochromic compounds according to further embodiments of the present invention can be described with reference to Formula (i), in which n is 3, X 1 is NH, X 2 is 0 » and L 1 is represented by the following Formula (VI),
  • trtvailing linking group L 1 can be a residue of a trimer of three moles of one or more diisocyanates, such as a trimer of hexamethyiene-1 ,6-diisocyanat .
  • the photochromic compounds of the present invention can be described with reference to Formula ⁇ I ⁇ , in which n is 3, X 1 is NH, X 2 is O, and L 1 is represented by Formula (VI), and additionally in which R 1 for each n is independently selected from linear or branched CTC 2 Q alky!.
  • Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared, with some embodiments, from a trifuncttonal isocyanate that is a trimer of three moles of one or more diisocyanates, such as a trimer of hexamethyiene-1 ,6- dsisocyanate, 084J
  • Photochromic compounds according to some embodiments of the present invention can be described with reference to: Formula (I), in which n is 3, X 1 is NH, X 2 is O, and L 1 Is represented by Formula (VI), and R 1 for each n is independently selected from linear or branched C1-C20 aikyl; and Formula (II), in which t is 0, p is from 1 to 5, and R 3 for each p is independently divalent linear or branched C 2 -C ]o aikyl.
  • Photochromic compounds according to such non-limiting embodiments of the present invention can, with some embodiments, be prepared by reaction of three moles of a hydroxy! functional photochromic reactant with one mole of a trimer of a diisocyanate, such as a trimer of hexamethylene ⁇ 1 ' ,6-diisocyanate.
  • a trimer of a diisocyanate such as a trimer of hexamethylene ⁇ 1 ' ,6-diisocyanate.
  • the photochromic compounds of the present invention can be described with reference to: Formula (I), in which n is 3, X 1 is NH, X 2 is O, and V is represented by Formula (VI), and R 1 for each n is independently selected from linear or branched C C 2 o alkyi; and Formula (II), In which t is from 1 to 10, R 2 for each f is independently selected from divalent linear or branched C C 0 alkyl, X 3 is a bond, X 4 is O, p is from 1 to 5, and R 3 for each p is Independently selected from divalent linear or branched C 2 -C 0 alkyl.
  • Photochromic compounds according to such non-limiting embodiments of the present invention can, with some embodiments, be prepared by reaction of one mole of a hydroxy! function photochromic reactant with one or more moles of a cyclic carboxylic acid ester, such as a lactone, for example, e-capro!actone, which results in the formation of a hydroxy! functional lactone extended photochromic intermediate.
  • a hydroxy! function photochromic reactant with one or more moles of a cyclic carboxylic acid ester, such as a lactone, for example, e-capro!actone
  • hydroxyl functional lactone extended photochromic intermediate can be reacted with one mole of a trimer of a diisocyanate, such as a trimer of hexamethylene-1 ,6-diisocyanate, which results in formation of a photochromic compound according to a non-limiting embodiment of the present invention.
  • a trimer of a diisocyanate such as a trimer of hexamethylene-1 ,6-diisocyanate
  • the photochromic compounds of the present invention can be described with reference to Formula (I), in which n is 3, and the photochromic compound has a first n-segment, a second n-segment, and a third n-segment, and L 1 is N.
  • the trivIER linking group L ' can be a residue of a trimer of a diisocyanate, that includes biuret linkages, such as hexamethlene-1 ,6-diisocyanate.
  • the photochromic compounds of the present invention can be described with reference to Formula (I) in which n is 3, and the photochromic compound has a first n-segment, a second n-segment, and a third n-segment, L is N, and additional in which: for said first n-segment, R 1 is divalent linear or branched optionally substituted d-Cao alkyl, X 1 is NH, and X 2 Is O; and for each of said second n-segment and said third n-segment, R 1 and X 1 together define a bond, and X 2 is NH.
  • the photochromic compounds of the present invention can be described with reference to: Formula (!) in which n is 3, and the photochromic compound has a first n-segment, a second n-segment, and a third n-segment, L 1 is N, and additional In which: for said first n-segment, R 1 is divalent linear or branched optionally substituted C G 2 o alkyt, X ' is NH, and X 2 is O; and for each of said second n-segment and said third n-segment, R 1 and X !
  • Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared by reaction of two moles of a hydroxyl functional photochromic reactani with one mole of a trimer of a drisocyanate, in the form of a biuret, such as hexarneth!ene-1 ,6-diisocyanate, such as DESMODUR N 3200 po!yisocyanate, which is commercially available from Bayer MaterialScience LLC.
  • a biuret such as hexarneth!ene-1 ,6-diisocyanate, such as DESMODUR N 3200 po!yisocyanate
  • Photochromic compounds in accordance with additional embodiments of the present invention can be described with reference to Formula (I), in which n is 2; L 1 for each n is independently divalent linear or branched optionally substituted Ci- C 2 alkyi; R 1 is a bond; X' is O; and X 2 is a bond.
  • Photochromic compounds according to some further embodiments of the present invention, can be described with reference to: Formula (I), in which n Is 2, L 1 for each n is independently divalent linear or branched optionally substituted C C 2 o alkyi, R 1 is a bond, X 1 is O, and X 2 is a bond, and Formula (II), in which t is 1 , R 2 is divalent linear or branched CrC 1Q aikyl, X 1' is a bond, and X 4 is O.
  • some photochromic compounds of the present invention can be described with reference to: Formula (I), in which n is 2, L 1 for each n Is independently divalent linear or branched optionally substituted C- Cao aikyl, R 1 is a bond, X 1 is O, and X 2 is a bond, and Formula (II), in which t is 1 , R 2 is divalent linear or branched G C 10 aikyl, X 3 is a bond, X 4 is O, p is 1 to 5, and R 3 for each p is independently divalent linear or branched C 2 -Ci 0 aikyl.
  • Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared, with some embodiments, by reaction of one mole of a hydroxy! functional photochromic compound and a cyclic carboxylic acid anhydride, such as, but not limited to, succinic anhydride, which results in the formation of a carboxylic acid functional photochromic intermediate.
  • a hydroxy! functional photochromic compound and a cyclic carboxylic acid anhydride, such as, but not limited to, succinic anhydride, which results in the formation of a carboxylic acid functional photochromic intermediate.
  • the hydroxy functionality of the hydroxyl functional photochromic compound is provided by: a hydroxyl functional alkoxy group, such as but not limited to, -0-R**-OH, where R** is a divalent hydrocarbyi group, such as divalent linear or branched Ci-C 20 aikyl, divalent C3-C 12 cycloalkyl, divalent C 3 ⁇ C 12 heterocycioalkyl, divalent aryl, divalent heieroaryi, and combinations of two or more thereof; or a hydroxy! functiona! hydrocarbyl group, such as -R * * ⁇ OH, where R ** is a described above.
  • R ** is a described above.
  • Two moles of the carboxylic acid functional photochromic intermediate can then be reacted, in some embodiments, with one mole of a dioL such as a linear or branched C 2 -C 2 o aikyl (or alkane) dio!, for example, dacane-1 ,10-dioi, with concurrent removal of water, which results in formation of a photochromic compound according to a non- limiting embodiment of the present invention.
  • a dioL such as a linear or branched C 2 -C 2 o aikyl (or alkane) dio!
  • dacane-1 ,10-dioi a photochromic compound according to a non- limiting embodiment of the present invention.
  • a photochromic compound for purposes of non-limiting illustration, see Formula (Vll-i) further herein.
  • Photochromic compounds in accordance with some embodiments of the present invention can be described with reference to Formula (I), in which n is 2, L ' is divalent !inear or branched optionaiiy substituted C r C 2 o aikyi, R 1 is a bond, X 1 is O, and X 2 is O.
  • the photochromic compounds of the present invention include at least one carbonate linkage between L 1 and at least one PC moiety.
  • photochromic compounds of the present invention can be described with reference to: Formula (I), in which n is 2, L 1 is divalent linear or branched optionally substituted C r C 20 afkyi, R 1 is a bond, X 1 is O, and X 2 is O; and Formula (II), in which t is 0, p is from 1 to 5, and R for each p is independently divalent linear or branched C 2 -C 10 a!kyL Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared, with some embodiments, by reaction of two moles of a hydroxy!
  • a bishaioformate such as a linear or branched C C 20 aikyl (or alkane) bishaioformate, for example 1 ,6-hexane bischioroformate, which results in the formation of a photochromic compound according to a non-limiting embodiment of the present invention.
  • a bishaioformate such as a linear or branched C C 20 aikyl (or alkane) bishaioformate, for example 1 ,6-hexane bischioroformate
  • Photochromic compounds in accordance with some embodiments of the present invention can be described with reference to: Formula (I), in which n is 2, L 1 is divalent linear or branched optionally substituted Ci-C 20 aikyi, R is a bond, X 1 is O, and X 2 is O; and Formula (ll), in which t is from 1 to 100, such as from 1 to 50, or 1 to 30, or 1 to 20, or 1 to 10, or 1 to 5, or 1 to 3, R 2 for each t is independently divalent linear or branched optionally substituted C C 2 o .alky!, X 3 and X 4 for each t are each O, and p is 0.
  • Formula (I) in which n is 2, L 1 is divalent linear or branched optionally substituted Ci-C 20 aikyi, R is a bond, X 1 is O, and X 2 is O; and Formula (ll), in which t is from 1 to 100, such as from 1 to 50, or 1 to 30, or 1 to 20, or 1
  • Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared, with some embodiments, by reaction of; a hydrocarb-diyl-dicarbonoha!odate (X(O iCO-R-GC(O)X, where R is a hydrocarb-diyl and X is halo), such as a hydrocarb-diyi-dicartionochioridaie, such as an a!kane-diyl-dicarbonochloridate, such as ethane-1 ,2-diyl-dicarbonochioridate; and a dioi, such as an aikane dioi, such as 1 ,6-hexane diof, in which the moles of hydrocarb-diyi-dicarbonohalodaie and moles of dioi are selected so as to result in the formation of a chain extended dicarbonohalodate functional intermediate.
  • hydrocarb-diyl-dicarbonoha!odaie hydrocarb-diyl-dicarbonoch!orsdate, alkane-diyi-dicarbonochforidate and ethane- 1 ,2- diyl-dicarbonochloridate are equivalent to hydrocarb-diol-bisha!oformate, hydrocarb- diol-bischioroformate, alkyleneg!yco!bischioroformate, and
  • photochromic compounds can, in accordance with some embodiments, be described as oSigomeric or polymeric polycarbonates having terminal photochromic moieties. For purposes of non-limiting illustration, see Formula (Vli-m) further herein.
  • Photochromic compounds in accordance with some embodiments of the present invention can be described with reference to Formula (I), in which n is 2, L for each n is independently selected from divalent linear or branched optionally substituted C 1 -C20 alkyi, divalent optionally substituted C 3 -C 2 cycloaikyl, divalent optionally substituted C 3 -C 12 heterocycioaikyl, divalent optionally substituted aryl, and combinations of two or more thereof, R 1 and X 1 together define a bond, and X 2 is O.
  • some photochromic compounds of the present invention can be described with reference to: Formula (I), in which n is 2, L 1 for each n is independently selected from divalent linear or branched optionally substituted C - C 2 o alkyi, divalent optionally substituted C 3 -Ci 2 cycloaikyl, divalent optionally substituted C3-C 12 heterocyc!oalkyi, divalent optionally substituted aryl, divalent optionally substituted heteroaryl, and combinations of two or more thereof, R and X 1 together define a bond, and X 2 is O; and Formula (ii), t is 0, p is from 1 to 5, and R 3 for each p is independently divalent linear or branched C 2 ⁇ Ci 0 alkyi.
  • Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared, with some embodiments, by reaction of two moles of a hydroxy! functional photochromic reactant and one moles of a bis oarboxyiic acid haiide, such as a linear or branched C 2 -C 2 Q alkyi (or afkane) bis carboxylic acid halide, for example decanedioyl dichioride (also referred to a sebacoyi chloride), which results in the formation of a photochrome compound according to a non-iimiting embodiment of the present invention.
  • a bis oarboxyiic acid haiide such as a linear or branched C 2 -C 2 Q alkyi (or afkane) bis carboxylic acid halide, for example decanedioyl dichioride (also referred to a sebacoyi chloride), which results in the formation of a photochrome compound according to a non-
  • Additional photochromic compounds in accordance with some embodiments of the present invention can be described with reference to Formula (1), in which n is 2, and said photochromic compound has a first n-segment and a second n-segment, and L is -(R -0 ⁇ a - For the first n-segment, R 1 and X 1 together define a bond. For the second n-segment, R 1 is a bond, and X 1 is O, For the first n-segment and said second n-segment, X 2 Is a bond.
  • t fs 1 , R 2 is linear or branched C1-C10 aikyi
  • X J is a bond
  • X 4 is 0,
  • p is from 1 to 5
  • 3 for each ⁇ is independently selected from divalent linear or branched C 2 -C 10 aikyi.
  • Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared, with some embodiments, by reaction of one mole of a hydroxy!
  • photochromic compounds according to the present invention include, but are not limited to, those represented by the following Formulas (VH-a) through (Vll-i).
  • each t is independently selected from 1 to 100, or 1 to 50, or 1 to 30, or 1 to 20, or 1 to 15, or 1 to 10, such as, with some embodiments, 4, 8, or 9.5.
  • each R b is represented by the following Formula (V!l-f-a) Formula (VH-f-a) o
  • each R 6 is represented by the following Formula (VH-g-a).
  • each t Is independently from 1 to 100, or 1 to 50, or 1 to 30, or 1 to 20, or 1 to 15, or 1 to 10, such as with some embodiments 4.5, or 8, or 10.
  • q is from 1 to 20, or from 1 to 10, or from 1 to 8, such as, with some embodiments, 4.
  • iT of each of the two n-segments is irsdependently at least 1 , such as with some embodiments from 1 to 49, or 1 to 40, or 1 to 30, or 1 to 20, or 1 to 10.
  • each R 3 is independently a residue of a dio!
  • each R b is independently a residue of a hydrocar -diyl-dicarbonohaiodate.
  • each R a and each R b can, with some embodiments, each be independently seiected from divending linear or branched optionally substituted C C 2 o aikyi, such as, but not limited to, n-hexane-1 ,6-diyi and ethane-1 ,2-dryj.
  • R a is the same as R and correspondingly R B is the same as R a ,
  • Each divalent linking group L 2 of the photochromic compounds of the present invention can, with some embodiments, be independently bonded to any appropriate portion of each photochromic rnosety ( PC), including any group bonded to the photochromic moiety.
  • L 2 can be bonded: (i) directly to a ring of the indeno-fused naphthopyran; or (li) to a group, such as an Interposed group, that is bonded to a ring of the indeno-fused naphihopyran.
  • Examples of groups, such as interposed groups, of the photochromic rnosety (PC) io which each L 2 can independently be bonded include, but are not limited to: -O; -S-; - NR*-, where R* is hydrogen or hydrocarbyl, such as, linear or branched Cr-C 2 o aikyi, C 3 ⁇ C 2 cycioaiky!, G 3 -C
  • the photochromic moieties (PC) of the photochromic compounds of to the present invention can be seiected from known photochromic moieties or substituents. While each photochromic moiety ca be selected from inorganic photochromic moieties and organic photochromic moieties, they are each typically and independently selected from organic photochromic moieties.
  • each photochromic moiety (PC), of the photochromic compounds of the present invention is independentl selected from, indeno-fused naphthopyrans, naphtho[1 ,2 ⁇ b]pyrans, naphtho[2,1 -b]pyrans, spirofiuoroeno[1 ,2-bJpyrans, phenanthropyrans, quinolinopyrans,
  • fluoroanthenopyrans spiropyrans, benzoxazines, naphthoxazines,
  • spiro(indoline)fluoranthenoxazines spiro(indoline)quinoxazines
  • fuigides fuigimides
  • diaryiethenes diaryiaikyiethenes
  • diaryiaikenylethenes thermally reversible phoiochromic compounds
  • non-thermaliy reversible phoiochromic compounds and mixtures thereof.
  • phoiochromic (PC) moiety of the photochromic compounds of the present invention, can be chosen include benzopyrans, naphthopyrans, e.g., napbiho[1 ,2-b]pyrans, naphtho[2, 1 -bjpyrans, indeno-fused naphthopyrans, such as those disclosed in U.S. Patent 5,645,767, and heterocydic-fused naphthopyrans, such as those disclosed in U.S. Patent Nos.
  • benzopyrans e.g., napbiho[1 ,2-b]pyrans, naphtho[2, 1 -bjpyrans
  • indeno-fused naphthopyrans such as those disclosed in U.S. Patent 5,645,767
  • heterocydic-fused naphthopyrans such as those disclosed in U.S. Patent Nos.
  • Non-limiting examples of photochromic oxaz nes from which each phoiochromic moiety (PC) can be independently chosen include benzoxazines, naphthoxazines, and spiro-oxazines, e.g., spiro(indoline)naphthoxazines,
  • Non-limiting examples of photochromic fulgides from which each photochromic moiety (PC) can be independently chosen include; fu!gimides, and the 3-furyl and 3-thienyl fulgides and tulgsmides, which are disclosed in U.S. Patent 4,931 ,220 (which are hereby specifically Incorporated by reference) and mixtures of any of the aforementioned photochromic materials/compounds.
  • each photochromic moiety of the photochromic compounds of the present invention are each independently selected from one or more indeno-fused naphthopyrans.
  • an indeno-fused naphthopyran typically has 10 to 12 available positions to which the divalent linking L 2 of Formula (I) can be bonded.
  • each photochromic moiety (PC) is Independently selected from an indeno-fused naphthopyran, which can be represented by the following general Formula (VIII), in which the ring atoms are numbered as shown,
  • the indeno-fused naphthopyran represented by general formula (Vfli) can be referred to as an indeno[2',3':3,4]naphtho[1 ; 2-b3pyran.
  • Each photochromic moiety (PC) can, with some embodiments, be independently selected from an indeno- naphthopyran, including, but not limited to, indeno[2 ⁇ 3 ⁇ ' 3,43naphtho[1 ,2 ⁇ b]pyrans represented by general formula (VIII), and/or one or more represented by the following general Formu!a- (IX), in which the ring atoms are numbered as shown, Formula (IX)
  • R s through R 14 , B and B' groups of the indeno[1 ⁇ 2':4,3]naphthoJ2, 1 -b]pyran represented by genera! Formula-(iX) are each as described herein with regard to the indenop' ⁇ S ⁇ jjnaphthoil ,2-bjpyran represented by general Formula (Vlli).
  • each photochromic moiety is independently selected from an indeno[2',3':3,4Jnaphtho[1 ,2 ⁇ b]pyran, such as represented by Formula (Vlli), and/or an
  • each photochromic moiety (PC) is independently selected from an indena[2 ⁇ 3':3,4]naphiho[1 ,2-b]pyran ; such as represented by Formula (VIII).
  • each photochromic moiety (PC) is independently selected from an indeno[2 ⁇ 3 ⁇ * 3,4]naphthop ,2 ⁇ b]pyran, such as represented by Formula (Vil I)
  • each such photochromic moiety (PC) can be independently bonded to L 2 at a ring position selected from ring position 3, ring position 8, ring position 7, ring position 1 1 , and ring position 13.
  • each photochromic moiety (PC) is independently selected from an indeno[2',3 J :3,43riaphtho[1 ,2-b]pyran, such as represented by Formula (VIII), each such photochromic moiety (PC) can be independently bonded to L 2 at a ring position selected from ring position 3, ring position 1 1 , and ring position 13.
  • each photochromic moiety (PC) is selected from an indeno[2',3 !
  • each photochromic moiety (PC) is selected from an !ndenoi2',3':3 ! 4jnaphtho[1 ,2-bjpyran, and each photochromic moiety (PC) is bonded to L 2 at ring position 11 .
  • each photochromic mosety (PC) is selected from an indeno[2 ⁇ 3':3,4]naphtho[1 ,2-b]pyran, and each photochromic moiety (PC) is bonded to L 2 at ring position 13.
  • Each photochromic moiety (PC) of the photochromic compounds of the present invention can, with some embodiments, be selected so as, in each case, to have an activated visible light absorbance spectra, and the activated visible light absorbance spectra of each photochromic moiety (PC) is substantially the same.
  • the activated visible light absorbance of each photochromic moiety (PC) can be determined in accordance with art-recognized methods using art-recognized analytical equipment.
  • each photochromic moiety (PC): is selected from an indeno-fused naphthopyran, such as an indeno[2',3':3,4]naphtho[1 !
  • 2-b]pyran or an indeno[ 1 ! ,2':4,3]naphiho[2, 1 -bjpyran; has substantially the same structure; and is bonded to L 2 at the same ring position of each photochromic moiety (PC).
  • PC photochromic moiety
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 1Z can each independently be selected in each case from: a reactive substituent; a compatiblizing substituent; hydrogen; fiuoro; chloro; C C 6 alkyi; C 3 -C 7 cyc!oalkyl; substituted or unsubstituted phenyl; -GR )0 ' or -OC(-O)R 0 ⁇ wherein R 0 * is hydrogen, C r C 6 alkyi, phenyl(C C 3 )a!kyl, mono(C C 6 )alky!
  • the phenyl substituents i.e., the substituents of the substituted phenyl
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R 11 and R 12 can each independently be selected in each case from: wherein R,,' and R 12 ' are each Independently hydrogen, C C 8 alkyi, phenyl, naphthyl, furany!, benzofuran-2-yi, benzofuran-3-yl, thieny!, benzothien- 2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyndyi, f!uorenyl, C C 8 aikylaryl, C 3 ⁇ C 20 cycioaikyl, C 4 -C 2 o bicyeloaSkyi, C 5 - C 20 tricycloalkyf or C C 20 aikoxyaikyi, wherein said ary!
  • R, i' and R 12 ' come together with the nitrogen atom to form a G 3 -C 20 hetero-bicyctoaiky! ring or a C 4 ⁇ C 20 hetero-iricycloa!ky! ring.
  • Each R 5 , R s , R 7 , R 8 , R 9 , R !0 , R 11 and R 12 group can independently be selected in each case from, a nitrogen containing ring substituent represented by the following general (or graphic) Formula X:
  • each - ⁇ - is independently chosen for each occurrence from -CH 2 -, -CH(R 13 ')-, -C(Ri3') ,
  • each R 13 ' is independently d-Ce alkyl
  • each ary! is independently phenyl or naphthyl
  • m is an integer 1 , 2 or 3
  • p is an integer 0, 1 , 2, or 3 and provided that when p is 0, Z is -Y-.
  • each R 5 , R 6 , R 7 , R 8 > R 9 , R 10 , R and R a group can independently be selected in each case from a nitrogen containing ring substituent represented by genera! formula (X8) and/or general formula (XC):
  • R- i5> R- t e, and R 17 are each independently selected from hydrogen, C r C 6 aikyl, phenyl, or naphthyl, or the groups R 5 and R f 6 together form a ring of 5 to 8 carbon atoms and each R d is independently for each occurrence selected from -Ce alkyi, C C3 ⁇ 4 alkoxy, fluoro or chloro, and Q is an integer 0, 1 , 2, or 3.
  • Each R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R and R 12 group can also independently be selected in each case from unsubstituted, mono-, or di-substituted C 4 -C 8 spirobicyciic amine, or unsubstituted, mono-, and di-substituted C4-C18 spirotricyciic amine.
  • the substituents of the spirobicyciic amines and the spirotricyciic amines can in each case be independently selected from aryl, C C e aikyi, C C 6 alkoxy, or phenyl(Ci-C6)alkyi.
  • R G and R 7 of the indeno-fused naphthopyran, can together form a group represented by the following general Formula (XD) or general Formula (XE),
  • T and T are each independently oxygen or the group - R i , where R 11 ( Ri 5 , and R 16 are each as set forth and described previously herein.
  • [0981 ⁇ 1 ® ⁇ '3 aR d 1 * groups of the indeno-fused naphthopyrans such as the indeno[2',3':3,4]naphtho[1 ,2-b3pyran represented by general Formula (Vili), and/or the indenoi1 v2':4,3]naphtho[2, 1 -b]pyran represented by general Formula (IX)
  • the phenyl, benzyl, or any! group substituents are each independently selected from C C-e alky! or Ci-C 6 alkoxy.
  • R 1j and R 4 groups of the indeno-fused naphthopyran can each independently also be an -0R 1S group, in which R 8 is selected from C r C 6 a!kyl, pbenyl(Ci-C 3 ⁇ alky!, mono(Ci ⁇ C 6 )aikyl substituted pbenyl(C r C 3 )alkyl, mono(C C e )a!koxy substituted phenyi ⁇ Ci-C3)alkyl, C C 6 aikoxy(C 2 -C 4 )aikyi, C 3 ⁇ C 7 cycioa!kyl, mono(CrC4)afkyl substituted C 3 -C 7 cycloalkyi, CrC 6 chforoaikyi, C r C 6 f uoroalkyl, allyl, or the group wherein R 9 is hydrogen or C1-C3 alky!
  • W is hydrogen, C C 6 alkyl, Ci-Ce aikoxy, the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthy!, phenoxy, mono-, or di-( C C 6 )alkyl substituted phenoxy, mono- or di-(CrC 6 )aikoxy substituted phenoxy, amino, mono(CrC 6 )alky!amino, di(CrCe)aikyiarriino, phenyiamino, mono- or di- ⁇ CrC 6 )alky!
  • substituted phenyiamino or mono- or di-(CrC 6 )aikoxy substituted phenyiamino.
  • the phenyl, benzyl, or aryl group substituents are each independently selected from C r O 6 alkyl or C C s aikoxy.
  • the R 3 and R 14 groups of the indeno-fused naphthopyran can each independently also be a mono-substituted phenyl, in which the phenyl has a substituent located at the para position thereof.
  • the substituent of the mono- substituted phenyl can be: a dicarboxylic acid residue or derivative thereof, a diamine residue or derivative thereof, an amino alcohol residue or derivative thereof, a poiyol residue o derivative thereof, -CH 2 ⁇ , -(CH 2 ) r , or -[0-(CH 2 )$]k-. in which (t) is selected from an integer of 2, 3, 4, 5 or 6, and k is an integer selected from 1 to 50.
  • the substituent of the mono-substituted phenyl is connected to an aryl group on another photochrome material
  • R 13 and R 4 can together form an oxo group, a spiro- carbocyclic group containing 3 to 6 carbon atoms, or a spiro-heterocyciic group containing 1 to 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom.
  • the spiro-carbocyclic and spiro-heterocyclic groups are annel!ated with 0, 1 or
  • the B and 8' groups of the indeno-fused naphthopyran can each be independently selected from: a substituted phenyl; a substituted aryl; a substituted 9- julolindinyl; a substituted heteroaromatic group chosen from pyridyl, furanyl, benzofuran-2-yi, benzofuran-3-yi, thienyi, benzothien-2-y!, benzothien-3-yi, dibenzofuranyl, dibenzothienyi, carbazoyl, benzopyridyi, irtdoiinyl, and fiuorenyi, wherein the phenyl, ary!, 9-juiolindinyl, or heteroaromatlc substituent is the reactive substituent R; an unsubstituted, mono-, di-, or tri-substituted phenyl or aryl group; 9- julolidinyl
  • R 22 is allyl, C C 6 a!kyi, phenyl, mono(CrCe)a!kyi substituted phenyl, mono(Ci-C e )alkoxy substituted phenyl, phenyl(Ci-C 3 )aiky!, mono(C C 6 )aikyi substituted phenyl ⁇ CrC 3 )alkyl, mono ⁇ C C 6 )alkoxy substituted phenyl(C r -C 3 )alkyl ! C -C e aikoxy(C 2 -C 4 )a!ky!
  • R 2 3 and R 2 are each independently C r C 6 alkyi, C 5 -C 7 cycloalkyl, phenyl or substituted phenyl, the phenyl substituents being C C 6 alkyl or C C 6 alkoxy, and said halo substituent Is chloro or fluoro, aryi, mono(CrC 12 )alkoxyary!, di(Ci- C 12 )alkoxyaryl, mono(C r Ci 2 )aiky!aryl, di(Ci-C 12 )alkytaryl, haloaryl, C3-C7 cycloa!kyiaryl, C3-C7 cycloalkyl, C 3 -C 7 cycloalky!oxy, CyCr cyc oalkyloxy ⁇ CrC 12 )alky1 ( C3-C7 cycloaikyioxy(CrC 12 )alkoxy :
  • the 8 and B ! groups can also each independently be an unsubstltuted or mono-substituted group chosen from pyrazolyl, imldazolyl, pyrazolinyl, imidazolinyl, pyrroiinyl, phenothiazinyi, phenoxazinyl, phenazinyl, and acridinyl.
  • the substituents of these mono-substituted groups can each independently selected from C 1 -C12 alkyi, Ci-Ci 2 alkoxy, phenyl, or halogen.
  • the B and B' groups can each be Independently selected from a group represented by the following general Formulas (XSA) or (XiB),
  • K is -CH 2 - or -0-
  • M is -O- or substituted nitrogen, provided thai when M is substituted nitrogen
  • K is - CHr-
  • the substituted nitrogen substituents are hydrogen, C C 12 alkyl, or C r C 2 acyl.
  • Each R 2S is independently selected for each occurrence from d-C 2 alkyl, C C 2 aikoxy, hydroxy, and halogen, and each u is independently an integer ranging from 0 to 2.
  • the R 26 and R 27 groups are each independently hydrogen or CrC 2 alkyl.
  • Each B and 8' group can independently be a group represented by the following general Formula (XN),
  • R z8 is hydrogen or CVC-. 2 alkyl
  • R 2 9 is an unsubstituted, mono- or di-substituted group chosen from naphthyS, phenyl, furany!, and thienyl.
  • the substitutents of the mono- or di-substituted naphthyis, phenyls, furanyls, and thienyls, are in each case independently selected from C r Ci2 alkyl, C r C 12 aikoxy, or halogen.
  • the B and 8 * groups can together form a member selected from, a fluoren-9-ylidene, a mono-substituted fluoren-9-ylidene, or a di-substituted fluoren-9- ylidene.
  • the substituents of the mono-substituted fluoren-9-ylidene, and the di- substituted fluoren-9-yfidene can in each case be independently selected from C r Ci 2 alkyl, C r Ci 2 aikoxy, or halogen.
  • each photochromic moiety is selected from an indeno[2 , ,3 3 ! 4]naphfho[1 ,2--b]pyran represented by Formula ⁇ VIII), each photochromic moiety is bonded to L 2 at ring
  • each phoiochromic moiety is selected from an indeno[2',3':3 ; 4]naphtho[1 ,2-bjpyran represented by Formula ⁇ VIII ⁇ and: each phoiochromic moiety is bonded to L 2 at ring position 3; R ' 3 and R 14 are each independently selected from linear or branched d- C 6 aikyi, such as methyl; R 5 through R 2 are each hydrogen; B is selected from phenyl and linear or branched C C 6 aikoxy substituted phenyl, such as me hoxy
  • B 1 is selected from n which I " is bonded to the oxygen of B'.
  • each photochromic moiety is selected from an lndeno[2 ⁇ 3 ⁇ 3,4)napbtho[1 ,2-- bjpyran represented by Formula (Vlll), each photochromic moiety is bonded to L 2 at ring position 13, R ' : is -0-, and L 2 is bonded to R 4 .
  • each photochromic moiety is selected from an indeno[2',3':3,4]naphtho[1 ,2- bjpyran represented by Formula (VIII) and; each photochromic moiety is bonded to L 2 at ring position 13;
  • B and B' are each independently selected from phenyl and linear or branched CrC 6 aikoxy substituted phenyl, such as methoxy substituted phenyl;
  • R 6 and R ' are each independently selected from linear or branched Ci-C 6 aikoxy, such as methoxy;
  • R 5 , R ! , R 8 ,. 9 and R 10 are each hydrogen;
  • R ° is linear or branched C C 6 alkyi, such as n-butyi; and
  • R 14 is -0-, in which L 2 is bonded to R 14 ,
  • each photochromic moiety is selected from an indeno[2',3':3,4]naphiho[1,2- bjpyran represented by Formula (VIII is bonded to L 2 at
  • R i1 is selected from nd L 2 is bonded to the oxygen of R 11 .
  • each photochromic moiety is selected from an indeno[2 ! ,3':3,4]naphtho[1 ,2- bjpyran represented by Formula (Vlli) and; each photochromic moiety is bonded to l at ring position 11 ; R '3 and R 4 are each independently selected from linear or branched d-C 6 aikyi, such as methyl. R 6 and R ?
  • R 11 is selected from which L 2 is bonded to the oxygen of R 1 .
  • the indeno-fused naphthopyrans from which each photochfomic moiety (PC) can be independently selected can include at least one of a reactive substituent and/or a compatibilizing substltuent.
  • a reactive substituent and/or a compatibilizing substltuent can include at least one of a reactive substituent and/or a compatibilizing substltuent.
  • the photochromic moiety includes multiple reactive substituents and/or multiple compatibilizing substituents, each reactive substituent and each compatibilizing substltuent can be independently chosen.
  • the reactive substituent and the compatibilizing substltuent can each independently be represented in each case by one of:
  • Non-limiting examples of groups that -D- can represent according to various non-limiting embodiments include a diamine residue or a derivative thereof, wherein a first amino nitrogen of said diamine residue can form a bond with -A'-, or a substituent or an available position on the Indeno-fused naphthopyran, and a second amino nitrogen of said diamine residue can form a bond with -E-, -G- or -J; and an amino alcohol residue or a derivative thereof, wherein an amino nitrogen of said amino alcohol residue can form a bond with -AX or a substituent or an available position on the indeno-fused naphthopyran, and an alcohol oxygen of said amino alcohol residue can form a bond with -E-, -G- or -J.
  • the amino nitrogen of said amino alcohol residue can form a bond with -E-, -G- or -J
  • said alcohol oxygen of said amino alcohol residue can form a bond with -A ' -, or a substituent or an available position on the indeno-fused naphthopyran
  • Non-limiting examples of suitable diamine residues that -D- can represent include an aliphatic diamine residue, a cyclo aliphatic diamine residue, a diazacycioalkane residue, an azacycio aliphatic amine residue, a diazacrown ether residue, and an aromatic diamine residue. More particular, illustrative and non- limiting examples of diamine residues that can be used in conjunction with various non-limiting embodiments disclosed herein include the following:
  • Non-limiting examples of suitable amino alcohol residues that -D- can represent include an aliphatic amino alcohol residue, a cyclo aliphatic amino alcohol residue, an azacycio aliphatic alcohol residue, a diazacycio aliphatic alcohol residue and an aromatic amino alcohol residue. More particular, illustrative and non-iimiting examples of amino alcohol residues that can be used in conjunction with various non-limiting embodiments disclosed herein include the following:
  • -E- can represent a dicarboxyiic acid residue or a derivative thereof, wherein a first carbonyi group of said dicarboxyiic acid residue can form a bond with -G- or -D-, and a second carbonyi group of said dicarboxyiic acid residue can form a bond with -G-.
  • suitable dicarboxyiic acid residues thai -E- can represent include an aliphatic dicarboxyiic acid residue, a cycloaiiphatic dicarboxyiic acid residue and an aromatic dicarboxyiic acid residue. More particular, i!fustrative and non-limiting examples of dicarboxyiic acid residues that can be used in conjunction with various non-iimiting embodiments disclosed herein include the following:
  • -G- can represent a group represented by the following general formula
  • x, y and z are each independently chosen and range from 0 to 50, and a sum of X, y, and z ranges from 1 to 50; a polyol residue or a derivative thereof, wherein a first polyol oxygen of said polyol residue can form a bond with -A'-, -D-, -E- , or a su stituent or an available position on the indeno-fused naphthopyran, and a second polyol oxygen of said poiyol can form a bond with -E- or -J; or a combination thereof, wherein the first polyol oxygen of the polyol residue forms a bond with a group ⁇ [(OC 2 H i5 )x ⁇ OC 3 H s ) y (OC 4 H 8 )j- (i.e., to form the group -[
  • po!yols from which the polyol residues that -G ⁇ can represent can be formed according to various non-limiting embodiments disclosed herein include (a) low molecuiar weight poiyols having an average molecular weight less than 500, such as, but not limited to, those set forth in U.S. Patent No. 6,555,028 at col. 4, lines 48-50, and col. 4, line 55 to col. 8, line 5, which disclosure is hereby specifically incorporated by reference herein; (b) polyester poiyols, such as, but not limited to, those set forth in U.S. Patent No, 6,555,028 at col.
  • -J can represent a group -K, wherein -K represents a group such as, but not limited to, -CH 2 COOH, ⁇ CH(CH 3 )COOH, -C(0)(CH 2 ) w COOH, -C 6 H 4 S0 3 H, -C S H, 0 SG 3 H, -C 4 H 8 S0 3 H, ⁇ C 3 H 6 SG 3 H, -C 6 .H 4 S0 3 H and -S0 3 H, wherein "w" ranges from 1 to 18.
  • -J can represent hydrogen that forms a bond with an oxygen or a nitrogen of linking group to form a reactive moiety such as -OH or -NH.
  • -j can represent hydrogen, provided that if -J represents hydrogen, -J is bonded to an oxygen of -D- or -G-, or a nitrogen of -D ⁇ . 0124J
  • -J can represent a group -I or residue thereof, wherein -L can represent a reactive moiety.
  • -L can represent a group such as, but not limited to, acryl, methacryi, crotyi, 2- ⁇ methacryloxy ⁇ ethyicarbarnyi, 2-(methacryloxy)ethoxycarbonyi, 4-vinyiphenyf, vinyl, 1-chiorovinyi or epoxy.
  • acry!, methacryi, crotyl, 2- ⁇ methacryioxy)ethylcarbamyf, 2-(methacryioxy)ethoxycarbonyi, 4-vinylphenyl, vinyl, 1-chlorovinyl, and epoxy refer to the following structures:
  • -G- can represent a residue of a po!yol, which Is defined herein to include hydroxy-containing carbohydrates, such as those set forth in U.S. Patent No. 6,555,028 at col. 7, line 56 to coS. 8, line 17, which disclosure Is hereby specifically incorporated by reference herein.
  • the poiyol residue can be formed, for example and without limitation herein, by the reaction of one or more of the poiyol hydroxy! groups with a precursor of -A'-, such as a carboxy!ic acid or a methylene halide, a precursor of poiyaikoxyiated group, such as po!yalkyiene glycol, or a hydroxy!
  • the poiyol can be represented by g ⁇ (QH) a and the residue of the poiyol can be represented by the formula ⁇ G-q-(OH) a- i, wherein q is the backbone or main chain of the polyhydroxy compound and "a" is at least 2.
  • one or more of the poiyoi oxygens of -G- can form a bond with -J (i.e., forming the group -G-J).
  • -J i.e., forming the group -G-J.
  • the reactive and/or compatib!izing substituent comprises the group -G-J
  • -G ⁇ represents a poiyol residue
  • -J represents a group -K that contains a carboxyi terminating group
  • -G-J can be produced by reacting one or more polyol hydroxy! groups to form the group -K (for example as discussed with respect to Reactions B and C at col. 13, line 22 to col. 16, line 15 of U.S. Patent No.
  • -J represents a group -K that contains a sulfo or suifono terminating group
  • -G-J can be produced by acidic condensation of one or more of the poiyol hydroxy! groups with HOC 6 H 4 S0 3 H; HOC 5 H 10 SO 3 H; HOC 4 H e S0 3 H; HOC 3 H 6 S(3 ⁇ 4H; HOC 2 H 4 S0 3 H; or H 2 S0 4 , respectively.
  • -G- represents a polyol residue and -J represents a group -L chosen from acryl, met ha cry i, 2-(methacryfoxy)ethylcarbamyi and epoxy
  • -L can be added by condensation of the polyoi residue with acryioyl chloride, methacryloyt chloride, 2-isocyanatoeihyi methacry!ate or epichlorohydrin, respectively.
  • -J of one or more of Formulas (XII I) through (XXI) is bonded to L 2 of Formula (I), in which case -J is a divalent linking group represented by -J-.
  • -J is a divalent linking group represented by -J-.
  • examples of divalent -J- include, but are not limited to: -0-; -S-; -NR* ⁇ where R* is hydrogen or hydrocarbyt such as, linear or branched C C 2 o a!kyi, C 3 -C 12 cycioalkyS, C 3 -C 12 heterocycloalkyl, ary!, and heteroary!; -CH 2 COO-; -CH(CH 3 )COO ⁇ ; -C(0)(CH 2 ) w COO-, where "w" is from 1 to 18; -C 6 H 4 S0 3 -; -C 5 H 0 SO 3 -; -C 4 H e S0 3 -; -C 3 H 6 SQ 3 ⁇ ; ⁇ C 2 H S0 3 -; -S0 3 -; and combinations of two or more thereof.
  • R* is hydrogen or hydrocarbyt such as, linear or branched C C 2 o a!kyi, C 3 -C 12
  • Indeno-fused naphthopyrans from which each photochromic moieties (PC) can be independently selected can be prepared by art-recognized methods.
  • the indeno-fused naphthopyrans, from which each photochromic moieties (PC) can be independently selected can be synthesized in accordance with the description provided in United States Patent No. 8,296,785, at column 10, Sine 52 through column 29, line 18, which disclosure is incorporated herein by reference.
  • the indeno-fused naphthopyrans, from which each photochromic moieties (PC) can be independently selected can be synthesized in accordance with the description provided in United States Patent No.
  • the phoiochromic compounds of the present invention can each be used alone, or in combination with other photochromic compounds according to various non-limiting embodiments disclosed herein, or in combination with one or more appropriate complementary conventional photochromic compounds.
  • the photochromic compounds of the present invention can be used in conjunction with conventional photochromic compounds having activated absorption maxima within the range of 300 to 000 nanometers.
  • the photochromic compounds according to the present invention can be used in conjunction with a complementar conventional polymerizable or a compatibiized photochromic compound, such as for example, those disclosed in U.S. Patent Nos. 6, 113,814 (at col. 2, Sine 39 to col. 8, line 41 ), and 6,555,028 (at co!. 2, line 65 to col. 12, line 56), which disclosures are hereby specifically incorporated by reference herein.
  • the photochromic compounds of the present invention can be used In combination with a mixture of other photochromic compounds.
  • mixtures of photochromic compounds can be used to attain certain activated colors such as a near neutral gray or near neutral brown. See, for example, U.S. Patent No, 5,645,767, col. 12, line 66 to col. 13, line 19, which describes the parameters that define neutral gray and brown colors and which disclosure is specifically incorporated by reference herein.
  • the present Invention also relates to a photochromic article that include one or more photochromic compounds according to the present invention, such as represented by Formulas (! and (II).
  • the photochromic articles of the present invention can be selected from ophthalmic articles or elements, display articles or elements, windows, mirrors, packaging material such as shrtnkwrap, and active and passive liquid crystal cell articles or elements.
  • ophthalmic articles or elements include, but are not limited to, corrective and non-corrective lenses, including single vision or multi-vision lenses, which can be either segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetically or otherwise) vision, including without limitation, contact tenses, intra-ocuiar ienses, magnifying ienses, and protective tenses or visors.
  • corrective and non-corrective lenses including single vision or multi-vision lenses, which can be either segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetically or otherwise) vision, including without limitation, contact tenses, intra-ocuiar ienses, magnifying ienses, and protective tenses or
  • Examples of display articles, elements and devices include, but are not limited to, screens, monitors, and security elements, including without Iimitation, security marks and authentication marks.
  • windows include, but are not limited to, automotive and aircraft transparencies, filters, shutters, and optical switches,
  • the photochromic article can be a security element.
  • security elements include, but are not limited to, security marks and authentication marks thai are connected to at least a portion of a substrate, such as; access cards and passes, e.g., tickets, badges, Identification or membership cards, debit cards, etc.; negotiable instruments and non-negotiable instruments e.g., drafts, checks, bonds, notes, certificates of deposit, stock certificates, etc.; government documents, e.g., currency, licenses, identification cards, benefit cards, visas, passports, official certificates, deeds etc.; consumer goods, e.g., software, compact discs ("CDs”), digital-video discs ("DVDs”), appliances, consumer electronics, sporting goods, cars, etc.; credit cards; and merchandise tags, labels and packaging.
  • CDs compact discs
  • DVDs digital-video discs
  • the security element can be connected to at least a portion of a substrate chosen from a transparent substrate and a reflective substrate.
  • a reflective substrate is required, if the substrate is not reflective or sufficiently reflective for the intended application, a reflective material can be first applied to at least a portion of the substrate before the security mark is applied thereto.
  • a reflective aluminum coating can be applied to the at least a portion of the substrate prior to forming the security element thereon.
  • the security element can be connected to at least a portion of a substrate chosen from untinted substrates, tinted substrates, photochromic substrates, tinted-photochromic substrates, linearly polarizing, circularly polarizing substrates, and elliptlcaily polarizing substrates.
  • security elements according to the aforementioned embodiments can further include one or more other coatings or films or sheets to form a multi-layer reflective security element with viewing angle dependent characteristics, such as described In U.S. Patent 6,641 ,874.
  • Photochromic articles according to the present invention can include a substrate and a photochromic material that includes the photochromic compound according to the present invention, in which the photochromic material is connected to at least a portion of the substrate.
  • the term "connected to” means associated with, either directly, or indirectly by means of another material or structure.
  • Photochromic articles according to the present invention can include, as discussed above, a substrate that can include one or more polymeric compounds of the present invention.
  • the photochromic compounds of the present invention can be incorporated into at least a portion of the polymeric material of the substrate; or by incorporating the photochromic compound(s) into at least a portion of the oiigomeric or rnonom.eric material from which the substrate is formed.
  • the photochromic compound can be incorporated into the polymeric material of the substrate by a casi-in-place method or by imbibition. The imbibition and the cast-in-piace methods are discussed in further detail herein below.
  • the photochromic compound is typically diffused into the polymeric material of a previously formed or fabricated article, such as a substrate or previously applied coating/film. Imbibition can be performed by immersing the polymeric material of a previously formed or fabricated article In a solution containing the photochromic compound, with or without heating. Thereafter, although not required, the photochromic compound can be bonded with the polymeric material (e.g.. of the substrate or coating).
  • the photochromic compound(s) can be mixed with: a polymer and/or oligomer composition in solution or melt form; or monomer composition in liquid form, so as to form a castabie photochromic composition.
  • the castabie photochromic composition is then typically introduced into the cavity of a mold (e.g., a lens mold).
  • the castabie photochromic composition is then set within the mold so as to form a photochromic article.
  • a photochromic compound(s) can be Included in a coating that is connected to at least a portion of the substrate,
  • the substrate can be a poiymeric substrate or an inorganic substrate (such as, but not limited to, a glass substrate).
  • the photochromic compound(s) can be incorporated into at least a portion of a coating composition prior to application of the coating composition to the substrate.
  • a coating composition can be applied to the substrate, at least partially set, and thereafter the photochromic compound(s) can be imbibed into at least a portion of the coating.
  • the terms "set” and “setting” include, without limitation, curing, polymerizing, cross-linking, cooling, and drying.
  • Photochromic articles according to the present invention can be formed by art-recognized In-mold coating (or in-mold casting) methods.
  • a photochromic coating composition that includes a photochromic compound(s) of the present invention, which can be a liquid coating composition or a powder coating composition, is applied to at least a portion of the interior surface of a mold, and then at least partiaily set Thereafter, a polymer solution or melt, or oligomeric or monomeric solution or mixture is cast or molded within the mold cavity and in contact with the previously applied photochromic coating composition, and at least partially set. The resulting photochromic article is then removed from the mold.
  • Non-limiting examples of powder coatings in which the photochromic materials according to various non-limiting embodiments disclosed herein can be employed are set forth in U.S. Patent No. 6,088,797 at col. 7, line 50 to col, 19, line 42, which disclosure Is hereby specifically incorporated by reference herein.
  • Photochromic articles according to the present invention can also be formed by art-recognized over-mold methods.
  • Over- nold methods typically involve forming a substrate within a moid, and then forming an interior space between the substrate and an interior surface of the moid, into which a photochromic coating composition is then subsequently introduced (e.g., injected) and then set (e.g., cured).
  • over-mold methods can involve introducing a previously formed substrate into a mold, such that an interior space is defined between the substrate and an interior mold surface, and thereafter a photochromic coating composition is introduced (e.g., injected) into the interior space.
  • the photochromic coating compositions include one or more photochromic compounds of the present invention.
  • Photochromic articles according to the present invention can also be formed by means of art-recognized lamination methods. With lamination methods, a film comprising the photochromic compound(s) according to the present invention can be adhered or otherwise connect to a portion of the substrate, with or without an adhesive and/or the application of heat and pressure. Thereafter, if desired, a second substrate can be applied over the first substrate and the two substrates can be laminated together (i.e., by the application of heat and pressure) to form an element wherein the film comprising the photochromic compound is interposed between the two substrates.
  • Methods of forming films comprising the photochromic compounds of the present invention can include for example and without limitation, combining a photochromic compound with a polymeric solution or oiigomeric solution or mixture, casting or extruding a film therefrom, and, if required, at least partially setting the film. Additionally or alternatively, a film can be formed (with or without a photochromic compound) and imbibed with the photochromic compound,
  • Coating compositions that include the photochromic compound(s) of the present Invention can be connected to at least a portion of the substrate of the photochromic article by art-recognized methods, such as applying a coating composition that includes the photochromic eompound(s) to at feast a portion of a surface of the substrate, and at least partially setting the coating composition. Additionally or alternatively, the coating that includes the photochromic cornpound(s) can be connected to the substrate, for example, through one or more additional coatings.
  • an additional coating composition can be applied to a portion of the surface of the substrate, at least partially set, and thereafter the coating composition that includes ihe photochromic cornpound(s) can be applied over the additiona! coating and at least partially set.
  • the coating composition that includes ihe photochromic cornpound(s) can be applied over the additiona! coating and at least partially set.
  • additional coatings and films that can be used In conjunction with the photochromic coatings and articles according to the present invention, include, but are not limited to: primer coatings and films ⁇ which typically reside under the photochromic coating); protective coatings and films (which are typically applied over the photochromic coating), including transitional coatings and fiims and abrasion resistant coatings and fiims; anti-reflective coatings and fiims; conventional photochromic coatings and films; polarizing coatings and films; and combinations thereof.
  • protective coating or film refers to coatings or films that can prevent wear or abrasion, provide a transition in properties from one coating or film to another, protect against the effects of polymerization reaction chemicals and/or protect against deterioration due to environmental conditions such as moisture, heat, ultraviolet light, oxygen, etc,
  • transitional coating and film means a coating or film that aids in creating a gradient in properties between two coatings or films, or a coating and a film .
  • a transitional coating can aid In creating a gradient in hardness between a relatively hard coating and a relatively soft coating.
  • Non-limiting examples of transitional coatings include radiation-cured, acrylate-based thin films as described in U.S. Patent Application Publication 2003/0165686 at paragraphs 79- 73, which are hereby specifically incorporated b reference herein.
  • abrasion resistant coating and film refers to a protective polymeric material that demonstrates a resistance to abrasion that is greater than a standard reference material, e.g., a polymer made of CR-39 ® monomer available from PPG Industries, fnc, as tested in a method comparable to ASTM F-735 . Standard Test Method for Abrasion Resistance of Transparent Plastics and Coatings Using the Oscillating Sand Method.
  • Non-limiting examples of abrasion resistant coatings include, for example, abrasion-resistant coatings comprising organosllanes, organosiloxanes, abrasion -resistant coatings based on inorganic maieriais such as silica, titania and/or zirconia, organic abrasion-resistant coatings of the type that are ultraviolet light curable, oxygen barrier-coatings, UV-shie!ding coatings, and combinations thereof.
  • Non-iirniting examples of antireffective coatings and films include a monolayer, multilayer or film of metal oxides, metal fluorides, or other such materials, which can be deposited onto the articles disclosed herein (or onto films that are applied to the articles ⁇ , for example, through vacuum deposition, sputtering, etc.
  • Non-iirn Sting examples of conventional photochromic coatings and films include, but are not limited to, coatings and films comprising conventional photochromic materials.
  • Non-limiting examples of polarizing coatings and films include, but are not limited to, coatings and films comprising dichroic compounds that are known in the art,
  • Additional coating compositions e.g., primers and over-coats
  • photochromic coating compositions according to the present invention and/or to form photochromic articles according to the present invention can be applied to / formed; on a substrate prior to application of the photochromic coating; and/or over a previously applied photochromic coating.
  • a primer coating can be formed on the substrate prior to applying a photochromic coating composition according to the present invention.
  • an additional coating or film can be applied (e.g., as an over-coat or over-coating) at least partially over a previously applied photochromic coating composition according to the present invention.
  • a transitional coating can be formed over a previously applied photochromic coating composition according to the present invention, and an abrasion resistant coating can then be applied over the transitional coating,
  • Photochromic coating compositions according to the present invention include: a photochromic compound according to the present invention, such as described previously herein with reference to Formulas (i) and (H); a curable resin composition; and optionally a solvent.
  • the photochromic coating composition can be in the form of art-recognized liquid coatings and powder coatings.
  • the photochromic coating compositio s of the present invention can be thermoplastic or thermosetting coating compositions.
  • the photochromic coating composition is a curable or thermosetting coating composition.
  • the curable resin composition of the curable photochromic coating compositions according to the present invention typically include: a first reactant (or component) having functional groups, e.g., an epoxide functional polymer reactant; and a second reactant (or component) that is a crossllnking agent having functional groups that are reactive towards and that can form covending bonds with the functional groups of the first reactant.
  • the first and second reactants of the curable resin composition of the curable photochromic coating composition can each independently include one or more functional species, and are each present in amounts sufficient to provide cured photochromic coatings having a desirable combination of physical properties, e.g., smoothness, optical clarity, solvent resistance and hardness.
  • epoxide functional polymer e.g., (meth)acfyltc polymers containing residues of glycidyi (meth)acrylate and epoxide reactive crossllnking agent
  • curable resin compositions comprising hydroxy functional polymer and capped (or blocked) isocyanate functional crossiinking agent
  • the curable resin composition of the photochromic coating composition of the present invention Is a curable urethane (or poiyurethane) resin composition.
  • Curable urethane resin compositions useful In the photochromic coating compositions of the present invention typically Include: an active hydrogen functional polymer, such as a hydroxy functional polymer; and a capped (or blocked) isocyanate functional crossiinking agent.
  • Hydroxy functional polymers that can be used In such compositions include, but are not limited to, art-recognized hydroxy functional vinyl polymers, hydroxy functional polyesters, hydroxy functional polyureihanes and mixtures thereof,
  • Vinyl polymers having hydroxy functionality can be prepared by free radical polymerization methods that are known to those of ordinary skill in the art.
  • the hydroxy functional vinyl polymer is prepared from a majority of (meth)acrylate monomers and Is referred to herein as a "hydroxy functional (meth)acry!ic polymer.”
  • Hydroxy functional polyesters useful in curable photochromic coating compositions comprising capped isocyanate functional crossiinking agent can be prepared by art-recognized methods. Typically, diois and dicarboxylic acids or diesters of dicarboxylic acids are reacted In a proportion such that the molar equivalents of hydroxy groups is greater than that of carboxylic acid groups (or esters of carboxylic acid groups) with the concurrent removal of water or alcohols from the reaction medium.
  • Hydroxy functional urethanes can be prepared by art-recognized methods, for example, as previously described herein. Typically one or more difunctional isocyanates are reacted with one or more materials having two active hydrogen groups (e.g., diois or dithiois), such that the ratio of active hydrogen groups to isocyanate groups is greater than 1 , as is known to the skilled artisan.
  • diois or dithiois two active hydrogen groups
  • capped ⁇ or blocked) isocyanate crossiinking agent is meant a crossiinking agent having two or more capped isocyanate groups that can decap (or deblock) under cure conditions, e.g., at elevated temperature, to form free isocyanate groups and free capping groups.
  • the free isocyanate groups formed by decapping of the crossiinking agent are preferably capable of reacting and forming substantially permanent covalent bonds with the active hydrogen groups of the active hydrogen functional polymer (e.g. , with the hydroxy groups of a hydroxy functional polymer).
  • the capping group of the capped isocyanate cross!inking agent not adversely affect the curable photochrome coating composition upon decapping from the isocyanate (i.e., when It becomes a free capping group). For example, it is desirable thai the free capping group neither become trapped in the cured film as gas bubbles nor excessively plastisize the cured film.
  • Capping groups useful in the present invention preferably have the characteristics of being nonfugitive or capable of escaping substantially from the forming coating prior to its vitrification. Typically, the free capping groups escape substantially from the forming (e.g,, curing) coating prior to its vitrification.
  • Classes of capping groups of the capped isocyanate crosslinking agent can be selected from: hydroxy functional compounds, e.g., linear or branched C 2 -C 8 alcohols, ethylene glycol butyl ether, phenol and p-hydroxy methy!benzoate; H- azoles, e.g., 1 H ⁇ 1 ,2,4-triazoie and 1 H ⁇ 2,5-dimeihy ⁇ pyrazoie lactams, e.g., e- caproiactarn and 2-pyrolidinone; ketoximes, e.g., 2-propanone oxime and 2-butanone oxime.
  • Other suitable capping groups include, morphoiine, 3-aminopropyS morpho!ine and N-hydroxy phthalimide,
  • the isocyanate or mixture of isocyanates of the capped isocyanate crosslinking agent has two or more Isocyanate groups (e.g., 3 or 4 isocyanate groups).
  • suitable isocyanates thai can be used to prepare the capped isocyanate crosslinking agent include, monomeric diisocyanates, e.g., a, a'-xylylene dtisocyanate, a, a, a', a' ⁇ teiramethylxylylene diisocyanate and 1-isocyanato-3- isocyanatomethyl-3,5,5-trimethylcyciohexane (isophorone diisocyanate or IPDI), and dtmers and trimers of monomeric diisocyanates containing isocyanurate, uretidino, biruet or aliophanate linkages, e.g., the trimer of !PDI.
  • the capped isocyanate crosslinking agent can also be selected from oiigomeric capped isocyanate functional adducts.
  • oiigomeric capped polyisocyanate functional adduct is meant a material that is substantially free of polymeric chain extension
  • Oiigomeric capped polyisocyanate functional adducts can be prepared by art-recognized methods from, for example, a compound containing three or more active hydrogen groups, e.g., trimethy!oipropane (T P), and an isocyanate monomer, e.g., 1 -isocyanato-3,3,5-trimethyi-5- ssoeyanatornethylcyciohexane (IPD!), In a molar ratio of 1 :3, respectively, in the case of TMP and IPDI, by employing art-recognized starved feed and/or dilute solution synthesis techniques
  • one or more catalysts are typically present in the curable photochromie coating composition in amounts of from, for example, 0.1 to 5 percent by weight, based on total resin solids of the composition.
  • Classes of useful catalysts include but are not limited to, metal compounds, In particular, organic fin compounds, e.g., tln(ll) octanoate and dibutyltin(iV) dilaurate, and tertiary amines, e.g., diazablcycio[2.2.2]octane.
  • Curable photochromie coating compositions according to the present invention which include hydroxy functional polymer and capped isocyanate functional crossiinking agent, typically have present therein hydroxy functional polymer In an amount of from 55 percent to 95 percent by weight, based on total resin solids weight of the composition, e.g. , from 75 percent to 90 percent by weight, based on total resin solids weight of the composition.
  • the capped isocyanate functional crossiinking agent is typically present in the curable resin composition in an amount corresponding to the balance of these recited ranges, i.e., 5 to 45, particularly 10 to 25, percent by weight.
  • the equivalent ratio of isocyanate equivalents in the capped isocyanate crossiinking agent to hydroxy equivalents In the hydroxy functional polymer is typically within the range of 1 :3 to 3;1 , e.g., 1 :2 to 2:1. While equivalent ratios outside of this range can be employed, they are generally less desirable due to performance deficiencies in cured photochromie films obtained therefrom.
  • Curable photochromie coating compositions according to the present invention that include hydroxy functional polymer and capped isocyanate functional crossiinking agent are typically cured at a temperature of from 120°C to 190°C over a period of from 10 to 80 minutes.
  • Photochromie coating compositions according to the present invention can, with some embodiments, optionally further include a solvent.
  • suitable solvents include, but art not limited to, acetates, alcohols, ketones, glycols, ethers, aiiphattcs, cycloaiiphaiics and aromatics.
  • acetates include, but are not limited to, ethy! acetate, butyl acetate, and glycol acetate
  • ketones include, but are not limited to, methyl ethyl ketone and methy!-N-amyl ketone.
  • aromatics include, but are not limited to, are toluene, naphthalene and xylene.
  • one or more solvents are added to each of the first reactant and the second reactant.
  • Suitable solvent blends can include, for example, one or more acetates, propanol and its derivatives, one or more ketones, one or more alcohols and/or one or more aromatics. If present, the solvent is typically present in an amount of from 5 to 60 percent b weight, or 5 to 40 percent by weight, or 10 to 25 percent by weight, based on the total weight of the photochromic coating composition (inclusive of the solvent weight).
  • Curable photochromic coating compositions according to the present invention can, with some embodiments, optionally contain additives such as waxes for flow and wetting, flow control agents, e.g., poly ⁇ 2-eihylhexyl)acrylate, adjuvant resin to modify and optimize coating properties, antioxidants and ultraviolet (UV) light absorbers.
  • additives such as waxes for flow and wetting, flow control agents, e.g., poly ⁇ 2-eihylhexyl)acrylate, adjuvant resin to modify and optimize coating properties, antioxidants and ultraviolet (UV) light absorbers.
  • useful antioxidants and UV light absorbers include those available commercially from Ciba-Geigy under the trademarks IRGANOX and TINUVIN.
  • These optional additives, when used, are typically present in amounts up to 20 percent by weight (e.g., from 0,5 to 10 percent by weight), based on total weight of resin solids of the curable resin composition.
  • Photochromic compositions, articles and coating compositions according to the present invention can, with some embodiments, further include art-recognized additives that aid or assist in the processing and/or performance of the compositions or articles.
  • additives include photoinittators, thermal initiators, polymerization inhibitors, solvents, light stabilizers (such as, but not limited to, ultraviolet light absorbers and light stabilizers, such as hindered amine light stabilizers (HALS)), heat stabilizers, mold release agents, rheology control agents, leveling agents (such as, but not limited to, surfactants), free radical scavengers, adhesion promoters (such as hexanediol diacrylate and coupling agents), and combinations and mixtures thereof.
  • light stabilizers such as, but not limited to, ultraviolet light absorbers and light stabilizers, such as hindered amine light stabilizers (HALS)
  • HALS hindered amine light stabilizers
  • leveling agents such as, but not limited to,
  • the photochromic compounds according to the present invention can be used in amounts (or ratios) such that the organic material or substrate (e.g., photochromic articles and photochromic coatings) into which the photochromic compounds are incorporated or otherwise connected exhibits desired optical properties.
  • the amount and types of photochromic compounds can be selected such thai the organic material or substrate is clear or co!orless when the photochromic compound is in the closed-form (e.g., in the bleached or unacttvated state), and can exhibit a desired resultant color when the photochromic compound is in the open-form (e.g., when activated by actinic radiation).
  • the precise amount of the photochromic compound that is utilized in the various photochromic compositions and articles described herein is not critical provided that a sufficient amount is used to produce the desired effect.
  • the particular amount of the photochromic compound used can depend on a variety of factors, such as but not limited to, the absorption characteristics of the photochromic compound, the color and intensity of the color desired upon activation, and the method used to incorporate or connect the photochromic compound to the substrate.
  • the amount of the photochromic compound thai is incorporated into an organic material can range from 0.01 to 40 weight percent, or from 0.05 to 15, or from 0, 1 to 5 weight percent, based on the weight of the organic material.
  • Photochromic Material A 3,3-di(4-methoxyphenyl)-6,11 ,13- trimeihyl-13 ⁇ (2 ⁇ (2 ⁇ (2-hydroxyethoxy)ethoxy)ethoxy-3H, 13H- can be prepared by following the process of Example 8 of U.S, Patent 6, 1 13,814, which example is incorporated herein by reference, except that in Step 7 of the process, triethyiene glycol is used in place of diethylene glycol.
  • a photochromic materia! such as 3-(4-(2-hydroxyethoxy)phenyl)-3-(4- methoxypheny!) ⁇ 13, 3-dimethyi ⁇ 3H, 13H-!ndeno[2',3':3 ( 4]rtaphthot ,2-bjpyran can be prepared by reacting 7,7-dimeihyl-5 ⁇ hydroxy-7H ⁇ benzo[C]fiuorene with 1 - ⁇ 4-(2- hydroxyethoxy)phenyi) ⁇ 1 -(4 ⁇ methoxyphenyl)-2-propyn-1 -of using procedures known to those skilled in the art.
  • a photochromic material such as 3- ⁇ 4-methoxyphenyi)-3-(4- ⁇ 2- hydroxyethoxy ⁇ phenyl)-6,7-dimethoxy ⁇ 1 l -trifluoromethyi-I S S-dimethyl-SH iSH- indenoP'.S ⁇ S ⁇ lnaphthofl ⁇ -bjpyran can be prepared following the procedure of Example 1 in U.S.
  • a photochromic material such as 3 1 3-di(4"methoxyphenyl)- 6, 1 1 - dimethoxy-13-buiyl-13-(2-hydroxyethoxy)-3H,13H-indeno[2' ) 3 , :3,4Jnaphtho[1 ,2- hjpyran can be prepared by using the same process as described above for
  • Photochromic Materia! A except that 3,3-di(4-methoxyphenyl ⁇ -6, 1 1 -dimethoxy-13- butyl-13-hydroxy-3H.13H-inden0[2',3':3,4]naphtho(1 ,2 ⁇ b]pyran and ethylene glycol are reacted together in Step 7 of Example 8 of U.S. 8,1 13,814.
  • a photochromic material such as 3-(4-morpholinophenyl)-3-(4- ⁇ 2- hydroxy)ethoxy)phenyl-l 3, 13-dimethyi-3H, 13H-indenoi2',3':3,4]naphtho[1 ,2 ⁇ b]pyran can be prepared following the procedure of Steps 1-5 of Example 7 in U.S.
  • the aqueous layer was recovered and extracted with ethyl acetate (2x600 mL each time). The organic layers were combined and washed with a saturated aqueous solution of sodium bicarbonate ⁇ 1 L), dried over sodium sulfate and concentrated by rotary evaporation to yield 231 grams of (4- bromophenyl)(3 ⁇ methoxypheny!methanone. The product was not purified and was used in the next reaction as is.
  • Step 1 the product of Step 1 (90,6 g) and potassium tert-butoxide (56 g) were stirred in toluene (900 ml) using a mechanical stirrer.
  • dimethyl succinate 70 mL slowly drop-wise using an addition funnel over a 1 hour period.
  • the exothermic reaction warmed to 40°C during the dimethyl succinate addition and became more viscous.
  • Additional toluene 400 mL was added.
  • the reaction mixture was stirred for an additional 2 hours.
  • the reaction mixture was slowly poured into a beaker containing deionized water (1 L) and ice.
  • Step 3 the product of Step 3 (126 g) was stirred in acetic anhydride (500 mL). The reaction mixture was heated to reflux for 3 hours and then coofed to room temperature. It was concentrated by rotary evaporation and toluene was added (2x200 mL) and evaporated to remove residual water. The resulting residue was purified by column chromatography on silica gel (1000 g ⁇ eluting with a solution of 25% ethyl acetate / 75% hexanes. Fractions containing desired product were combined and concentrated by rotary evaporation. The resulting residue was recrystallized in methanol. The crystals were collected by vacuum filtration. Methyl 4-acetoxy- 1 - ⁇ 4-bromophenyi)-7-methoxy-2-naphthoate (23 g) was isolated. This step was repeated to produce additional product for the next- step.
  • Step 3 In an oven-dried flask placed under a nitrogen atmosphere, the product of Step 3 (25 g), 2,4-dimethoxyphenyiboronic acid (11 .1 g) and sodium carbonate (1 .2 g) were stirred in 1 ,2-dimethoxyethane (125 mL) and deionized water (40 mL), A nitrogen purge fine was inserted directly into the reaction mixture for 10 minutes and then removed. Tetrakis(tripheny!phosphine)paliadium(0) (1.4 g) was added to the reaction mixture. Si was heated to reflux for 4 hours. After cooling to room temperature, the reaction mixture was poured into a beaker containing deionized water (1 L) and ice.
  • the resulting residue was purified by a chromatography column of silica gel (200 g) eiuting with a solution of 50% ethyl acetate / 50% hexanes. Fractions containing product were combined and concentrated by rotary evaporation. The resulting residue weighed 26 grams and was composed of 4-(2' ) 4' « dimethoxy-[1 1 1 '-biphenyl ⁇ 4-y!)-3-(4-hydroxyheptan-4-yi)-6- methoxynaphtha!en-1-ol and several impurities, it was used In the next reaction as is.
  • Step 7 The product of Step 7 (5.3 g), triethyiamine (2.0 g), and tetrahydrofuran (50 mL) were combined in a reaction flask, and the mixture was stirred at room temperature. Sebacoyi chloride (1.3 g) was added drop-wise to the solution and the mixture was further stirred at room temperature for 2 hours. The mixture was filtered through a short silica gel plug and concentrated. The product was isolated by silica gei chromatography (ethyl acetate/metby!ene chloride (v/v), 1/20). The recovered product was precipitated from methylene chioride/methanol (v/v: 1/4) and filtered off as a purple-tinted powder (3.5 g).
  • the nuclear magnetic resonance (NMR) spectrum showed the product to have a structure consistent with bis(2-(4-(3-(4- methoxypheny ⁇ )-7-methoxy-1 1 -(2,4 ⁇ dimethoxyphenyi)-13, 13-dipropyl-3H, 13H- indeno[2 , ,3':3 l 4]naphtho 1 ,2-blpyran-3-yl)phenoxy)ethyi) decanedioate shown in the following graphic formula:
  • the reaction mixture was cooled to room temperature, and then poured into 200 ml of ethyl acetate. This mixture was washed twice, each time with 250 mL of a 1 :1 mixture of saturated aqueous NaHC0 3 and water. The organic layer was recovered, dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting residue was purified by column chromatography. The pure fractions were combined, rotovaped and dried under vacuum to obtain 6.1 grams of a yeiiowish-greenish foam.
  • Step 1 the product of Step 1 (121 g) and 3,4 ⁇ dihydro-2H-pyran ⁇ 106 mL) were stirred in dschloromethane (1100 mL). To this was added p-ioiuenesu!fonic acid (4.4 g). The reaction mixture was stirred at room temperature for 2 hours, it was then transferred to a separatory funnel and washed with a saturated aqueous solution of sodium bicarbonate (1 L), dried over sodium sulfate and concentrated by rotary evaporation to yield an oil.
  • Step 3 In an oven-dried flask placed under a nitrogen atmosphere, the anhydrous product of Step 2 ⁇ 160 g) was stirred in dimethylformamide that had been saturated with acetylene gas (640 mL). The reaction flask was placed in an ice bath and to the reaction fiask was added an 18wt% slurry of sodium acetyiide in xylenes and mineral oil (310 g) drop-wise using an addition funnel ove a 40 minute period. The reaction was warmed to room temperature and stirred for 2 hours, it was slowly poured into a beaker containing deionized water (2 L), ice and chloroform (1 L).
  • the recovered aqueous layer was extracted with dichioromet ane (600 mL). The organic layers were combined and washed with a saturated aqueous solution of sodium bicarbonate (1 L), dried over sodium sulfate and concentrated by rotary evaporation. The resulting residue was purified by column chromatography on silica gel (1300 g) eluting with a solution of 50% ethyl acetate / 50% hexanes. The fractions containing product were combined and concentrated by rotary evaporation. The resulting residue was further purified with a second silica gel column ⁇ 1300 g) eluting with 25% ethyl acetate / 75% hexanes.
  • the product from Step 5 was dissolved in xylene (400 mL) In a 2 L single- neck flask equipped with Dean-Stark trap and water condenser. Bismuth trif uoromethanesulionate (1 ,6 g) was added to the flask. The reaction mixture was heated to reflux for 4 hours. The resulting mixture was cooled to room temperature and filtered through a silica gel piug. The major fraction was collected and condensed to less volume.
  • Solid product (6.5 g) was recrystaiized out from t-butyl methyl ether/hexane solution to yield an off-white solid, 9-phenyi-2-methoxy-7,7-dipropyi-7H- benzo[c]fluoren-5-ol.
  • Step 1 The product of Step 1 (4.0 grams), the product of Step 3 (4.0 grams), and 100 mL of chloroform were combined in a reaction flask and stirred at 40°C. Sufficient dodecylbenzenesu!fonic acid was added (3-5 drops) to produce a deep black coloration to the solution. After two hours, the reaction mixture was cooled and washed with 100 ml. of water. The organic layer was separated, dried over sodium sulfate, and concentrated by rotary evaporation to yield dark oil. Methanol (100ml) was added to the product. Upon warming and stirring, the product readily crystallized. The crystals were filtered, washed with fresh methanol and dried to yield 4.2 grams of an off-white solid.
  • Step 4 The product of Step 4 (4.16 g), succinic anhydride (2.2 g), 4- dimethy!aminopyridine (45 mg), and anhydrous tetrahydrofuran (80 mL) were combined in a reaction flask. The reaction mixture was heated at reflux for 4 hours and then stirred at 55 C C overnight. The reaction mixture was concentrated.
  • Step 5 The product of Step 5 (4.49 g), decanediol (0.58 g) s , ⁇ '- dicyclohexylcarbodiimide (1.52 g), 4-dimethy!aminopyridine (0,49 g), dodecy! benzenesulfonic acid (1 .09 g), and methylene chloride (70 ml.) were combined in a reaction flask. The reaction mixture was stirred at room temperature overnight. The mixture was filtered and concentrated. The product was isolated by silica gel chromatography (methylene chloride and then ethyl acetate/methylene chloride (v/v), 1/6), yielding 3.0 g of a green-tinted solid.
  • reaction mixture was stirred at room iemperature for 4 hours and further additions of 1 ⁇ (4-methoxyphenyl)-1 '- ⁇ 4-(2- hydroxy)ethoxyphenyl)-2-propyn-1-ol (2.0 g), and PTSA (p-tciuene-su!fonic acid, 0.5 g) were made.
  • the reaction mixture was stirred overnight and then washed with 400 ml of a 1 : 1 mixture of saturated aqueous NaHCG 3 and wafer.
  • the organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation.
  • the resulting residue was purified by purified by chromatography to get 8.4 grams of a grayish solid.
  • Step 2 The product of Step 2 (3.90 g), succinic anhydride (1.6 g), 4- dtmethyiaminopyridine (33 mg), and anhydrous tetrahydrofuran (80 mL ⁇ were combined in a reaction flask. The reaction mixture was heated at reflux for 4 hours and then stirred at 55°C overnight.
  • Step 3 The product of Step 3 (4.0 g), decanedlol (0.41 g), ⁇ , ⁇ '- dicyciohexy!carbodiimide (1 .09 g), 4-dirnethylaminopyridine (0.35 g), dodecy! benzenesuifonic acid (0.79 g), and methylene chloride (60 mL) were combined in a reaction flask. The reaction mixture was stirred at room temperature overnight. The mixture was filtered and concentrated. The product was isolated by silica gel chromatography using methylene chloride and then ethyl acetate/methylene chloride (v/v), 1/20, yielding 2.5 g of a green-tinted solid.
  • Step 1 The product of Step 1 (3.6 g), decanediof (0.408 g), ⁇ , ⁇ '- dicyciohexylcarbodilmide (1,06 g), 4-dimethyiaminopyridine (0.343 g), dodecy! benzenesuifonic acid (0.764 g), and methylene chloride (120 mL) were combined in a reaction flask. The reaction mixture was stirred at room temperature overnight. The mixture was filtered and concentrated.
  • Step 2 The product of Step 1 (4.0 g), 1 « (4 ⁇ 2-hydroxyethoxy)pheny!-1 ⁇ (4 ⁇ morpholiRophenyl)-2-propyn ⁇ 1-ol (3.7 g, made as described in Step 3 of Example 7 of U.S. 2006/0022176A1), which disclosure is incorporated herein by reference, dodecylbenzene sulfonic acid (0.2 g) and chloroform (preserved with pentene, 250 mL) were combined in a reaction flask and stirred at room temperature for 5 hours. The reaction mixture was washed with 50 % saturated aqueous NaHCC (200 mL ⁇ and the organic layer was dried over anhydrous Na 2 S0 . The solvent was removed by rotary evaporation. Hot methanol was added to the resulting residue and the solution cooled to room temperature. The resulting precipitate was collected by vacuum filtration and washed with cold methanol yielding 4,7 g of
  • Step 3 The product of Step 3 (2.1 g), succinic anhydride (0.49 g), 4- dimethylaminopyridine (15 mg), and anhydrous tetrahydrofuran (30 mL) were combined in a reaction flask. The reaction mixture was heated at reflux for 4 hours and then stirred a! 55C overnight. The reaction mixture was concentrated.
  • Step 4 The product of Step 4 (1.8 g), decanediol (0.165 g), ' , ⁇ '- dicyciohexyicarbodiimide (0.43 g), 4-dimethyiaminopyridine (0,14 g), dodecyl benzenesulfonic acid ⁇ 0.31 g), and methylene chloride (42 mL) were combined in a reaction fiask. The reaction mixture was stirred a! room temperature overnight, The mixture was filtered and concentrated. The product was isolated by silica gel chromatography (ethyl acetate/hexanes (v/v): 4/1 ), yielding 1.2 g of a purpfe-tinted solid.
  • Step 1 The product of Step 1 (1.53 g), decanedio ⁇ (0.176 g), ⁇ , ⁇ '- dicyclo exyicarbodiimlde (0.457 g), 4-dimethylamjnopyrtdine (0.148 g), dodecyl benzenesulfonic acid (0.33 g), and methylene chloride (52 mL) were combined in a reaction flask. The reaction mixture was stirred at room temperature overnight. The mixture was filtered and concentrated.
  • Step 1 The product of Step 1 (1 .0 g), Methylene glycol (0.108 g), ⁇ , ⁇ '- dicyclohexyicarbodumide (0.325 g), 4-dimethylaminopyridine (0.105 g), dodecyl benzenesuifonic acid (0.235 g), and methylene chloride (40 mL) were combined in a reaction flask. The reaction mixture was stirred at room temperature overnight. The mixture was filtered and concentrated. The product was isolated by silica gel chromatography (ethyl acetate/hexanes (v/v): 2/1 ), yielding 0.5 g of a blue-tinted solid.
  • Step 1 The product of Step 1 (3.0 g), 1 -(4-methoxyphenyi) ⁇ 1 -(4-morphoiinophenyl)-2- propyn-1-oi (3.0 g, made as described in Step 1 of Example 1 of U.S. Patent No. 5,458,814, which disclosure is incorporated herein by reference, dodecyibenzene sulfonic acid (0.2 g) and chloroform (preserved with pentene, 250 mL) were combined in a reaction flask and stirred at room temperature for 5 hours. The reaction mixture was washed with 50 % saturated aqueous NaHC0 3 (200 mL) and the organic layer was dried ove anhydrous Na 2 S0 4 . The solvent was removed by rotary evaporation. Hot methanol was added to the resulting residue and the solution cooled to room temperature, The resulting precipitate was collected by vacuum filtration and washed with cold methanol yielding 3.4 g of
  • Step 2 The product of Step 2 (3.0 g), succinic anhydride (0,82 g), 4- dimeihyiaminopyridine (25 mg) r and anhydrous tetrahydrofuran (30 mL) were combined in a reaction flask. The reaction mixture was heated at reflux for 4 hours and then stirred at 55°C overnight, The reaction mixture was concentrated.
  • Step 3 The product of Step 3 (1 .0 g), decanediol (0, 10 g), , '- dicyclohexylcarbodiimide (0.27 g ⁇ , 4-d!methyiaminopyridine (0,09 g), dodecyl benzenesulfonic acid (0.20 g), and methylene chloride (30 mL) were combined in a reaction flask. The reaction mixture was stirred at room temperature overnight. The mixture was filtered and concentrated. The product was Isolated by silica gel chromatography (ethyl acetate/hexanes (v/v); 2/1 ), yielding 0.6 g of a green-tinted solid.
  • SH.I SH-indenop'.S ⁇ S ⁇ jnaphfhoil ⁇ -bjpyrars (3.5 g), 1 ,6-hexane diisocyanate (0,56 g), butyiated hydroxytoluene (23 mg), dibutyitin di!aurate (23 mg), and ethyl acetate (30 mL) were combined in a reaction flask, and the mixture was heated at reflux for 2. hours. Methanol (5 ml) was added to the mixture to quench excess 1 ,6-hexane diisocyanate. The mixture was concentrated and the residue was purified by siiica gel chromatography (ethyl acetate/hexanes (v/v): 1/1 ).
  • Step 1 The product of Step 1 (4.9 g), meta-ietramethylxylySene diisocyanate (0.388 g), butyiated hydroxyto!uene (1 1 mg), dibutyltin di la urate (1 1 mg), and ethyl acetate (30 mL) were combined in a reaction flask, and the mixture was heated at reflux for 2 hours. Methanol (5 ml) was added to the mixture to quench excess meta- tetramethylxyiylene diisocyanate. The mixture was concentrated and the residue was purified fay silica gel chromatography (ethyl acetate/hexanes (v/V): 1/1 , 2/1).
  • the toluene layer was recovered, concentrated and the residue was purified by silica gel chromatography (ethyl acefate/hexanes (v/v), 1/2, 1/1 ), yielding 4.4 g of a purple- tinted oil, 1 -(4-(3-(4-meihoxyphenyi)-13,13-dimethy!-3H,13H- indeno ⁇ 2',3 , :3 > 4]naphtho[1 ,2 ⁇ b]pyran-3-y!phenoxy)-poly(caprolactone-1000) hydroxyiate.
  • Step 1 The product of Step 1 (3.2 g), DESMODUR® N 3600 poiyisocyanate (0,379 g), butyiated hydroxyto!uene ⁇ 7 mg), dibutyltin dilaurate (7 mg). and ethyl acetate (30 g) were combined in a reaction flask, and the mixture was heated at reflux for 2 hours. Methanol (5 mL) was added to the mixture to quench excess DESMODUR ® N 3800 poiyisocyanate. The mixture was concentrated and the residue was purified by silica gel chromatography (ethyl acetate/hexanes (v/v): 1/1 , 2/1 ). The product was obtained as a purple-tinted oil (1.5 g).
  • the photochromic performance of the photochromic materials of Examples 1- 22 were tested as follows, A quantity of the photochromic material to be tested, calculated to yield a 1 .5 x 10 ⁇ 3 M solution, was added to a fiask containing 50 grams of a monomer blend of 4 parts ethoxyiaied bispheno! A dimethacrylate (BRA 2EO DMA), 1 part po!y(ethylene giycoi) 600 dimethacrylate, and 0.033 weight percent 2,2'- azobis(2-meihyi propionitrt!e) (AIBN). The photochromic material was dissolved into the monomer blend by stirring and gentle heating.
  • the photochromic test squares prepared as described above were tested for photochromic response o an optical bench. Prior to testing on the optica! bench, the photochromic test squares were exposed to 365 nm ultraviolet light for about 15 minutes to cause the photochrornrc material to transform from the ground state-form to an activated-state form, and then placed In a 75°C oven for about 15 minutes to allow the photochrome material to revert back to the ground state-form. The test squares were then cooled to room temperature, exposed to fluorescent room lighting for at least 2 hours, and then kept covered (that is, in a dark environment ⁇ for at least 2 hours prior to testing on an optical bench maintained at 73°F (23°C).
  • the bench was fitted with a 300-watt xenon arc lamp, a remote controlled shutter, a Melles Griot KG2 filter that modifies the UV and IR wavelengths and acts as a heat-sink, neutral density filter(s) and a sample holder, situated within a water bath, in which the square to be tested was inserted, A coliimated beam of light from a tungsten lamp was passed through the square at a small angle (approximately 30°) normal to the square. After passing through the square, the light from the tungsten lamp was directed to a collection sphere, where the light was blended, and on to an Ocean Optics S2000 spectrometer where the spectrum of the measuring beam was collected and analyzed. The A max .
  • vjs Is the wavelength in the visible spectrum at which the maximum absorption of the activated-state form of the phoiochromic compound in a test square occurs.
  • S wavelength was determined by testing the phoiochromic test squares in a Varian Cary 300 UV-Visible spectrophotometer, it may also be calculated from the spectrum obtained by the S2000 spectrometer on the optical bench,
  • the saturated optica! density (“Sat'd OD”) for each test square was determined by opening the shutter from the xenon lamp and measuring the transmittance after exposing the test chip to 3W/m2 UVA radiation for 30 minutes.
  • the Amax.yis at the Sat'd OD was calculated from the activated data measured by the S2000 spectrometer on the optical bench.
  • the First Fade Half Life ⁇ ' ⁇ , /2 " ⁇ or Bleach Rate is the time interval in seconds for the absorbance of the activated -state form of the phoiochromic materia! In the test squares to reach one half the Sat'd OD absorbance value at room temperature (23°C), after removal of the source of activating fight.

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Abstract

The present invention relates to photochromic compounds that include at least two photochromic moieties that are linked together by a multivalent linking group. The multivalent linking group can be selected so as to be flexible and/or substantially prevent electronic interaction between any two photochromic moieties through the multivalent linking group. The present invention also relates to photochromic compositions and articles that include at least a photochromic amount of one or more photochromic compounds of the present invention.

Description

PHOTOCHROMIC COMPOUNDS HAVING AT LEAST TWO PHOTOCHROME
MOIETIES
CROSS REFERENCE TO RELATED APPLICATIONS
[001] This application Is a continuation-in-part of U.S. Patent Application Serial Number 12/873,735 fiied September 1 , 2010, which is a continuation-in-part of 12/136,339 filed June 10, 2008, which is a divisional of 11/102,279 filed April 8, 2005, ail of which documents are hereby incorporated herein by reference In their entireties.
FIELD
002j The present invention relates to photochromic compounds that have at least two photochromic moieties, in which the photochromic moieties are linked together by a multivalent linking group that can, with some embodiments, be flexible and/or substantially prevent electronic interaction between the photochromic moieties through the multivalent linking group,
BACKGROUND
[003] In response to certain wavelengths of electromagnetic radiation (or "actinic radiation"), photochromic compounds, such as indenofused naphthopyrans, typically undergo a transformation from one form or state to another form, with each form having a characteristic or distinguishable absorption spectrum associated therewith. Typically, upon exposure to actinic radiation, many photochromic compounds are transformed from a closed-form, which corresponds to an unactivated (or bleached, e.g., substantially colorless) state of the photochromic compound, to an open-form, which corresponds to an activated (or colored) state of the photochromic compound, in the absence of exposure to actinic radiation, such photochromic compounds are reversibly transformed from th activated (or colored) state, back to the unactivated (or bleached) state. Compositions and articles, such as eyewear lenses, that contain photochromic compounds or have photochromic compounds applied thereto (e.g., in form of a photochromic coating composition) typically display colorless (e.g., clear) and colored states that correspond to the colorless and colored states of the photochromic compounds contained therein or applied thereto.
[004] Upon exposure to actinic radiation (e.g., sunlight), the photochromic compound typically is transformed from the unactivated (or bleached) state to the activated (or colored) state over a period of time that is referred to as an activation time. Correspondingly, when exposure to actinic radiation Is haited (e.g., due to shielding of sunlight), the photochrome compound typscaily is transformed from the activated (or colored) state to the unactivated (or bleached) state over a period of time that is referred to as a fade time, ft is generally desirable that the activation time and the fade time associated with a phoiochromic material in each case be minimized. In addition, it is desirable that the fade rate associated with a photochromic compound be substantially linear. With photochromic eyewear, such as photochromic lenses, a linear fade rate allows the wearer's eyes to adjust more smoothly and less noticeably to the wearer as the lenses transform from a colored to a bleached state.
£0051 Since phoiochromic compounds can be expensive, it is typically desirable to minimize the amount of phoiochromic compound or compounds used without compromising the photochromic properties, such as optical density, of the photochromic article with which the phoiochromic compounds are associated. With some applications, the photochromic compounds are present in a layer, such as a coating, thai is applied over an underlying article, such as an optical !ens, and/or the photochromic compound is present within the article itself, which can be achieved by methods such as Imbibition and/or cast-in-piace methods.
[0Q8J Photochromic compounds can be subject to migration within the matrix, such as an organic matrix, in which they reside, With, for example, a photochromic layer or coating, the photochromic compounds can migrate out of the layer, which can result in an undesirable decrease in the photochromic properties of the photochromic layer. In some cases, a photochromic compound can migrate from a relatively soft coating layer in which the phoiochromic compound has favorable properties, such as good fade kinetics, into an abutting coating layer that is relatively hard and in which ihe phoiochromic compound has less favorable properties, such as undesirable fade kinetics. The overall effect, in such cases, can be a photochromic article having undesirable photochromic properties, such as undesirable fade kinetics.
[007] Si would be desirable to develop phoiochromic compounds that are subject to reduced migration or substantially no migration within a matrix, such as an organic matrix, in which they reside, it would also be desirable thai such newly developed photochromic compounds provide a desirable level of photochromic properties. SUMMARY
[008] In accordance with the present invention, there is provided a photochromic compound represented by the following Formula (I),
Formula (I)
Figure imgf000004_0001
n
With reference to Formula (I), L1 is a muftivafeni linking group selected from multivalent amine, multivalent linear or branched CrC2c a!kyl, multivalent optionally substituted C3-C12 cycioalkyi, multivalent optionally substituted C3-C12 heterocycloalkyi, multivalent optionally substituted aryl, multivalent optionally substituted heteroaryi. ~(R ~0)q- where R4 for each q is independently selected from divalent linear or branched C C12 aikyl and q is from 1 to 50, and combinations of two or more thereof. Subscript n of Formula (!) is at least 2. With further reference to Formula (I), R1 for each n is independently selected from a bond, divalent linear or branched C -C2o aikyl, divalent optionally substituted C3-C12 cycioalkyi, divalent optionally substituted C3~C12 heterocycloalkyi, divalent optionally substituted aryl, divalent optionall substituted heteroaryi, and combinations of two or more thereof With additional reference to Formula (i), X1 for each n and X2 for each n are each independently selected from O, NH, and a bond, provided that when R1 is a bond and X1 is a bond, R1 and X1 together define a bond.
[009] With still further reference to Formula {!), L2 for each n is independently selected from a group represented by the following Formula (II),
Formula {11}
Figure imgf000004_0002
The R2 group of Formula (II), for each t, is independently selected from a bond, divaient linear or branched C C2o alkyl, divalent optionally substituted C3-C 2 cycioalkyi, divalent optionally substituted aryl, divalent optionally substituted heteroaryi, and combinations of two or more thereof. The R3 group of Formula (II), for each p, is independently selected from divalent linear or branched C C2o alkyi, divalent optionally substituted C3-C12 cycloaky!, divalent optionally substituted ary!, divalent optionally substituted heieroaryi, and combinations of two or more thereof. W th further reference to Formula (il), X3 for each t and X4 for each t are each independently selected from O, NH, and a bond. With regard to X2, R2 and X3 of Formula {il) there are the fo!iowing provisos: provided that when R2 is a bond and X3 is a bond, R2 and X3 together define a bond; and provided that when X2 is a bond, R2 is a bond, X3 is a bond, and t is greater than 0, X2, R2 and X3 together define a bond. Subscript t of Formula (li), for each n, Is 0 to 100, Subscript p, for each n, is 0 to 20. With regard to t and p of Formula (H), there is the foilowing proviso, provided that the sum of t and p is greater than 0. With reference to Formula {(), PC for each n is independently a photochrome moiety or group. The invention also provides photochrome compositions and articles comprising the aforementioned compound,
DETAILED DESCRIPTION
[010] As used herein, the articles "a," "an," and "the" include plural referents untess otherwise expressly and unequivocally limited to one referent.
[011] Unless otherwise indicated, ail ranges or ratios disclosed herein are to be understood to encompass any and ail subranges or subratios subsumed therein. For example, a stated range or ratio of "1 to 10" should be considered to include any and all subranges between (and inciusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges or subratios beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, such as but not limited to, 1 to 6.1 , 3.5 to 7.8, and 5.5 to 10.
|012| As used herein, unless otherwise indicated, left-to-right representations of linking groups, such as divalent linking groups, are inciusive of other appropriate orientations, such as, but not limited to, right-to-ieft orientations. For purposes of non-limiting illustration, the left-to-right representation of the divalent linking group o
. c O or equivalent^ -C{Q)G-, is Inclusive of the right-to-left
O
i
representation thereof, ~~~~~~0 C , or equivalent^ -0(0)0 or -OC(0)~. [013| Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in ail instances by the term "about,"
[014] The photochrome compounds of the present invention as described herein, including photochromie compounds represented by Formula (I) and Formula (M), and related photochromie compounds, in each case optionally further include one or more coproducts, such as, but not limited to oligomers, resulting from the synthesis of such photochromie compounds.
[015] As used herein, the term "multivalent" with regard to multivalent linking groups, means a group that has at least two covalent bonds that serve to link the linking group to two or more photochromie moieties. As used herein, the term "divalent" with regard to divalent linking groups, means a group that has two covalent bonds that serve to link the linking group to two substituertts or portions of the photochromie compound.
[018] As used herein, the term "actinic radiation" means electromagnetic radiation that is capable of causing a response in a material, such as, but not limited to, transforming a photochromie material from one form or state to another as will be discussed in further detail herein,
[017] As used herein, the term "photochromie" and similar terms, such as "photochromie compound" means having an absorption spectrum for at least visible radiation that varies in response to absorption of at least actinic radiation. Further, as used herein the term "photochromie material" means any substance that is adapted to display photochromie properties (i.e. adapted to have an absorption spectrum for at least visible radiation thai varies in response to absorption of at least actinic radiation) and which includes at least one photochromie compound.
[018] As used herein, the term "photochromie compound" includes thermally reversible photochromie compounds and non-thermally reversible photochromie compounds. The term "thermally reversible photochromie compounds/materials" as used herein means compounds/materials capable of converting from a first state, for example a "clear state," to a second state, for example a "colored state," in response to actinic radiation, and reverting back to the first state in response to thermal energy. The term "non-thermally reversible photochromie compounds/materials" as used herein means compounds/materials capable of converting from a first state, for example a "clear state," to a second state, for example a "colored state," in response to actinic radiation, and reverting back to the first state in response to actinic radiation of substantially the same wavelength(s) as the absorption(s) of the colored state (e.g., discontinuing exposure to such actinic radiation).
[019] As used herein to modify the term "state," the terms "first" and "second" are not intended to refer to any particular order or chronology, but instead refer to two different conditions or properties. For purposes of non-limiting illustration, the first state and the second state of a photochrornic compound can differ with respect to at least one optical property, such as but not limited to the absorption of visible and/or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, the photochrornic compounds of the present invention can have a different absorption spectrum in each of the first and second state. For example, while not limiting herein, a photochrornic compound of the present invention can be clear in the first state and colored in the second state. Alternatively, a photochrornic compound of the present invention can have a first color in the first state and a second color in the second state.
[0203 As used herein the term "optical" means pertaining to or associated with light and/or vision. For example, according to various non-limiting embodiments disclosed herein, the optical article or element or device can be chosen from ophthalmic articles, elements and devices, display articles, elements and devices, windows, mirrors, and active and passive liquid crystal cell articles, elements and devices.
[021] As used herein the term "ophthalmic" means pertaining to or associated with the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses, including single vision or multi-vision lenses, which can be either segmented or non-segmented mufti-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetically or otherwise) vision, Including without limitation, contact lenses, intra-ocu!ar lenses, magnifying lenses, and protective lenses or visors.
£022] As used herein the term "ophthalmic substrate" means lenses, partially formed lenses, and lens blanks. [023J As used herein the term "display" means the visible o machine-readable representation of information in words, numbers, symbols, designs or drawings. Non-limiting examples of display articles, elements and devices include screens, monitors, and security elements, such as security marks.
[024] As used herein the term "window" means an aperture adapted to permit the transmission of radiation therethrough. Non-limiting examples of windows include automotive and aircraft transparencies, filters, shutters, and optical switches.
|025] As used herein the term "mirror" means a surface that specularly reflects a large or substantial fraction of incident light.
[026] As used herein the term liquid crystal cell" refers to a structure containing a liquid crystal material that is capable of being ordered. Active liquid crystal ceils are cells in which the liquid crystal material is capable of being reversibly and controilabiy switched or converted between ordered and disordered states, or between two ordered states by the application of an external force, such as electric or magnetic fields. Passive liquid crystal cells are cells in which the liquid crystal material maintains an ordered state. A non-limiting example of an active liquid crystal cell element or device is a liquid crystal display,
[027] As used herein the term "coating" means a supported film derived from a flowabfe composition, which can or can not have a uniform thickness, and specifically excludes polymeric sheets. A layer that includes one or more photochromic compounds of the present invention can, with some embodiments, be a photochromic coating.
[028] As used herein the term "sheet" means a pre-forrned film having a generally uniform thickness and capable of self-support.
[029] As used herein the term "connected to" means in direct contact with an object or indirect contact with an object through one or more other structures or materials, at least one of which is in direct contact with the object. For purposes of non-limiting illustration, a coating containing one or more photochromic compounds of the present invention, for example, can be In direct contact (e.g., abutting contact) with at least a portion of a substrate, such as an optical article, or it can be In indirect contact with at least a portion of the substrate through one or more other interposed structures or materials, such as a monomoiecuiar layer of a coupling or adhesive agent.. For example, although not limiting herein, a coating containing one or more photochromic compounds of the present invention, can be in contact with one or more other interposed coatings, polymer sheets or combinations thereof, at least one of which is in direct contact with at least a portion of the substrate.
[030] As used herein, the term "photosensitive material" means materials that physically or chemically respond to electromagnetic radiation, including, but not limited to, phosphorescent materials and fluorescent materials.
[031] As used herein, the term "non-photosensitive materials" means materials that do not physically or chemically respond to electromagnetic radiation, including, but not limited to, static dyes.
[032] As used herein, moiecular weight values of polymers, such as weight average molecular weights ( w) and number average molecular weights (Mn), are determined by gel permeation chromatography using appropriate standards, such as polystyrene standards.
[033] As used herein, polydi'spersity index (PDf) values represent a ratio of the weight average moiecular weight {Mw) to the number average molecular weight (Mn) of the polymer (i.e., Mw/ n).
[034] As used herein, the term "polymer"' means homopoiymers (e.g., prepared from a single monomer species), copolymers (e.g., prepared from at least two monomer species), and graft polymers.
[OSS] As used herein, the term "(meth)acryiate" and similar terms, such as "(meth)acryiic acid ester" means methacrylates and/or acrylates. As used herein, the term "(meth)acrylic acid" means methacrylic acid and/or acrylic acid.
[036] Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be under stood as modified in all instances by the term "about."
[037] As used herein, spatial or directional terms, such as "left", "right", "Inner", "outer", "above", "below", and the like, relate to the invention as it is depicted in the drawing figures. However, it is to be understood that the invention can assume various alternative orientations and, accordingly, such terms are not to be considered as limiting. [038] As used herein, the terms "formed over,1'' "deposited over," "provided over," "applied over/' residing over," or "positioned over," mean formed, deposited, provided, applied, residing, or positioned on but not necessarily in direct (or abutting) contact with the underlying element, or surface of the underlying element. For example, a layer "positioned over" a substrate does not preclude the presence of one or more other layers, coatings, or films of the same or different composition located between the positioned or formed layer and the substrate.
[039] Ail documents, such as but not limited to issued patents and patent applications, referred to herein, and unless otherwise indicated, are to be considered to be "incorporated by reference" in their entirety.
[040] As used herein, recitations of "linear or branched" groups, such as linear or branched aikyi, are herein understood to include; a methylene group or a methyl group; groups that are linear, such as linear C2-Cw aikyi groups; and groups that are appropriately branched, such as branched C3-C¾) alky! groups.
£041] As used herein, recitations of "optionally substituted" group, means a group, including but not limited to, aikyi group, cycloalkyl group, heterocycioalkyl group, ary! group, and/or heteroaryf group, in which at least one hydrogen thereof has been optionally replaced or substituted with a group that is other than hydrogen, such as, but not limited to, bafo groups (e.g., F, Ci, I, and Br), hydroxy! groups, ether groups, thiol groups, thio ether groups, carboxyiic acid groups, carboxyiic acid ester groups, phosphoric acid groups, phosphoric acid ester groups, sulfonic acid groups, sulfonic acid ester groups, nitro groups, cyano groups, hydrocarbyi groups (including, but not limited to; aikyi; alkenyl; alkynyl; cycloalkyl, including poly-fused-ring cycloalkyl and polycyciocalkyl; heterocycioalkyl; aryl, including hydroxyl substituted aryl, such as phenol, and including poly-fused-ring aryl; heteroaryf, including poly- fused-ring heteroaryf; and aralky! groups), and amine groups, such as -N(R1 )(R12) where R11 and R12 are each independently selected from hydrogen, linear or branched C -C2o aikyi. C3-Ci2 cycloaky!, C3-C12 heterocycioalkyl, aryl, and heteroaryf.
[042] As used herein, the term "aikyi8 means linear or branched Ci~CZ0 aikyi, such as, but not limited to linear or branched C Ci0 aikyi or linear or branched C2-CIQ alkyl. Examples of a!kyl groups from which the various a!kyl groups of the present invention can be selected from, include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, sec-butyl, tert-buty!, pentyl, neopenty!, hexyl, heptyf, octy!, nonyl and decyi. Aikyi groups of the various compounds of the present invention can, with some embodiments, include one or more unsaturated linkages selected from -CH-CH- groups and/or one or more -C≡C- groups, provided the alkyl group is free of two or more conjugated unsaturated linkages. With some embodiments, the aikyl groups are free of unsaturated linkages, such as -CH=CH- groups and ~CsC- groups.
[043] As used herein, the term "cycioaik!" means groups that are appropriately cyclic, such as C3-C12 cycloa!kyl (including, but not limited to, cyclic .C5~C? alkyl) groups. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyciobutyi, cyclopentyl, cyciohexyi, and cyclooctyl. The term "cycloalkyl" as used herein also includes: polycycloa!kyl groups (or poiycyciic alky! groups), such as but not Hmited to, bicycfo[2.2.1]heptyi (or norbornyl) and bscyclo(2.2.2]octyl; and fused ring poiycyciic alkyl groups, such as, but not limited to, octahydro-1 H~indenyl, and decahydronaphthalenyl.
[044] As used herein, the term "heterocycfoalkyi" means groups that are appropriately cyclic, such as C3-C12 heierocycloaikyi groups or C5-C6 heierocycloaikyi groups, and which have at least one hetera atom in the cyclic ring, such as, but not limited to, O, S, N, P, and combinations thereof, Examples of heierocycloaikyi groups include, but are not limited to, ietrahydrofuranyi, tetrahydropyranyl and piperidinyl. The term "heterocycioaikyl" as used herein also includes: poiycyciic heterocycloalkyi groups, such as but not limited to, 7-oxabicycio[2.2.1]heptanyf; and fused ring poiycyciic heierocycloaikyi groups, such as but not limited to, octahydrocyc!opentaibjpyranyl, and octahydro-1 H-isochromenyi.
[0451 As used herein, the term "aryl" includes, but is not limited to, C8-C18 ary!, such as but not limited to, C5~C 0 aryl (including poiycyciic fused ring aryl groups). Examples of aryl groups include, but are not limited to, phenyl, naphthyi, and anthracenyi.
[046] As used herein, the term "heteroaryl/' includes but is not limited to C-C-,, heteroaryl, such as but not limited to C5-C 0 heteroaryl (including poiycyciic fused ring heteroaryl groups) and means an aryf group having at least one hetero atom in the aromatic ring. Examples of heteroaryl groups include, but are not limited to, furanyl, pyranyl and pyridinyi.
[047] As used herein, the term "aralkyi, " includes but is not limited to C6-C24. araikyl, such as but not limited to C6-C10 aralkyi, means an aryl group substituted with an aikyi group that is bonded (or linked) to another group, hxamp!es of ara!kyl groups include, but are not limited to, benzyl, and phenethyi.
[048] As used herein the term "n-segrnenf means a segment of a photochrome compound according to the present invention that is bonded to the multivalent linking group t\ For purposes of non-limiting illustration, and with reference to Formula (1), when n is 3, the photochrome compound can be described as having three n- segments that are each bonded to thvalent linking group L1; the three n-segments can be further described as a first n-segment, a second n-segment, and a third n- segment, in which any one such n-segment is the same or different than any other such n-segment.
[049] The photochromic compounds of the present invention, and compositions containing such photochromic compounds, will be described in further detail as follows.
[Q50| With reference to Formula (f), subscript n is at least 2. With some embodiments, subscript n can be from 2 to 10, or from 2 to 5, or from 2 to 4, or from 2 to 3. Subscript q of -(R4-0)q- of L of Formula (!) can be, with some embodiments, from 1 to 50, or from 1 to 30, or from 1 to 20, or from 1 to 10, or from 1 to 5, or from 1 to 3. With reference to Formula (IS), subscript t can, with some embodiments, be from 0 to 100, or from 0 to 50, or from 0 to 30, or from 0 to 20, or from 0 to 15, or from 0 to 10, or from 0 to 5, or from 0 to 3, With further reference to Formula (II), and with some embodiments, subscript p can be from 0 to 20, or from 0 to 15, or from 0 to 10, or from 0 to 5, or from 0 to 3.
[051] With reference to Formulas (I) and (II), the aikyi groups, cycioalkyl groups, heterocycloalky! groups, ary! groups, and heteroary! groups from which the various multivalent and divalent Sinking groups, such as multivalent linking group L1, divalent R\ divalent R2, divalent R3, and divalent R4 can each be Independently selected include, but are not limited to, those classes and examples of alky! groups, cycioalkyl groups, heterocycioalkyl groups, aryi groups, and heteroary! groups as described previously herein.
[052] The photochromic moieties (PC) of the photochromic compounds, with some embodiments, are linked together by linkages or linking groups that limit, or inhibit, or prevent electronic interaction between any two photochromic moieties through the linking group. An example of electronic interaction includes, but is not limited to, extension of the pi-conjugated system of one photochromic moiety through the linking group with the pi-conjugated system of another photochromic moiety bonded to the same linking group. In accordance with some embodiments, L1, R1, X1, X2 and L2 are each selected so as to substantially prevent electronic interaction between any two photochromic moieties of the photochromic compound through L \ R1, X1 , X2 and L2. In accordance with some further embodiments, L\ R\ X1, X2 and L2 are each selected so as to substantially prevent extension of the pi-conjugated system of any photochromic moiety through L1 , R1, X1 , X2 and L2 with the pi- conjugated system of any other photochromic moiety of the photochromic compound, in accordance with some further additional embodiments, L1, R1 , X ' , Xz and L2 are each selected so as to be substantially free of conjugated pi-bonds that provide extension of the pi-conjugated system of any photochromic moiety through L1, R1, X1, X2 and L2 with the pi-conjugated system of any other photochromic moiety of the photochromic compound.
[053] in addition or alternatively to preventing electronic interaction between any two photochromic moieties therethrough, I1, R , X1, X2 and L2 are each selected, with some embodiments, so as to provide a flexible linkage between each photochromic moiety (PC) of the photochromic compounds of the present invention. With some embodiments, L\ R , R2 and R3 are each independently selected from mu!tivalent divalent linear or branched optionally substituted C C20 alkyf, mu!tSvalent/divalent optionally substituted C3-C12 cycloalkyi, multivalent/divajent optionally substituted C,r-C½ heterocydoalky), and combinations of two or more thereof, and alternatively or additionally, R1 and R2 can each be Independently selected from a bond, subject to the provisos as recited previously herein.
|054] With some embodiments, so as to (i) prevent, or substantially prevent, electronic Interaction between the photochromic moieties (such as, between any two photochromic moieties) therethrough, and/or (ii) provide a flexible linkage between each photochromic moiety (PC) of the photochromic compounds of the present invention, L1, R1, R2 and R3 are each, independently selected from multivalent/divalent linear or branched optionally substituted C1-C20 alkyi, and/or multivalent divalent optionally substituted C3-C12 cycloalkyi, and combinations of two or more thereof, and alternatively or additionally, R1 and R2 can each be independently selected from a bond, subject to the provisos as recited previously herein. |055j With reference to Formula ij), and with some embodiments of the present invention: n is 2; L1 is a divalent linking group selected from divalent linear or branched optionally substituted Ci-C2o, divalent optionally substituted C3-C12 cycioa!kyi, divalent optionally substituted aryl, divalent optionally substituted heieroaryl, and combinations of two or more thereof; R! is a bond; X1 is NH; and X2 is O.
[056] When X1 is NH and X2 is O, the photochrome compounds of the present invention can, with some embodiments, be prepared from isocyanate functional materials having at least two isocyanate groups. Examples of isocyanate functional materials from which the photochrome compounds of the present invention can be prepared include, but are not limited to: aikylene diisocyanates, such as hexamethylene diisocyanate; aromatic isocyanates, such as toluene diisocyanate, methylene diphenyi 4,4 -diisocyanate, meta-tetramethy!xy!ene diisocyanate (also referred to as m-T XDI), triphenyfmethan8-4>4',4'!-triisocyanate, naphthalene diisocyanate, such as naphthalene 1 ,5-dtisocyanate, and pheny!ene diisocyanate, such as p-phenylene diisocyanate; cycioa!kyl isocyanates, such as, isocyanato-1- (isocyanatomethyl)-1 ,3,3 rimethyl-cyclohexane, for example 5- isocyanato-1- (isocyanafomefhyl)-1 ,3f3-tnmethyl-cyclohexane (alos referred to as isophorone diisocyanate or iPDi), and methylene dicyclohexyi diisocyanate, such as methylene dicyclohexyi 4,4'-diisocyanate; and dimmers and trimers of any combination of such isocyanate functional materials (such as diisocyanates) containing Isocyanurate, uretidino, biruet and/or ailophanate linkages,
|057J PhotochromiG compounds according to some embodiments of the present invention, can be described with reference to: Formula (1} In which n is 2, L1 is a divalent linking group selected from divalent linear or branched optionally substituted CrC¾ , divalent optionally substituted C3-C12 cycioalkyl, divalent optionally substituted aryi, divalent optionally substituted heieroaryl, and combinations of two or more thereof, R1 is a bond, X1 is NH, and X2 Is O; and Formula (II) in which i is 0, p is from 1 to 5, and R3 for each p is independently divalent linear or branched C2-C10 aiky!, such as ethan-1,2-diyi or pram-1 ,2-diyi. Photochromic compounds according to such non-!imiting embodiments of the present invention can, with some embodiments, be prepared by reaction of 2 moles of a hydroxyi functional photochromic reactant (or intermediate) with one mole of a difunctionaf isocyanate. [058] With some embodiments, the photochromic compounds of the present invention can be described with reference to: Formula (I) in which n is 2, L is a divalent linking group selected from divalent linear or branched optionally substituted C1-C20. divalent optionally substituted C3~Ci2 cycioalkyi, divalent optionally substituted any!, divalent optionally substituted heteroaryi, and combinations of two or more thereof, R is a bond, X1 is NH, and X2 is O; and Formula (il) in which t is from 1 to 10, R2 for each t is independently selected from divalent linear or branched Ci-C10 alkyi, X3 is a bond, X4 is O, p is from 1 to 5, and R3 for each p is independently divalent linear or branched CVC10 alkyl, Photochromlc compounds according to such non-iimiting embodiments of the present invention can, with some embodiments, be prepared by reaction of one mole of a hydroxyi functional photochromic reactant with one or more moles of a cyclic carboxylic acid ester, such as a lactone, including but not limited to e-capro!actone, which results in the formation of a hydroxyi functional lactone extended photochromic intermediate. Two moies of the hydroxyi functional lactone extended photochromic intermediate can then be reacted, with some embodiments, with a difunctionai isocyanate,
[059] In accordance with some embodiments, the photochromic compounds of the present invention can be described with reference to Formula (I) in which n is 2, R1 is a bond, X1 is NH, X2 is O, and V is more particularly selected from: divalent linear or branched optionally substituted C C2o alkyi, such as divalent linear or branched CrCs alkyl, such as hexamethan-1 ,6-diyi; a structure represented by the following Formula (111),
(HI)
Figure imgf000015_0001
a structure represented by the following Formula (IV),
Figure imgf000016_0001
a structure represented by the following Formula (V),
(V)
Figure imgf000016_0002
For purposes of non-limiting illustration, see Formulas (VH-a) through (Vil-e) further herein.
As discussed previously herein with reference to Formula (I), when X is
NH and X' is O, the photochfomic compounds of the present invention can, with some embodiments, be prepared from isocyanate functional materials having at ieasi two isocyanate groups. With some embodiments, when the multivalent linking group V is selected from divalent linear or branched C1-C20 alky!, multivalent linking group L1 can be a residue of a diisocyanate, such as, but not limited to, hexamethylene diisocyanate, for example, 1 ,6-hexamethylene diisocyanate. With some additional embodiments, the divalent linking group L' represented by Formula (Ml) is a residue of a diisocyanate, such as tetramethylxy!ene diisocyanate, for example, meta- tetramethyixy!ene diisocyanate. With some further embodiments, the divalent linking group L represented by Formufa (IV) is a residue of a diisocyanate, such as methylene dicyciohexyi diisocyanate, for example, methylene drcyc!obexyl 4,4'~ diisocyanate. In accordance with some additional embodiments, the divalent linking group L1 represented by Formula (V) is a residue of a diisocyanate, such as isocyanato-1-(!socyanatomethyl)-1 ,3,3-inmethyl-cyc(ohexane, for example, 5- isocyanato-1-(isocyanatomethyl)-1 ,3,3--trimetnyi-cyclohexane (also called isophorone diisocyanate). [061] Photochromic compounds according to further embodiments of the present invention can be described with reference to Formula (i), in which n is 3, X1 is NH, X2 is 0» and L1 is represented by the following Formula (VI),
Figure imgf000017_0001
[062J When, in accordance with some embodiments of the present invention with reference to Formula (I), n is 3, X1 is NH, X2 is O, R1 is not a bond, and L1 is represented by Formula (VI), the trtvaient linking group L1 can be a residue of a trimer of three moles of one or more diisocyanates, such as a trimer of hexamethyiene-1 ,6-diisocyanat .
[0631 With some embodiments, the photochromic compounds of the present invention can be described with reference to Formula {I}, in which n is 3, X1 is NH, X2 is O, and L1 is represented by Formula (VI), and additionally in which R1 for each n is independently selected from linear or branched CTC2Q alky!. Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared, with some embodiments, from a trifuncttonal isocyanate that is a trimer of three moles of one or more diisocyanates, such as a trimer of hexamethyiene-1 ,6- dsisocyanate, 084J Photochromic compounds according to some embodiments of the present invention, can be described with reference to: Formula (I), in which n is 3, X1 is NH, X2 is O, and L1 Is represented by Formula (VI), and R1 for each n is independently selected from linear or branched C1-C20 aikyl; and Formula (II), in which t is 0, p is from 1 to 5, and R3 for each p is independently divalent linear or branched C2-C ]o aikyl. Photochromic compounds according to such non-limiting embodiments of the present invention can, with some embodiments, be prepared by reaction of three moles of a hydroxy! functional photochromic reactant with one mole of a trimer of a diisocyanate, such as a trimer of hexamethylene~1 ' ,6-diisocyanate. For purposes of non-limiting illustration, see Formulas (Vll-f) and (Vll-f-a) further herein. [065] According to some embodiments the photochromic compounds of the present invention can be described with reference to: Formula (I), in which n is 3, X1 is NH, X2 is O, and V is represented by Formula (VI), and R1 for each n is independently selected from linear or branched C C2o alkyi; and Formula (II), In which t is from 1 to 10, R2 for each f is independently selected from divalent linear or branched C C 0 alkyl, X3 is a bond, X4 is O, p is from 1 to 5, and R3 for each p is Independently selected from divalent linear or branched C2-C 0 alkyl. Photochromic compounds according to such non-limiting embodiments of the present invention can, with some embodiments, be prepared by reaction of one mole of a hydroxy! function photochromic reactant with one or more moles of a cyclic carboxylic acid ester, such as a lactone, for example, e-capro!actone, which results in the formation of a hydroxy! functional lactone extended photochromic intermediate. Subsequently, three moles of the hydroxyl functional lactone extended photochromic intermediate can be reacted with one mole of a trimer of a diisocyanate, such as a trimer of hexamethylene-1 ,6-diisocyanate, which results in formation of a photochromic compound according to a non-limiting embodiment of the present invention. For purposes of non-limiting illustration, see Formulas (Vlf-g) and (VH-g-a) further herein.
£068] In accordance with some embodiments, the photochromic compounds of the present invention can be described with reference to Formula (I), in which n is 3, and the photochromic compound has a first n-segment, a second n-segment, and a third n-segment, and L1 is N. In accordance with such non-limiting embodiments of the present invention, the trivaient linking group L ' can be a residue of a trimer of a diisocyanate, that includes biuret linkages, such as hexamethlene-1 ,6-diisocyanate.
[067] With some additional embodiments, the photochromic compounds of the present invention can be described with reference to Formula (I) in which n is 3, and the photochromic compound has a first n-segment, a second n-segment, and a third n-segment, L is N, and additional in which: for said first n-segment, R1 is divalent linear or branched optionally substituted d-Cao alkyl, X1 is NH, and X2 Is O; and for each of said second n-segment and said third n-segment, R1 and X1 together define a bond, and X2 is NH.
[068] With some further embodiments, the photochromic compounds of the present invention can be described with reference to: Formula (!) in which n is 3, and the photochromic compound has a first n-segment, a second n-segment, and a third n-segment, L1 is N, and additional In which: for said first n-segment, R1 is divalent linear or branched optionally substituted C G2o alkyt, X' is NH, and X2 is O; and for each of said second n-segment and said third n-segment, R1 and X! together define a bond, and X2 is NH; and Formula (II), in which t is 0, p is from 1 to 5, and R3 for each p is independently divalent linear or branched C2-C10 aikyL Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared by reaction of two moles of a hydroxyl functional photochromic reactani with one mole of a trimer of a drisocyanate, in the form of a biuret, such as hexarneth!ene-1 ,6-diisocyanate, such as DESMODUR N 3200 po!yisocyanate, which is commercially available from Bayer MaterialScience LLC. For purposes of non- limiting illustration, see, for example, Formula {VI Lh) further herein.
[069] Photochromic compounds in accordance with additional embodiments of the present invention can be described with reference to Formula (I), in which n is 2; L1 for each n is independently divalent linear or branched optionally substituted Ci- C2 alkyi; R1 is a bond; X' is O; and X2 is a bond.
[070J Photochromic compounds according to some further embodiments of the present invention, can be described with reference to: Formula (I), in which n Is 2, L1 for each n is independently divalent linear or branched optionally substituted C C2o alkyi, R1 is a bond, X1 is O, and X2 is a bond, and Formula (II), in which t is 1 , R2 is divalent linear or branched CrC1Q aikyl, X1' is a bond, and X4 is O.
[071] With some embodiments, some photochromic compounds of the present invention can be described with reference to: Formula (I), in which n is 2, L1 for each n Is independently divalent linear or branched optionally substituted C- Cao aikyl, R1 is a bond, X1 is O, and X2 is a bond, and Formula (II), in which t is 1 , R2 is divalent linear or branched G C10 aikyl, X3 is a bond, X4 is O, p is 1 to 5, and R3 for each p is independently divalent linear or branched C2-Ci0 aikyl. Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared, with some embodiments, by reaction of one mole of a hydroxy! functional photochromic compound and a cyclic carboxylic acid anhydride, such as, but not limited to, succinic anhydride, which results in the formation of a carboxylic acid functional photochromic intermediate. In accordance with some embodiments, the hydroxy functionality of the hydroxyl functional photochromic compound is provided by: a hydroxyl functional alkoxy group, such as but not limited to, -0-R**-OH, where R** is a divalent hydrocarbyi group, such as divalent linear or branched Ci-C20 aikyl, divalent C3-C12 cycloalkyl, divalent C3~C12 heterocycioalkyl, divalent aryl, divalent heieroaryi, and combinations of two or more thereof; or a hydroxy! functiona! hydrocarbyl group, such as -R**~OH, where R** is a described above. Two moles of the carboxylic acid functional photochromic intermediate can then be reacted, in some embodiments, with one mole of a dioL such as a linear or branched C2-C2o aikyl (or alkane) dio!, for example, dacane-1 ,10-dioi, with concurrent removal of water, which results in formation of a photochromic compound according to a non- limiting embodiment of the present invention. For purposes of non-limiting illustration, see Formula (Vll-i) further herein.
[072] Photochromic compounds in accordance with some embodiments of the present invention can be described with reference to Formula (I), in which n is 2, L ' is divalent !inear or branched optionaiiy substituted CrC2o aikyi, R1 is a bond, X1 is O, and X2 is O. When X1 and X? of Formula (1) are each O, the photochromic compounds of the present invention include at least one carbonate linkage between L1 and at least one PC moiety.
[073] With some embodiments, some photochromic compounds of the present invention can be described with reference to: Formula (I), in which n is 2, L1 is divalent linear or branched optionally substituted CrC20 afkyi, R1 is a bond, X1 is O, and X2 is O; and Formula (II), in which t is 0, p is from 1 to 5, and R for each p is independently divalent linear or branched C2-C10 a!kyL Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared, with some embodiments, by reaction of two moles of a hydroxy! functional photochromic reactant and one mole of a bishaioformate, such as a linear or branched C C20 aikyl (or alkane) bishaioformate, for example 1 ,6-hexane bischioroformate, which results in the formation of a photochromic compound according to a non-limiting embodiment of the present invention. For purposes of non-limiting illustration, see Formula (Vll-j) further herein,
[074] Further photochromic compounds in accordance with some embodiments of the present invention, can be described with reference to: Formula (I), in which n is 2, L1 is divalent linear or branched optionally substituted Ci-C20 aikyi, R is a bond, X1 is O, and X2 is O; and Formula (ll), in which t is from 1 to 100, such as from 1 to 50, or 1 to 30, or 1 to 20, or 1 to 10, or 1 to 5, or 1 to 3, R2 for each t is independently divalent linear or branched optionally substituted C C2o .alky!, X3 and X4 for each t are each O, and p is 0. Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared, with some embodiments, by reaction of; a hydrocarb-diyl-dicarbonoha!odate (X(O iCO-R-GC(O)X, where R is a hydrocarb-diyl and X is halo), such as a hydrocarb-diyi-dicartionochioridaie, such as an a!kane-diyl-dicarbonochloridate, such as ethane-1 ,2-diyl-dicarbonochioridate; and a dioi, such as an aikane dioi, such as 1 ,6-hexane diof, in which the moles of hydrocarb-diyi-dicarbonohalodaie and moles of dioi are selected so as to result in the formation of a chain extended dicarbonohalodate functional intermediate. For purposes of non-!imiting illustration, the terms hydrocarb-diyl-dicarbonoha!odaie, hydrocarb-diyl-dicarbonoch!orsdate, alkane-diyi-dicarbonochforidate and ethane- 1 ,2- diyl-dicarbonochloridate are equivalent to hydrocarb-diol-bisha!oformate, hydrocarb- diol-bischioroformate, alkyleneg!yco!bischioroformate, and
ethyieneglycolbisch!oroformate, respectively. The chain extended dicarbonohalodate functional intermediate is then reacted with two moles of an active hydrogen functional photochromic reactant, such as a hydroxy! functional photochromic reactant, which results in the formation of a photochromic compound according to some embodiments of the present invention. Such photochromic compounds can, in accordance with some embodiments, be described as oSigomeric or polymeric polycarbonates having terminal photochromic moieties. For purposes of non-limiting illustration, see Formula (Vli-m) further herein.
[075] Photochromic compounds in accordance with some embodiments of the present invention can be described with reference to Formula (I), in which n is 2, L for each n is independently selected from divalent linear or branched optionally substituted C1-C20 alkyi, divalent optionally substituted C3-C 2 cycloaikyl, divalent optionally substituted C3-C12 heterocycioaikyl, divalent optionally substituted aryl, and combinations of two or more thereof, R1 and X1 together define a bond, and X2 is O.
[076] With some embodiments, some photochromic compounds of the present invention can be described with reference to: Formula (I), in which n is 2, L1 for each n is independently selected from divalent linear or branched optionally substituted C - C2o alkyi, divalent optionally substituted C3-Ci2 cycloaikyl, divalent optionally substituted C3-C12 heterocyc!oalkyi, divalent optionally substituted aryl, divalent optionally substituted heteroaryl, and combinations of two or more thereof, R and X1 together define a bond, and X2 is O; and Formula (ii), t is 0, p is from 1 to 5, and R3 for each p is independently divalent linear or branched C2~Ci0 alkyi. Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared, with some embodiments, by reaction of two moles of a hydroxy! functional photochromic reactant and one moles of a bis oarboxyiic acid haiide, such as a linear or branched C2-C2Q alkyi (or afkane) bis carboxylic acid halide, for example decanedioyl dichioride (also referred to a sebacoyi chloride), which results in the formation of a photochrome compound according to a non-iimiting embodiment of the present invention. For purposes of non-limiting i!iustration, see Formula (VH-k) further herein.
{077] Additional photochromic compounds in accordance with some embodiments of the present invention can be described with reference to Formula (1), in which n is 2, and said photochromic compound has a first n-segment and a second n-segment, and L is -(R -0}a- For the first n-segment, R1 and X1 together define a bond. For the second n-segment, R1 is a bond, and X1 is O, For the first n-segment and said second n-segment, X2 Is a bond. With further accordance with this non- limiting embodiment of the present invention, and with reference to Formula (if), for the first n-segment and the second n-segment, t fs 1 , R2 is linear or branched C1-C10 aikyi, XJ is a bond, X4 is 0, p is from 1 to 5, and 3 for each ρ is independently selected from divalent linear or branched C2-C10 aikyi. Photochromic compounds according to such non-limiting embodiments of the present invention can be prepared, with some embodiments, by reaction of one mole of a hydroxy! functional photochromic reactant and one mote of an cyclic carboxyiic acid anhydride, such as, but not limited to, succinic anhydride, which results in the formation of a carboxy!ic acid functional photochromic Intermediate. Two moles of the carboxylic acid functional photochromic intermediate can then be reacted, In some embodiments, with one mole of a polyalkyiene glycol, such as a polyethylene glycol, for example tetraethylene glycol, with the concurrentl removal of water, which results in the formation of a photochromic compound according to a non-ismiti.ng embodiment of the present invention. For purposes of non-limiting illustration, see Formula (VIM) further herein.
[078] Examples of photochromic compounds according to the present invention include, but are not limited to, those represented by the following Formulas (VH-a) through (Vll-i). Formula (Vll-a)
Figure imgf000023_0001
Figure imgf000023_0002
Formula (Vll-c)
Figure imgf000023_0003
Formula (Vi!-d)
Figure imgf000024_0001
Figure imgf000024_0002
Where with Formula (VN-e), each t is independently selected from 1 to 100, or 1 to 50, or 1 to 30, or 1 to 20, or 1 to 15, or 1 to 10, such as, with some embodiments, 4, 8, or 9.5.
Formula (Vll-f)
Figure imgf000024_0003
With Formula (Vll-f), each Rb is represented by the following Formula (V!l-f-a) Formula (VH-f-a) o
-NH— C ~--Q---(- CH2 -0 -
Formula (Vii-g)
Figure imgf000025_0001
With Formula (Vli-g), each R6 is represented by the following Formula (VH-g-a).
Formuia (VH-g-a)
Figure imgf000025_0002
With Formula (VH-g-a), each t Is independently from 1 to 100, or 1 to 50, or 1 to 30, or 1 to 20, or 1 to 15, or 1 to 10, such as with some embodiments 4.5, or 8, or 10.
Formula (Vli-h)
Figure imgf000025_0003
Formula (VH-ϊ)
Figure imgf000026_0001
Formula (Vlf-j)
Figure imgf000026_0002
Formula (Vl!-k)
Figure imgf000026_0003
Formula (VIM)
Figure imgf000026_0004
With Formula (Vll-i), q is from 1 to 20, or from 1 to 10, or from 1 to 8, such as, with some embodiments, 4.
Formula (Vlf-m)
Figure imgf000026_0005
With reference to Formula {Vll-m), iT of each of the two n-segments is irsdependently at least 1 , such as with some embodiments from 1 to 49, or 1 to 40, or 1 to 30, or 1 to 20, or 1 to 10. With some embodiments, each R3 is independently a residue of a dio!, and each Rb is independently a residue of a hydrocar -diyl-dicarbonohaiodate. With further reference to Formula (Vfl-m), each Ra and each Rb can, with some embodiments, each be independently seiected from divaient linear or branched optionally substituted C C2o aikyi, such as, but not limited to, n-hexane-1 ,6-diyi and ethane-1 ,2-dryj. In accordance with some embodiments, Ra is the same as R and correspondingly RB is the same as Ra,
[079] Each divalent linking group L2 of the photochromic compounds of the present invention can, with some embodiments, be independently bonded to any appropriate portion of each photochromic rnosety ( PC), including any group bonded to the photochromic moiety. For purposes of non-limiting illustration, with a photochromic moiety selected from an indeno-fused naphihopyran, L2 can be bonded: (i) directly to a ring of the indeno-fused naphthopyran; or (li) to a group, such as an Interposed group, that is bonded to a ring of the indeno-fused naphihopyran. Examples of groups, such as interposed groups, of the photochromic rnosety (PC) io which each L2 can independently be bonded include, but are not limited to: -O; -S-; - NR*-, where R* is hydrogen or hydrocarbyl, such as, linear or branched Cr-C2o aikyi, C3~C 2 cycioaiky!, G3-C |2 heterocycioa!kyl, aryl, and heteroary ; -C(O)-; ~OC(0)s -O- C(0)-0-; -NR*-C(0)-, were R* is as described above; -NH-C(0)-0-; divaient linear or branched C C2o aikyi; divalent C3-C12 cyc!oaikyi; divalent C3-C12 heterocycloaikyl; divaient aryl; divalent heteroaryl; divalent poiy(alkyiene oxide); and combinations of two or more thereof.
[080J The photochromic moieties (PC) of the photochromic compounds of to the present invention can be seiected from known photochromic moieties or substituents. While each photochromic moiety ca be selected from inorganic photochromic moieties and organic photochromic moieties, they are each typically and independently selected from organic photochromic moieties.
[081 j With some embodiments, each photochromic moiety (PC), of the photochromic compounds of the present invention, is independentl selected from, indeno-fused naphthopyrans, naphtho[1 ,2~b]pyrans, naphtho[2,1 -b]pyrans, spirofiuoroeno[1 ,2-bJpyrans, phenanthropyrans, quinolinopyrans,
fluoroanthenopyrans, spiropyrans, benzoxazines, naphthoxazines,
spiro(indoline)naphthoxazines., spiro{indoline)pyridobenzoxazines,
spiro(indoline)fluoranthenoxazines, spiro(indoline)quinoxazines, fuigides, fuigimides, diaryiethenes, diaryiaikyiethenes, diaryiaikenylethenes, thermally reversible phoiochromic compounds, and non-thermaliy reversible phoiochromic compounds, and mixtures thereof.
[082] Non-iimiting examples of photochromic pyrans from which the
phoiochromic (PC) moiety, of the photochromic compounds of the present invention, can be chosen include benzopyrans, naphthopyrans, e.g., napbiho[1 ,2-b]pyrans, naphtho[2, 1 -bjpyrans, indeno-fused naphthopyrans, such as those disclosed in U.S. Patent 5,645,767, and heterocydic-fused naphthopyrans, such as those disclosed in U.S. Patent Nos. 5,723,072, 5,698,141 , 6,153,126, and 6,022,497, which are hereby incorporated by reference; spiro-9-fluoreno[1 ,2-b'jpyrans; phenanihropyrans;
quinopyrans; fiuoroanthenopyrans; spiropyrans, e.g.,
sptro(benzindoline)naphthopyrans, spiro{indo!ine)benzopyrans.
spiro(indoiine)naphthopyrans, spiro{indoiine)quinopyrans and spiro{indoline)pyrans. Further examples of naphthopyrans and complementary organic photochromic compounds are described in U.S. Patent 5,658,501 , which are hereby specifically incorporated by reference herein. Sptro(indoline)pyrans are also described in the text, Techniques in Chemistry, Volume HI, "Photochromism", Chapter 3, Glenn H. Brown, Editor, John Wiley and Sons, Inc., New York, 1971 , which is hereby
Incorporated by reference.
[083J Non-limiting examples of photochromic oxaz nes from which each phoiochromic moiety (PC) can be independently chosen include benzoxazines, naphthoxazines, and spiro-oxazines, e.g., spiro(indoline)naphthoxazines,
sptro(indoiine)pyridobenzoxazines, spiro(benzindoiine)pyridobenzoxazines,
spiro(benzindofine)naphthoxazsnes, spiro{indoline)benzoxazines,
spiro(indoiine)fiuoranthenoxazine, and spiro(indo!ine)quinoxazine. Non-limiting examples of photochromic fulgides from which each photochromic moiety (PC) can be independently chosen include; fu!gimides, and the 3-furyl and 3-thienyl fulgides and tulgsmides, which are disclosed in U.S. Patent 4,931 ,220 (which are hereby specifically Incorporated by reference) and mixtures of any of the aforementioned photochromic materials/compounds.
[084] With some embodiments, each photochromic moiety of the photochromic compounds of the present invention are each independently selected from one or more indeno-fused naphthopyrans. As will be discussed in further detail herein, an indeno-fused naphthopyran typically has 10 to 12 available positions to which the divalent linking L2 of Formula (I) can be bonded. [085] In accordance with some embodiments, each photochromic moiety (PC) is Independently selected from an indeno-fused naphthopyran, which can be represented by the following general Formula (VIII), in which the ring atoms are numbered as shown,
Formula {VII I)
Figure imgf000029_0001
The B and B' groups of the indeno-fused naphthopyran represented by general formula {VI If) are each independently selected, with some embodiments, from substituted and unsubstituted aromatic groups, and substituted and unsubstituted heteroaromatic groups, or B and 8' taken together can form, with some embodiments, an unsubstituted or substituted fiuoren~9-yiidene,
[086] The indeno-fused naphthopyran represented by general formula (Vfli) can be referred to as an indeno[2',3':3,4]naphtho[1 ;2-b3pyran. Each photochromic moiety (PC) can, with some embodiments, be independently selected from an indeno- naphthopyran, including, but not limited to, indeno[2^3\'3,43naphtho[1 ,2~b]pyrans represented by general formula (VIII), and/or one or more
Figure imgf000029_0002
represented by the following general Formu!a- (IX), in which the ring atoms are numbered as shown, Formula (IX)
Figure imgf000030_0001
The Rs through R14, B and B' groups of the indeno[1 \2':4,3]naphthoJ2, 1 -b]pyran represented by genera! Formula-(iX) are each as described herein with regard to the indenop'^S^jjnaphthoil ,2-bjpyran represented by general Formula (Vlli).
{087J With some embodiments, each photochromic moiety (PC) is independently selected from an indeno[2',3':3,4Jnaphtho[1 ,2~b]pyran, such as represented by Formula (Vlli), and/or an
Figure imgf000030_0002
represented by general Formula (IX). In accordance with some further embodiments, each photochromic moiety (PC) is independently selected from an indena[2\3':3,4]naphiho[1 ,2-b]pyran; such as represented by Formula (VIII).
[088J When, as with some embodiments, each photochromic moiety (PC) is independently selected from an indeno[2\3\*3,4]naphthop ,2~b]pyran, such as represented by Formula (Vil I), each such photochromic moiety (PC) can be independently bonded to L2 at a ring position selected from ring position 3, ring position 8, ring position 7, ring position 1 1 , and ring position 13.
|089] When, as with some embodiments, each photochromic moiety (PC) is independently selected from an indeno[2',3J:3,43riaphtho[1 ,2-b]pyran, such as represented by Formula (VIII), each such photochromic moiety (PC) can be independently bonded to L2 at a ring position selected from ring position 3, ring position 1 1 , and ring position 13. [090] In accordance with some embodiments, each photochromic moiety (PC) is selected from an indeno[2',3!:3,43naphtho[1 ,2-b]pyran, and each photochromic moiety (PC) is bonded to L2 at ring position 3, In accordance with some further embodiments, each photochromic moiety (PC) is selected from an !ndenoi2',3':3!4jnaphtho[1 ,2-bjpyran, and each photochromic moiety (PC) is bonded to L2 at ring position 11 . I s accordance with some additional embodiments, each photochromic mosety (PC) is selected from an indeno[2\3':3,4]naphtho[1 ,2-b]pyran, and each photochromic moiety (PC) is bonded to L2 at ring position 13.
[091] Each photochromic moiety (PC) of the photochromic compounds of the present invention can, with some embodiments, be selected so as, in each case, to have an activated visible light absorbance spectra, and the activated visible light absorbance spectra of each photochromic moiety (PC) is substantially the same. The activated visible light absorbance of each photochromic moiety (PC) can be determined in accordance with art-recognized methods using art-recognized analytical equipment. In accordance with some embodiments, each photochromic moiety (PC): is selected from an indeno-fused naphthopyran, such as an indeno[2',3':3,4]naphtho[1 !2-b]pyran, or an indeno[ 1 !,2':4,3]naphiho[2, 1 -bjpyran; has substantially the same structure; and is bonded to L2 at the same ring position of each photochromic moiety (PC).
[092] With the indeno-fused naphthopyrans as represented by general formulas (VHI) and/or (XI), R5, R6, R7, R8, R9, R10, R11 and R1Z can each independently be selected in each case from: a reactive substituent; a compatiblizing substituent; hydrogen; fiuoro; chloro; C C6 alkyi; C3-C7 cyc!oalkyl; substituted or unsubstituted phenyl; -GR)0 ' or -OC(-O)R 0\ wherein R 0 * is hydrogen, CrC6 alkyi, phenyl(C C3)a!kyl, mono(C C6)alky! substituted phenyl(Ci-C3)alkyi, mono(C Ce)alkoxy substituted phenyi(C C3)aikyl, (CrC6)alkoxy(CrC4)a!kyl, C3-C7 cycioalkyl, or mono(Ci-C4)aikyl substituted C3-C? cycioalkyl. The phenyl substituents (i.e., the substituents of the substituted phenyl) can be selected from hydroxy!, halogen, carbony!, C C6 aikoxycarbonyl, cyano, halo(C C6)alkyi, C Ce a!kyl or C C6 alkoxy.
[093] Alternatively or in addition to the previously recited classes and examples, R5, R6, R7, R8, R9, R 0, R11 and R12 can each independently be selected in each case from:
Figure imgf000031_0001
wherein R,,' and R12' are each Independently hydrogen, C C8 alkyi, phenyl, naphthyl, furany!, benzofuran-2-yi, benzofuran-3-yl, thieny!, benzothien- 2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyndyi, f!uorenyl, C C8 aikylaryl, C3~C20 cycioaikyl, C4-C2o bicyeloaSkyi, C5- C20 tricycloalkyf or C C20 aikoxyaikyi, wherein said ary! group is phenyl or nap thyl, or R, i' and R12' come together with the nitrogen atom to form a G3-C20 hetero-bicyctoaiky! ring or a C4~C20 hetero-iricycloa!ky! ring.
Ϊ094] Each R5, Rs, R7, R8, R9, R!0, R11 and R12 group can independently be selected in each case from, a nitrogen containing ring substituent represented by the following general (or graphic) Formula X:
Figure imgf000032_0001
With the nitrogen ring substituent represented by general Formula X, each -Ύ- is independently chosen for each occurrence from -CH2-, -CH(R13')-, -C(Ri3') ,
-CH(aryl)-, -C(aryl)2-, and -C(R13')(aryl)-, and Z is -Y-, -0-, -S-, -3(0}-, -S02-, -NH-, -N(Ri3 , or -N(aryi)-, wherein each R13' is independently d-Ce alkyl, each ary! is independently phenyl or naphthyl, m is an integer 1 , 2 or 3, and p is an integer 0, 1 , 2, or 3 and provided that when p is 0, Z is -Y-.
[095] Additionally, each R5, R6, R7, R8 > R9, R10, R and R a group can independently be selected in each case from a nitrogen containing ring substituent represented by genera! formula (X8) and/or general formula (XC):
Figure imgf000032_0002
For the nitrogen containing ring substituents represented by genera! formulas (XB) and (XC), R-i5> R-te, and R17 are each independently selected from hydrogen, CrC6 aikyl, phenyl, or naphthyl, or the groups R 5 and Rf 6 together form a ring of 5 to 8 carbon atoms and each Rd is independently for each occurrence selected from -Ce alkyi, C C¾ alkoxy, fluoro or chloro, and Q is an integer 0, 1 , 2, or 3. [0961 Each R5, R6, R7, R8, R9, R 0, R and R12 group can also independently be selected in each case from unsubstituted, mono-, or di-substituted C4-C 8 spirobicyciic amine, or unsubstituted, mono-, and di-substituted C4-C18 spirotricyciic amine. The substituents of the spirobicyciic amines and the spirotricyciic amines can in each case be independently selected from aryl, C Ce aikyi, C C6 alkoxy, or phenyl(Ci-C6)alkyi.
[097] With some embodiments, RG and R7, of the indeno-fused naphthopyran, can together form a group represented by the following general Formula (XD) or general Formula (XE),
(XD) (XE)
Figure imgf000033_0001
With the groups represented by general Formulas (XD) and (XE), T and T are each independently oxygen or the group - Ri , where R11 ( Ri5, and R16 are each as set forth and described previously herein.
[0981 Ή1® ^ '3 aRd 1* groups of the indeno-fused naphthopyrans, such as the indeno[2',3':3,4]naphtho[1 ,2-b3pyran represented by general Formula (Vili), and/or the indenoi1 v2':4,3]naphtho[2, 1 -b]pyran represented by general Formula (IX), can each be independently selected from: a reactive substituent; a compatib!izing substituent; hydrogen; hydroxy; C-rCe a!kyl; hydroxy(C C6 )alkyi; C3-C7 cycioaikyl; ally!; substituted or unsubstituted phenyl; substituted or unsubstituted benzyl; chloro; fluoro; the group -C(~0)W, wherein W is hydrogen, hydroxy, Ci-C6 alkyi, C C6 alkoxy, the unsubstituted, mono-or di-substituted aryl groups phenyl or naphfhyl, phenoxy, mono- or di-{ C-,-C6)alkoxy substituted phenoxy, mono- or di-(d-C6)a!koxy substituted phenoxy, amino, mono(C C6)alkyiaminoi di(C,-C6)alkyiamino, phenylamino, mono- or di-( C C6)a!kyi substituted phenylamino, or mono- or di-( Ci- Ce)alkoxy substituted phenylamino. The phenyl, benzyl, or any! group substituents (e.g., the substituents of the substituted phenyl, substituted benzyl and substituted aryl groups) are each independently selected from C C-e alky! or Ci-C6 alkoxy.
[099] The R1j and R 4 groups of the indeno-fused naphthopyran can each independently also be an -0R1S group, in which R 8 is selected from CrC6 a!kyl, pbenyl(Ci-C3}alky!, mono(Ci~C6)aikyl substituted pbenyl(CrC3)alkyl, mono(C Ce)a!koxy substituted phenyi{Ci-C3)alkyl, C C6 aikoxy(C2-C4)aikyi, C3~C7 cycioa!kyl, mono(CrC4)afkyl substituted C3-C7 cycloalkyi, CrC6 chforoaikyi, CrC6 f uoroalkyl, allyl, or the group
Figure imgf000034_0001
wherein R 9 is hydrogen or C1-C3 alky! and Y' is CN, CF3, or COOR20, wherein R20 is hydrogen or C C3 alkyl, or R18 is the group, - C(=0)W". wherein W" is hydrogen, C C6 alkyl, Ci-Ce aikoxy, the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthy!, phenoxy, mono-, or di-( C C6)alkyl substituted phenoxy, mono- or di-(CrC6)aikoxy substituted phenoxy, amino, mono(CrC6)alky!amino, di(CrCe)aikyiarriino, phenyiamino, mono- or di-{CrC6)alky! substituted phenyiamino, or mono- or di-(CrC6)aikoxy substituted phenyiamino. The phenyl, benzyl, or aryl group substituents (e.g., the substituents of the substituted phenyl, substituted benzyl and substituted aryl groups) are each independently selected from CrO6 alkyl or C Cs aikoxy.
[0100] The R 3 and R14 groups of the indeno-fused naphthopyran can each independently also be a mono-substituted phenyl, in which the phenyl has a substituent located at the para position thereof. The substituent of the mono- substituted phenyl can be: a dicarboxylic acid residue or derivative thereof, a diamine residue or derivative thereof, an amino alcohol residue or derivative thereof, a poiyol residue o derivative thereof, -CH2~, -(CH2)r, or -[0-(CH2)$]k-. in which (t) is selected from an integer of 2, 3, 4, 5 or 6, and k is an integer selected from 1 to 50. The substituent of the mono-substituted phenyl is connected to an aryl group on another photochrome material
[0101] Alternatively, R13 and R 4 can together form an oxo group, a spiro- carbocyclic group containing 3 to 6 carbon atoms, or a spiro-heterocyciic group containing 1 to 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom. The spiro-carbocyclic and spiro-heterocyclic groups are annel!ated with 0, 1 or
2 benzene rings. 0102] The B and 8' groups of the indeno-fused naphthopyran can each be independently selected from: a substituted phenyl; a substituted aryl; a substituted 9- julolindinyl; a substituted heteroaromatic group chosen from pyridyl, furanyl, benzofuran-2-yi, benzofuran-3-yi, thienyi, benzothien-2-y!, benzothien-3-yi, dibenzofuranyl, dibenzothienyi, carbazoyl, benzopyridyi, irtdoiinyl, and fiuorenyi, wherein the phenyl, ary!, 9-juiolindinyl, or heteroaromatlc substituent is the reactive substituent R; an unsubstituted, mono-, di-, or tri-substituted phenyl or aryl group; 9- julolidinyl; or an unsubstituted, mono- or di-substituted heteroaromatlc group chosen from pyridyi, furany!, benzofuran-2-yi, benzofuran-3-yl, thlenyl, benzothien~2~yi, benzoihien~3-yl, dibenzofuranyi, dibenzothienyl, carbazoyi, benzopyridyi, indoliny!, and fsuorenyl.
[0103] The phenyl, aryi and heteroaromatic substituents (i.e., the substituents of the substituted phenyl, aryi and heteroaromatic groups) of the B and 8' groups can each be independently selected from: hydroxyl, a group -C(=0)R21, wherein R2; is ~ OR22, - (R23)R24. piperidino, or morpholino, wherein R22 is allyl, C C6 a!kyi, phenyl, mono(CrCe)a!kyi substituted phenyl, mono(Ci-Ce)alkoxy substituted phenyl, phenyl(Ci-C3)aiky!, mono(C C6)aikyi substituted phenyl{CrC3)alkyl, mono{C C6)alkoxy substituted phenyl(Cr-C3)alkyl! C -Ce aikoxy(C2-C4)a!ky! or Ci~C6 haloalky!, R23 and R2 are each independently CrC6 alkyi, C5-C7 cycloalkyl, phenyl or substituted phenyl, the phenyl substituents being C C6 alkyl or C C6 alkoxy, and said halo substituent Is chloro or fluoro, aryi, mono(CrC12)alkoxyary!, di(Ci- C12)alkoxyaryl, mono(CrCi2)aiky!aryl, di(Ci-C12)alkytaryl, haloaryl, C3-C7 cycloa!kyiaryl, C3-C7 cycloalkyl, C3-C7 cycloalky!oxy, CyCr cyc oalkyloxy{CrC12)alky1( C3-C7 cycloaikyioxy(CrC12)alkoxy: aryl(CrC12)alkyl, aryi(C Ci2)alkoxy, aryloxy,
Figure imgf000035_0001
mono- or di-(Ci-C<2)alkoxyaryf(C C-]2)a!kyi, mono- or di-(C -Ci2)alkylaryi(Cr C12)alkoxy, mono- or dl-(C1-C12)aikoxyaryl(Ci-C z)alkoxy, amino, mono- or di-(Cr Ci2)aikyiamino, diaryiamino, piperazino, W-(Ci-Ci2)aikylpiperaz}no, W-aryl piperazino, aziridino, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinoiino, tetrahydroisoquinoiino, pyrroiidyl, C C½ alkyl, Cr-Ci2 haioalkyl, Cr-C12 alkoxy, mono(C C12 }alkoxy(C -C12 )a!kyi, aeryloxy, methacryioxy, or halogen.
[0104] The 8 and B! groups can also each independently be an unsubstltuted or mono-substituted group chosen from pyrazolyl, imldazolyl, pyrazolinyl, imidazolinyl, pyrroiinyl, phenothiazinyi, phenoxazinyl, phenazinyl, and acridinyl. The substituents of these mono-substituted groups can each independently selected from C1-C12 alkyi, Ci-Ci2 alkoxy, phenyl, or halogen.
£0105] In addition, the B and B' groups can each be Independently selected from a group represented by the following general Formulas (XSA) or (XiB),
Figure imgf000036_0001
Independently with each of genera! formulas (XIA) and (X!B), K is -CH2- or -0-, and M is -O- or substituted nitrogen, provided thai when M is substituted nitrogen, K is - CHr- The substituted nitrogen substituents are hydrogen, C C12 alkyl, or CrC 2 acyl. Each R2S is independently selected for each occurrence from d-C 2 alkyl, C C 2 aikoxy, hydroxy, and halogen, and each u is independently an integer ranging from 0 to 2. The R26 and R27 groups are each independently hydrogen or CrC 2 alkyl.
[0106] Each B and 8' group can independently be a group represented by the following general Formula (XN),
Figure imgf000036_0002
With the group represented by general Formula (XH), Rz8 is hydrogen or CVC-.2 alkyl, and R29 is an unsubstituted, mono- or di-substituted group chosen from naphthyS, phenyl, furany!, and thienyl. The substitutents of the mono- or di-substituted naphthyis, phenyls, furanyls, and thienyls, are in each case independently selected from CrCi2 alkyl, CrC12 aikoxy, or halogen.
[0107] The B and 8* groups can together form a member selected from, a fluoren-9-ylidene, a mono-substituted fluoren-9-ylidene, or a di-substituted fluoren-9- ylidene. The substituents of the mono-substituted fluoren-9-ylidene, and the di- substituted fluoren-9-yfidene can in each case be independently selected from CrCi2 alkyl, CrCi2 aikoxy, or halogen.
[0108] In accordance with some embodiments of the present invention, each photochromic moiety (PC) is selected from an indeno[2,,3 3!4]naphfho[1 ,2--b]pyran represented by Formula {VIII), each photochromic moiety is bonded to L2 at ring
position 3, and B' is selected from
Figure imgf000036_0003
, in which L.2 is bonded to the oxygen. [0109] In accordance with some embodiments of the present invention, each phoiochromic moiety (PC) is selected from an indeno[2',3':3;4]naphtho[1 ,2-bjpyran represented by Formula {VIII} and: each phoiochromic moiety is bonded to L2 at ring position 3; R '3 and R14 are each independently selected from linear or branched d- C6 aikyi, such as methyl; R5 through R 2 are each hydrogen; B is selected from phenyl and linear or branched C C6 aikoxy substituted phenyl, such as me hoxy
substituted phenyl; and B1 is selected from
Figure imgf000037_0001
n which I" is bonded to the oxygen of B'.
[0110] in accordance with some further embodiments of the present invention, each photochromic moiety (PC) is selected from an lndeno[2\3^3,4)napbtho[1 ,2-- bjpyran represented by Formula (Vlll), each photochromic moiety is bonded to L2 at ring position 13, R ' : is -0-, and L2 is bonded to R 4.
[0111] In accordance with some further embodiments of the present invention, each photochromic moiety (PC) is selected from an indeno[2',3':3,4]naphtho[1 ,2- bjpyran represented by Formula (VIII) and; each photochromic moiety is bonded to L2 at ring position 13; B and B' are each independently selected from phenyl and linear or branched CrC6 aikoxy substituted phenyl, such as methoxy substituted phenyl; R6 and R ' are each independently selected from linear or branched Ci-C6 aikoxy, such as methoxy; R5, R!, R8,. 9 and R10 are each hydrogen; R ° is linear or branched C C6 alkyi, such as n-butyi; and R14 is -0-, in which L2 is bonded to R14,
[0112] In accordance with some further embodiments of the present invention, each photochromic moiety (PC) is selected from an indeno[2',3':3,4]naphiho[1,2- bjpyran represented by Formula (VIII is bonded to L2 at
ring position 1 1 , Ri1 is selected from
Figure imgf000037_0002
nd L2 is bonded to the oxygen of R11.
[0113] In accordance with some further embodiments of the present invention, each photochromic moiety (PC) is selected from an indeno[2!,3':3,4]naphtho[1 ,2- bjpyran represented by Formula (Vlli) and; each photochromic moiety is bonded to l at ring position 11 ; R'3 and R 4 are each independently selected from linear or branched d-C6 aikyi, such as methyl. R6 and R? are each independently selected from linear or branched C Cs aikoxy, such as methoxy; Rs, R8, R9, R10 and Ri2 are each hydrogen; 8 is pheny!morpholine; B' is selected from phenyl and linear or branched Ci-C6 alkoxy substiiuied phenyl, such as methoxy substituted phenyl; and
R11 is selected from
Figure imgf000038_0001
which L2 is bonded to the oxygen of R 1.
[0114] As previously discussed, the indeno-fused naphthopyrans from which each photochfomic moiety (PC) can be independently selected, can include at least one of a reactive substituent and/or a compatibilizing substltuent. Any one or more of the groups R5 through R14, 8 and B' of the indeno-fused naphthopyran (e.g., represented by general formulas- Viii and/or -IX) can include at least one of a reactive substituent and/or a compatibilizing substltuent. if the photochromic moiety includes multiple reactive substituents and/or multiple compatibilizing substituents, each reactive substituent and each compatibilizing substltuent can be independently chosen.
[0115] The reactive substituent and the compatibilizing substltuent can each independently be represented in each case by one of:
-A'-D-E-G-J (Xlli); -G-E-G-J (XVI); -D-E-G-J (XIX);
-A'-D-J (X!V); -D-G-J (XVII); -D-J (XX);
-A'-G-J (XV); ~G~J (XVIII); and -A'-J (XXI).
101181 With formulas (Xlli) through (XXI), non-limiting examples of groups that - A'- can represent according to various non-limiting embodiments disclosed herein include -0-, -C(=0 , -CH2-, -OC(=0>- and -NHC{=0)-, provided that if -A'- represents -0-, -A!- forms at least one bond with -J.
[0117] Non-limiting examples of groups that -D- can represent according to various non-limiting embodiments include a diamine residue or a derivative thereof, wherein a first amino nitrogen of said diamine residue can form a bond with -A'-, or a substituent or an available position on the Indeno-fused naphthopyran, and a second amino nitrogen of said diamine residue can form a bond with -E-, -G- or -J; and an amino alcohol residue or a derivative thereof, wherein an amino nitrogen of said amino alcohol residue can form a bond with -AX or a substituent or an available position on the indeno-fused naphthopyran, and an alcohol oxygen of said amino alcohol residue can form a bond with -E-, -G- or -J. Alternatively, according to various non-limiting embodiments disclosed herein the amino nitrogen of said amino alcohol residue can form a bond with -E-, -G- or -J, and said alcohol oxygen of said amino alcohol residue can form a bond with -A'-, or a substituent or an available position on the indeno-fused naphthopyran,
[0118] Non-limiting examples of suitable diamine residues that -D- can represent include an aliphatic diamine residue, a cyclo aliphatic diamine residue, a diazacycioalkane residue, an azacycio aliphatic amine residue, a diazacrown ether residue, and an aromatic diamine residue. More particular, illustrative and non- limiting examples of diamine residues that can be used in conjunction with various non-limiting embodiments disclosed herein include the following:
Figure imgf000039_0001
R*
[0119] Non-limiting examples of suitable amino alcohol residues that -D- can represent include an aliphatic amino alcohol residue, a cyclo aliphatic amino alcohol residue, an azacycio aliphatic alcohol residue, a diazacycio aliphatic alcohol residue and an aromatic amino alcohol residue. More particular, illustrative and non-iimiting examples of amino alcohol residues that can be used in conjunction with various non-limiting embodiments disclosed herein include the following:
Figure imgf000040_0001
[0120] With continued reference to formulas (XIII) through (XXI) above, according to various non-iimiting embodiments disclosed herein, -E- can represent a dicarboxyiic acid residue or a derivative thereof, wherein a first carbonyi group of said dicarboxyiic acid residue can form a bond with -G- or -D-, and a second carbonyi group of said dicarboxyiic acid residue can form a bond with -G-. Non-limiting examples of suitable dicarboxyiic acid residues thai -E- can represent include an aliphatic dicarboxyiic acid residue, a cycloaiiphatic dicarboxyiic acid residue and an aromatic dicarboxyiic acid residue. More particular, i!fustrative and non-limiting examples of dicarboxyiic acid residues that can be used in conjunction with various non-iimiting embodiments disclosed herein include the following:
Figure imgf000040_0002
[0121] According to various non-limiting embodiments disclosed herein, -G- can represent a group represented by the following general formula,
-[(OC2H4)x(OC3He)y(OC4H8)J-0- in which x, y and z are each independently chosen and range from 0 to 50, and a sum of X, y, and z ranges from 1 to 50; a polyol residue or a derivative thereof, wherein a first polyol oxygen of said polyol residue can form a bond with -A'-, -D-, -E- , or a su stituent or an available position on the indeno-fused naphthopyran, and a second polyol oxygen of said poiyol can form a bond with -E- or -J; or a combination thereof, wherein the first polyol oxygen of the polyol residue forms a bond with a group ~[(OC2Hi5)x{OC3Hs)y(OC4H8)j- (i.e., to form the group -[{OCg ttMOCsHeJy (OC4Hs)J-0-), and the second polyol oxygen forms a bond with -E- or -J. Non- limiting examples of suitable po!yoi residues that -G-- can represent Include an aliphatic polyol residue, a cycle aliphatic polyol residue and an aromatic polyoi residue.
[0122] More particular, illustrative and non-limiting examples of po!yols from which the polyol residues that -G~ can represent can be formed according to various non-limiting embodiments disclosed herein include (a) low molecuiar weight poiyols having an average molecular weight less than 500, such as, but not limited to, those set forth in U.S. Patent No. 6,555,028 at col. 4, lines 48-50, and col. 4, line 55 to col. 8, line 5, which disclosure is hereby specifically incorporated by reference herein; (b) polyester poiyols, such as, but not limited to, those set forth in U.S. Patent No, 6,555,028 at col. 5, lines 7-33, which disclosure is hereby specifically incorporated by reference herein; (c) po!yether poiyols, such as but not limited to those set forth In U.S. Paten! No. 6,555,028 at col. 5, lines 34-50, which disclosure is hereby specifically incorporated by reference herein; (d) amide-containing poiyols, such as, but not limited to, those set forth in U.S. Patent No. 6,555,028 at col. 5, lines 51-62, which disclosure is hereby specifically incorporated by reference; (e) epoxy poiyols, such as, but not limited to, those set forth in U.S. Patent No. 6,555,028 at cot, 5 line 63 to col. 6, line 3, which disclosure is hereby specifically Incorporated by reference herein; {f} poiyhydric polyvinyl alcohols, such as, but not limited to, those set forth in U.S. Patent No. 6,555,028 at col. 6, lines 4-12, which disclosure is hereby specifically incorporated by reference herein; (g) urethane poiyols, such as, but not limited to those set forth in U.S. Patent No. 6,555,028 at col. 6, lines 13-43, which disclosure is hereby specifically Incorporated by reference herein; (h) poiyacryllc poiyols, such as, but not limited to those set forth in U.S. Patent No. 6,555,028 at col. 6, lines 43 to col, 7, line 40, which disclosure is hereby specifically incorporated by reference herein; (i) polycarbonate poiyols, such as, but not limited to, those set forth in U.S. Patent No. 6,555,028 at col. ?, lines 41 -55, which disclosure is hereby specifically incorporated by reference herein; and (j) mixtures of such po!yols.
[0123] With further reference to formulas {XIII) through {XXI}, according to various non-limiting embodiments disclosed herein, -J can represent a group -K, wherein -K represents a group such as, but not limited to, -CH2COOH, ~ CH(CH3)COOH, -C(0)(CH2)wCOOH, -C6H4S03H, -CSH,0SG3H, -C4H8S03H, ~C3H6SG3H, -C6.H4S03H and -S03H, wherein "w" ranges from 1 to 18. According to other non-limiting embodiments -J can represent hydrogen that forms a bond with an oxygen or a nitrogen of linking group to form a reactive moiety such as -OH or -NH. For example, according to various non-iimiting embodiments disciosed herein, -j can represent hydrogen, provided that if -J represents hydrogen, -J is bonded to an oxygen of -D- or -G-, or a nitrogen of -D~. 0124J According to still further non-iimiting embodiments, -J can represent a group -I or residue thereof, wherein -L can represent a reactive moiety. For example, according to various non-iimiiing embodiments disclosed herein -L can represent a group such as, but not limited to, acryl, methacryi, crotyi, 2- {methacryloxy}ethyicarbarnyi, 2-(methacryloxy)ethoxycarbonyi, 4-vinyiphenyf, vinyl, 1-chiorovinyi or epoxy. As used herein, the terms acry!, methacryi, crotyl, 2- {methacryioxy)ethylcarbamyf, 2-(methacryioxy)ethoxycarbonyi, 4-vinylphenyl, vinyl, 1-chlorovinyl, and epoxy refer to the following structures:
Figure imgf000042_0001
[0125] As previously discussed, -G- can represent a residue of a po!yol, which Is defined herein to include hydroxy-containing carbohydrates, such as those set forth in U.S. Patent No. 6,555,028 at col. 7, line 56 to coS. 8, line 17, which disclosure Is hereby specifically incorporated by reference herein. The poiyol residue can be formed, for example and without limitation herein, by the reaction of one or more of the poiyol hydroxy! groups with a precursor of -A'-, such as a carboxy!ic acid or a methylene halide, a precursor of poiyaikoxyiated group, such as po!yalkyiene glycol, or a hydroxy! substituent of the indeno-fused naphthopyran. The poiyol can be represented by g~(QH)a and the residue of the poiyol can be represented by the formula ~G-q-(OH)a-i, wherein q is the backbone or main chain of the polyhydroxy compound and "a" is at least 2.
[0126] Further, as discussed above, one or more of the poiyoi oxygens of -G- can form a bond with -J (i.e., forming the group -G-J). For example, although not limiting herein, wherein the reactive and/or compatib!izing substituent comprises the group -G-J, if -G~ represents a poiyol residue and -J represents a group -K that contains a carboxyi terminating group, -G-J can be produced by reacting one or more polyol hydroxy! groups to form the group -K (for example as discussed with respect to Reactions B and C at col. 13, line 22 to col. 16, line 15 of U.S. Patent No. 6,555,028, which disclosure is hereby specifically incorporated by reference herein) to produce a carboxy!ated polyol residue. Alternatively, if -J represents a group -K that contains a sulfo or suifono terminating group, although not limiting herein, -G-J can be produced by acidic condensation of one or more of the poiyol hydroxy! groups with HOC6H4S03H; HOC5H10SO3H; HOC4HeS03 H; HOC3H6S(¾H; HOC2H4S03H; or H2S04, respectively. Further, although not limiting herein, if -G- represents a polyol residue and -J represents a group -L chosen from acryl, met ha cry i, 2-(methacryfoxy)ethylcarbamyi and epoxy, -L can be added by condensation of the polyoi residue with acryioyl chloride, methacryloyt chloride, 2-isocyanatoeihyi methacry!ate or epichlorohydrin, respectively.
10127] In accordance with some embodiments, -J of one or more of Formulas (XII I) through (XXI) is bonded to L2 of Formula (I), in which case -J is a divalent linking group represented by -J-. With some embodiments, when bonded to L? of Formula (I), examples of divalent -J- Include, but are not limited to: -0-; -S-; -NR*~ where R* is hydrogen or hydrocarbyt such as, linear or branched C C2o a!kyi, C3-C12 cycioalkyS, C3-C12 heterocycloalkyl, ary!, and heteroary!; -CH2COO-; -CH(CH3)COO~; -C(0)(CH2)wCOO-, where "w" is from 1 to 18; -C6H4S03-; -C5H 0SO3-; -C4HeS03-; -C3H6SQ3~; ~C2H S03-; -S03-; and combinations of two or more thereof.
[0128] Indeno-fused naphthopyrans from which each photochromic moieties (PC) can be independently selected can be prepared by art-recognized methods. With some embodiments, the indeno-fused naphthopyrans, from which each photochromic moieties (PC) can be independently selected, can be synthesized in accordance with the description provided in United States Patent No. 8,296,785, at column 10, Sine 52 through column 29, line 18, which disclosure is incorporated herein by reference. With some further embodiments, the indeno-fused naphthopyrans, from which each photochromic moieties (PC) can be independently selected, can be synthesized in accordance with the description provided in United States Patent No. 7,527,754 B2 at column 13, line 52 through column 14, line 62, which disclosure is incorporated herein by reference. With some additional further embodiments, the indeno-fused naphthopyrans, from which each photochromic moieties (PC) can be independently selected, can be synthesized in accordance with the description provided in United States Patent No. 5,645,767, at column 5, line 6 through column 1 1 , line 31 , which disclosure is incorporated herein by reference.
[0129J The phoiochromic compounds of the present invention can each be used alone, or in combination with other photochromic compounds according to various non-limiting embodiments disclosed herein, or in combination with one or more appropriate complementary conventional photochromic compounds. For example, the photochromic compounds of the present invention can be used in conjunction with conventional photochromic compounds having activated absorption maxima within the range of 300 to 000 nanometers. Further, the photochromic compounds according to the present invention can be used in conjunction with a complementar conventional polymerizable or a compatibiized photochromic compound, such as for example, those disclosed in U.S. Patent Nos. 6, 113,814 (at col. 2, Sine 39 to col. 8, line 41 ), and 6,555,028 (at co!. 2, line 65 to col. 12, line 56), which disclosures are hereby specifically incorporated by reference herein.
[01301 The photochromic compounds of the present invention can be used In combination with a mixture of other photochromic compounds. For example, although not limiting herein, mixtures of photochromic compounds can be used to attain certain activated colors such as a near neutral gray or near neutral brown. See, for example, U.S. Patent No, 5,645,767, col. 12, line 66 to col. 13, line 19, which describes the parameters that define neutral gray and brown colors and which disclosure is specifically incorporated by reference herein.
[0131] The present Invention also relates to a photochromic article that include one or more photochromic compounds according to the present invention, such as represented by Formulas (!) and (II).
[0132] In accordance with further embodiments of the present invention, the photochromic articles of the present invention can be selected from ophthalmic articles or elements, display articles or elements, windows, mirrors, packaging material such as shrtnkwrap, and active and passive liquid crystal cell articles or elements.
[0133] Examples of ophthalmic articles or elements include, but are not limited to, corrective and non-corrective lenses, including single vision or multi-vision lenses, which can be either segmented or non-segmented multi-vision lenses (such as, but not limited to, bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetically or otherwise) vision, including without limitation, contact tenses, intra-ocuiar ienses, magnifying ienses, and protective tenses or visors.
[0134] Examples of display articles, elements and devices include, but are not limited to, screens, monitors, and security elements, including without Iimitation, security marks and authentication marks.
|0135] Examples of windows include, but are not limited to, automotive and aircraft transparencies, filters, shutters, and optical switches,
[0136] With some embodiments, the photochromic article can be a security element. Examples of security elements include, but are not limited to, security marks and authentication marks thai are connected to at least a portion of a substrate, such as; access cards and passes, e.g., tickets, badges, Identification or membership cards, debit cards, etc.; negotiable instruments and non-negotiable instruments e.g., drafts, checks, bonds, notes, certificates of deposit, stock certificates, etc.; government documents, e.g., currency, licenses, identification cards, benefit cards, visas, passports, official certificates, deeds etc.; consumer goods, e.g., software, compact discs ("CDs"), digital-video discs ("DVDs"), appliances, consumer electronics, sporting goods, cars, etc.; credit cards; and merchandise tags, labels and packaging.
I0137J With further embodiments, the security element can be connected to at least a portion of a substrate chosen from a transparent substrate and a reflective substrate. Alternatively, according to further embodiments In which a reflective substrate is required, if the substrate is not reflective or sufficiently reflective for the intended application, a reflective material can be first applied to at least a portion of the substrate before the security mark is applied thereto. For example, a reflective aluminum coating can be applied to the at least a portion of the substrate prior to forming the security element thereon. Additionally or alternatively, the security element can be connected to at least a portion of a substrate chosen from untinted substrates, tinted substrates, photochromic substrates, tinted-photochromic substrates, linearly polarizing, circularly polarizing substrates, and elliptlcaily polarizing substrates.
[9138] Furthermore, security elements according to the aforementioned embodiments can further include one or more other coatings or films or sheets to form a multi-layer reflective security element with viewing angle dependent characteristics, such as described In U.S. Patent 6,641 ,874.
[0139] Photochromic articles according to the present invention, such as optical elements, can include a substrate and a photochromic material that includes the photochromic compound according to the present invention, in which the photochromic material is connected to at least a portion of the substrate. As used herein, the term "connected to" means associated with, either directly, or indirectly by means of another material or structure.
[0140] Photochromic articles according to the present invention can include, as discussed above, a substrate that can include one or more polymeric compounds of the present invention. The photochromic compounds of the present invention can be incorporated into at least a portion of the polymeric material of the substrate; or by incorporating the photochromic compound(s) into at least a portion of the oiigomeric or rnonom.eric material from which the substrate is formed. For example, according to one non-limiting embodiment, the photochromic compound can be incorporated into the polymeric material of the substrate by a casi-in-place method or by imbibition. The imbibition and the cast-in-piace methods are discussed in further detail herein below.
[0141] In the imbibition method, the photochromic compound is typically diffused into the polymeric material of a previously formed or fabricated article, such as a substrate or previously applied coating/film. Imbibition can be performed by immersing the polymeric material of a previously formed or fabricated article In a solution containing the photochromic compound, with or without heating. Thereafter, although not required, the photochromic compound can be bonded with the polymeric material (e.g.. of the substrate or coating).
[0142] With cast-in-place methods, the photochromic compound(s) can be mixed with: a polymer and/or oligomer composition in solution or melt form; or monomer composition in liquid form, so as to form a castabie photochromic composition. The castabie photochromic composition is then typically introduced into the cavity of a mold (e.g., a lens mold). The castabie photochromic composition is then set within the mold so as to form a photochromic article.
[01431 With photochromic articles according to the present invention that include a substrate, a photochromic compound(s) can be Included in a coating that is connected to at least a portion of the substrate, The substrate can be a poiymeric substrate or an inorganic substrate (such as, but not limited to, a glass substrate). The photochromic compound(s) can be incorporated into at least a portion of a coating composition prior to application of the coating composition to the substrate. Alternatively, a coating composition can be applied to the substrate, at least partially set, and thereafter the photochromic compound(s) can be imbibed into at least a portion of the coating. As used herein, the terms "set" and "setting" include, without limitation, curing, polymerizing, cross-linking, cooling, and drying.
|01441 Photochromic articles according to the present invention can be formed by art-recognized In-mold coating (or in-mold casting) methods. With in-mold coating methods, a photochromic coating composition that includes a photochromic compound(s) of the present invention, which can be a liquid coating composition or a powder coating composition, is applied to at least a portion of the interior surface of a mold, and then at least partiaily set Thereafter, a polymer solution or melt, or oligomeric or monomeric solution or mixture is cast or molded within the mold cavity and in contact with the previously applied photochromic coating composition, and at least partially set. The resulting photochromic article is then removed from the mold. Non-limiting examples of powder coatings in which the photochromic materials according to various non-limiting embodiments disclosed herein can be employed are set forth in U.S. Patent No. 6,088,797 at col. 7, line 50 to col, 19, line 42, which disclosure Is hereby specifically incorporated by reference herein.
[0145] Photochromic articles according to the present invention can also be formed by art-recognized over-mold methods, Over- nold methods typically involve forming a substrate within a moid, and then forming an interior space between the substrate and an interior surface of the moid, into which a photochromic coating composition is then subsequently introduced (e.g., injected) and then set (e.g., cured). Alternatively, over-mold methods can involve introducing a previously formed substrate into a mold, such that an interior space is defined between the substrate and an interior mold surface, and thereafter a photochromic coating composition is introduced (e.g., injected) into the interior space. The photochromic coating compositions include one or more photochromic compounds of the present invention.
[0146] Photochromic articles according to the present invention can also be formed by means of art-recognized lamination methods. With lamination methods, a film comprising the photochromic compound(s) according to the present invention can be adhered or otherwise connect to a portion of the substrate, with or without an adhesive and/or the application of heat and pressure. Thereafter, if desired, a second substrate can be applied over the first substrate and the two substrates can be laminated together (i.e., by the application of heat and pressure) to form an element wherein the film comprising the photochromic compound is interposed between the two substrates. Methods of forming films comprising the photochromic compounds of the present invention can include for example and without limitation, combining a photochromic compound with a polymeric solution or oiigomeric solution or mixture, casting or extruding a film therefrom, and, if required, at least partially setting the film. Additionally or alternatively, a film can be formed (with or without a photochromic compound) and imbibed with the photochromic compound,
£0147] Coating compositions that include the photochromic compound(s) of the present Invention can be connected to at least a portion of the substrate of the photochromic article by art-recognized methods, such as applying a coating composition that includes the photochromic eompound(s) to at feast a portion of a surface of the substrate, and at least partially setting the coating composition. Additionally or alternatively, the coating that includes the photochromic cornpound(s) can be connected to the substrate, for example, through one or more additional coatings. For example, while not limiting herein, according to various non-limiting embodiments, an additional coating composition can be applied to a portion of the surface of the substrate, at least partially set, and thereafter the coating composition that includes ihe photochromic cornpound(s) can be applied over the additiona! coating and at least partially set. Non-limiting and art-recognized methods of applying coatings compositions to substrates are discussed herein below,
|0148] Examples of additional coatings and films that can be used In conjunction with the photochromic coatings and articles according to the present invention, include, but are not limited to: primer coatings and films {which typically reside under the photochromic coating); protective coatings and films (which are typically applied over the photochromic coating), including transitional coatings and fiims and abrasion resistant coatings and fiims; anti-reflective coatings and fiims; conventional photochromic coatings and films; polarizing coatings and films; and combinations thereof. As used herein the term "protective coating or film" refers to coatings or films that can prevent wear or abrasion, provide a transition in properties from one coating or film to another, protect against the effects of polymerization reaction chemicals and/or protect against deterioration due to environmental conditions such as moisture, heat, ultraviolet light, oxygen, etc,
[0149] As used herein, the term "transitional coating and film" means a coating or film that aids in creating a gradient in properties between two coatings or films, or a coating and a film , For example, although not limiting herein, a transitional coating can aid In creating a gradient in hardness between a relatively hard coating and a relatively soft coating. Non-limiting examples of transitional coatings include radiation-cured, acrylate-based thin films as described in U.S. Patent Application Publication 2003/0165686 at paragraphs 79- 73, which are hereby specifically incorporated b reference herein.
[0150] As used herein the term "abrasion resistant coating and film" refers to a protective polymeric material that demonstrates a resistance to abrasion that is greater than a standard reference material, e.g., a polymer made of CR-39® monomer available from PPG Industries, fnc, as tested in a method comparable to ASTM F-735. Standard Test Method for Abrasion Resistance of Transparent Plastics and Coatings Using the Oscillating Sand Method. Non-limiting examples of abrasion resistant coatings include, for example, abrasion-resistant coatings comprising organosllanes, organosiloxanes, abrasion -resistant coatings based on inorganic maieriais such as silica, titania and/or zirconia, organic abrasion-resistant coatings of the type that are ultraviolet light curable, oxygen barrier-coatings, UV-shie!ding coatings, and combinations thereof.
[0151] Non-iirniting examples of antireffective coatings and films Include a monolayer, multilayer or film of metal oxides, metal fluorides, or other such materials, which can be deposited onto the articles disclosed herein (or onto films that are applied to the articles}, for example, through vacuum deposition, sputtering, etc. Non-iirn Sting examples of conventional photochromic coatings and films include, but are not limited to, coatings and films comprising conventional photochromic materials. Non-limiting examples of polarizing coatings and films Include, but are not limited to, coatings and films comprising dichroic compounds that are known in the art,
[0152] Additional coating compositions (e.g., primers and over-coats) that can be used with photochromic coating compositions according to the present invention and/or to form photochromic articles according to the present invention, can be applied to / formed; on a substrate prior to application of the photochromic coating; and/or over a previously applied photochromic coating. For example, a primer coating can be formed on the substrate prior to applying a photochromic coating composition according to the present invention. Additionally or alternatively, an additional coating or film can be applied (e.g., as an over-coat or over-coating) at least partially over a previously applied photochromic coating composition according to the present invention. For example, a transitional coating can be formed over a previously applied photochromic coating composition according to the present invention, and an abrasion resistant coating can then be applied over the transitional coating,
[0153] Photochromic coating compositions according to the present invention include: a photochromic compound according to the present invention, such as described previously herein with reference to Formulas (i) and (H); a curable resin composition; and optionally a solvent. The photochromic coating composition can be in the form of art-recognized liquid coatings and powder coatings. The photochromic coating compositio s of the present invention can be thermoplastic or thermosetting coating compositions. In an embodiment, the photochromic coating composition is a curable or thermosetting coating composition.
[0154] The curable resin composition of the curable photochromic coating compositions according to the present invention typically include: a first reactant (or component) having functional groups, e.g., an epoxide functional polymer reactant; and a second reactant (or component) that is a crossllnking agent having functional groups that are reactive towards and that can form covaient bonds with the functional groups of the first reactant. The first and second reactants of the curable resin composition of the curable photochromic coating composition can each independently include one or more functional species, and are each present in amounts sufficient to provide cured photochromic coatings having a desirable combination of physical properties, e.g., smoothness, optical clarity, solvent resistance and hardness.
[0155] Examples of curable resin compositions that can be used with the curable photochromic coating compositions according to the present invention include, but are not limited to: curable resin compositions comprising epoxide functional polymer (e.g., (meth)acfyltc polymers containing residues of glycidyi (meth)acrylate and epoxide reactive crossllnking agent (e.g., containing active hydrogens, such as hydroxyls, thiols and amines); and curable resin compositions comprising hydroxy functional polymer and capped (or blocked) isocyanate functional crossiinking agent,
[0156] In an embodiment, the curable resin composition of the photochromic coating composition of the present invention Is a curable urethane (or poiyurethane) resin composition. Curable urethane resin compositions useful In the photochromic coating compositions of the present invention typically Include: an active hydrogen functional polymer, such as a hydroxy functional polymer; and a capped (or blocked) isocyanate functional crossiinking agent. Hydroxy functional polymers that can be used In such compositions include, but are not limited to, art-recognized hydroxy functional vinyl polymers, hydroxy functional polyesters, hydroxy functional polyureihanes and mixtures thereof,
[0157] Vinyl polymers having hydroxy functionality can be prepared by free radical polymerization methods that are known to those of ordinary skill in the art. In an embodiment of the present invention, the hydroxy functional vinyl polymer is prepared from a majority of (meth)acrylate monomers and Is referred to herein as a "hydroxy functional (meth)acry!ic polymer."
[01 SB] Hydroxy functional polyesters useful in curable photochromic coating compositions comprising capped isocyanate functional crossiinking agent can be prepared by art-recognized methods. Typically, diois and dicarboxylic acids or diesters of dicarboxylic acids are reacted In a proportion such that the molar equivalents of hydroxy groups is greater than that of carboxylic acid groups (or esters of carboxylic acid groups) with the concurrent removal of water or alcohols from the reaction medium.
[0159] Hydroxy functional urethanes can be prepared by art-recognized methods, for example, as previously described herein. Typically one or more difunctional isocyanates are reacted with one or more materials having two active hydrogen groups (e.g., diois or dithiois), such that the ratio of active hydrogen groups to isocyanate groups is greater than 1 , as is known to the skilled artisan.
101601 By "capped {or blocked) isocyanate crossiinking agent" is meant a crossiinking agent having two or more capped isocyanate groups that can decap (or deblock) under cure conditions, e.g., at elevated temperature, to form free isocyanate groups and free capping groups. The free isocyanate groups formed by decapping of the crossiinking agent are preferably capable of reacting and forming substantially permanent covalent bonds with the active hydrogen groups of the active hydrogen functional polymer (e.g. , with the hydroxy groups of a hydroxy functional polymer).
[0181] It is desirable that the capping group of the capped isocyanate cross!inking agent not adversely affect the curable photochrome coating composition upon decapping from the isocyanate (i.e., when It becomes a free capping group). For example, it is desirable thai the free capping group neither become trapped in the cured film as gas bubbles nor excessively plastisize the cured film. Capping groups useful in the present invention preferably have the characteristics of being nonfugitive or capable of escaping substantially from the forming coating prior to its vitrification. Typically, the free capping groups escape substantially from the forming (e.g,, curing) coating prior to its vitrification.
£0162] Classes of capping groups of the capped isocyanate crosslinking agent can be selected from: hydroxy functional compounds, e.g., linear or branched C2-C8 alcohols, ethylene glycol butyl ether, phenol and p-hydroxy methy!benzoate; H- azoles, e.g., 1 H~1 ,2,4-triazoie and 1 H~2,5-dimeihy{ pyrazoie lactams, e.g., e- caproiactarn and 2-pyrolidinone; ketoximes, e.g., 2-propanone oxime and 2-butanone oxime. Other suitable capping groups include, morphoiine, 3-aminopropyS morpho!ine and N-hydroxy phthalimide,
[0163] The isocyanate or mixture of isocyanates of the capped isocyanate crosslinking agent has two or more Isocyanate groups (e.g., 3 or 4 isocyanate groups). Examples of suitable isocyanates thai can be used to prepare the capped isocyanate crosslinking agent include, monomeric diisocyanates, e.g., a, a'-xylylene dtisocyanate, a, a, a', a'~teiramethylxylylene diisocyanate and 1-isocyanato-3- isocyanatomethyl-3,5,5-trimethylcyciohexane (isophorone diisocyanate or IPDI), and dtmers and trimers of monomeric diisocyanates containing isocyanurate, uretidino, biruet or aliophanate linkages, e.g., the trimer of !PDI.
[0164] The capped isocyanate crosslinking agent can also be selected from oiigomeric capped isocyanate functional adducts. As used herein, by "oiigomeric capped polyisocyanate functional adduct" is meant a material that is substantially free of polymeric chain extension, Oiigomeric capped polyisocyanate functional adducts can be prepared by art-recognized methods from, for example, a compound containing three or more active hydrogen groups, e.g., trimethy!oipropane (T P), and an isocyanate monomer, e.g., 1 -isocyanato-3,3,5-trimethyi-5- ssoeyanatornethylcyciohexane (IPD!), In a molar ratio of 1 :3, respectively, in the case of TMP and IPDI, by employing art-recognized starved feed and/or dilute solution synthesis techniques, an oligomeric adduct having an average isocyanate functionality of 3 can be prepared (e.g., "TMP-3IPDI"). The three free isocyanate groups per TMP-3IPD! adduct are then capped with a capping group, e.g., a linear or branched C2-C8 alcohol..
[0165] To catalyze the reaction between the isocyanate groups of the capped polyisocyanate crossiinking agent and the hydroxy groups of the hydroxy functional polymer, one or more catalysts are typically present in the curable photochromie coating composition in amounts of from, for example, 0.1 to 5 percent by weight, based on total resin solids of the composition. Classes of useful catalysts include but are not limited to, metal compounds, In particular, organic fin compounds, e.g., tln(ll) octanoate and dibutyltin(iV) dilaurate, and tertiary amines, e.g., diazablcycio[2.2.2]octane.
[0166] Curable photochromie coating compositions according to the present invention, which include hydroxy functional polymer and capped isocyanate functional crossiinking agent, typically have present therein hydroxy functional polymer In an amount of from 55 percent to 95 percent by weight, based on total resin solids weight of the composition, e.g. , from 75 percent to 90 percent by weight, based on total resin solids weight of the composition. The capped isocyanate functional crossiinking agent is typically present in the curable resin composition in an amount corresponding to the balance of these recited ranges, i.e., 5 to 45, particularly 10 to 25, percent by weight.
[0167] With the curable urethane resin compositions of the curable photochromie coating compositions of the present invention, the equivalent ratio of isocyanate equivalents in the capped isocyanate crossiinking agent to hydroxy equivalents In the hydroxy functional polymer is typically within the range of 1 :3 to 3;1 , e.g., 1 :2 to 2:1. While equivalent ratios outside of this range can be employed, they are generally less desirable due to performance deficiencies in cured photochromie films obtained therefrom. Curable photochromie coating compositions according to the present invention that include hydroxy functional polymer and capped isocyanate functional crossiinking agent are typically cured at a temperature of from 120°C to 190°C over a period of from 10 to 80 minutes.
|0168] Photochromie coating compositions according to the present invention can, with some embodiments, optionally further include a solvent. Examples of suitable solvents include, but art not limited to, acetates, alcohols, ketones, glycols, ethers, aiiphattcs, cycloaiiphaiics and aromatics. Examples of acetates include, but are not limited to, ethy! acetate, butyl acetate, and glycol acetate, Examples of ketones include, but are not limited to, methyl ethyl ketone and methy!-N-amyl ketone. Examples of aromatics include, but are not limited to, are toluene, naphthalene and xylene. In an embodiment, one or more solvents are added to each of the first reactant and the second reactant. Suitable solvent blends can include, for example, one or more acetates, propanol and its derivatives, one or more ketones, one or more alcohols and/or one or more aromatics. If present, the solvent is typically present in an amount of from 5 to 60 percent b weight, or 5 to 40 percent by weight, or 10 to 25 percent by weight, based on the total weight of the photochromic coating composition (inclusive of the solvent weight).
[0169] Curable photochromic coating compositions according to the present invention can, with some embodiments, optionally contain additives such as waxes for flow and wetting, flow control agents, e.g., poly{2-eihylhexyl)acrylate, adjuvant resin to modify and optimize coating properties, antioxidants and ultraviolet (UV) light absorbers. Examples of useful antioxidants and UV light absorbers include those available commercially from Ciba-Geigy under the trademarks IRGANOX and TINUVIN. These optional additives, when used, are typically present in amounts up to 20 percent by weight (e.g., from 0,5 to 10 percent by weight), based on total weight of resin solids of the curable resin composition.
[0170] Photochromic compositions, articles and coating compositions according to the present invention can, with some embodiments, further include art-recognized additives that aid or assist in the processing and/or performance of the compositions or articles. Non-limiting examples of such additives include photoinittators, thermal initiators, polymerization inhibitors, solvents, light stabilizers (such as, but not limited to, ultraviolet light absorbers and light stabilizers, such as hindered amine light stabilizers (HALS)), heat stabilizers, mold release agents, rheology control agents, leveling agents (such as, but not limited to, surfactants), free radical scavengers, adhesion promoters (such as hexanediol diacrylate and coupling agents), and combinations and mixtures thereof.
[0171] The photochromic compounds according to the present invention can be used In amounts (or ratios) such that the organic material or substrate (e.g., photochromic articles and photochromic coatings) into which the photochromic compounds are incorporated or otherwise connected exhibits desired optical properties. For example, the amount and types of photochromic compounds can be selected such thai the organic material or substrate is clear or co!orless when the photochromic compound is in the closed-form (e.g., in the bleached or unacttvated state), and can exhibit a desired resultant color when the photochromic compound is in the open-form (e.g., when activated by actinic radiation). The precise amount of the photochromic compound that is utilized in the various photochromic compositions and articles described herein is not critical provided that a sufficient amount is used to produce the desired effect. The particular amount of the photochromic compound used can depend on a variety of factors, such as but not limited to, the absorption characteristics of the photochromic compound, the color and intensity of the color desired upon activation, and the method used to incorporate or connect the photochromic compound to the substrate. Although not limiting herein, according to various non-limiting embodiments disclosed herein, the amount of the photochromic compound thai is incorporated into an organic material can range from 0.01 to 40 weight percent, or from 0.05 to 15, or from 0, 1 to 5 weight percent, based on the weight of the organic material.
[0172J The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations therein will be apparent to those skilled in the art. Unless otherwise specified, ail parts and all percentages are by weight.
EXAMPLES
Photochromic Materials (PM)
Methods of making photochromic materials with and without at least one po!ymerizabie group are well known to those skilled in the art. For example, and without limitation, Photochromic Material A (PM-A) 3,3-di(4-methoxyphenyl)-6,11 ,13- trimeihyl-13~(2~(2~(2-hydroxyethoxy)ethoxy)ethoxy-3H, 13H-
Figure imgf000055_0001
can be prepared by following the process of Example 8 of U.S, Patent 6, 1 13,814, which example is incorporated herein by reference, except that in Step 7 of the process, triethyiene glycol is used in place of diethylene glycol.
PM-B, a photochromic materia! such as 3-(4-(2-hydroxyethoxy)phenyl)-3-(4- methoxypheny!)~13, 3-dimethyi~3H, 13H-!ndeno[2',3':3(4]rtaphthot ,2-bjpyran can be prepared by reacting 7,7-dimeihyl-5~hydroxy-7H~benzo[C]fiuorene with 1 -{4-(2- hydroxyethoxy)phenyi)~1 -(4~methoxyphenyl)-2-propyn-1 -of using procedures known to those skilled in the art.
P -C, a photochromic material such as 3-{4-methoxyphenyi)-3-(4-{2- hydroxyethoxy}phenyl)-6,7-dimethoxy~1 l -trifluoromethyi-I S S-dimethyl-SH iSH- indenoP'.S^S^lnaphthofl ^-bjpyran can be prepared following the procedure of Example 1 in U.S. Patent Application Publication 2008/0103301 except that 1-(4-(2- hydroxyethoxy)phenyi)"1-{4-methoxyphenyi)-2-propyn~1-oi would be used in place of 1 , 1 -bis(4-methoxyphenyl)-2-propyn-1 -ol in Step 8, which example is hereby incorporated herein by reference,
PM-D, a photochromic material such as 313-di(4"methoxyphenyl)- 6, 1 1 - dimethoxy-13-buiyl-13-(2-hydroxyethoxy)-3H,13H-indeno[2')3,:3,4Jnaphtho[1 ,2- hjpyran can be prepared by using the same process as described above for
Photochromic Materia! A, except that 3,3-di(4-methoxyphenyl}-6, 1 1 -dimethoxy-13- butyl-13-hydroxy-3H.13H-inden0[2',3':3,4]naphtho(1 ,2~b]pyran and ethylene glycol are reacted together in Step 7 of Example 8 of U.S. 8,1 13,814.
P -E, a photochromic material such as 3-(4-morpholinophenyl)-3-(4-{2- hydroxy)ethoxy)phenyl-l 3, 13-dimethyi-3H, 13H-indenoi2',3':3,4]naphtho[1 ,2~b]pyran can be prepared following the procedure of Steps 1-5 of Example 7 in U.S.
2006/0022176A1 , which disclosure is incorporated herein by reference.
Various non-limiting embodiments disclosed herein will now be illustrated in the following non-limiting examples,
EXAMPLES
In Part 1 of the Examples, the synthesis procedures used to make photochromic materials according to various non-limiting embodiments disclosed herein are set forth In Examples 1 -22. In Part 2, the photochromic performance testing is described. In Part 3, the test results are reported.
PART 1 - PHOTOCHROMIC MATERIALS - SYNTHESIS
In an oven-dried flask placed under a nitrogen atmosphere and equipped with a Dean-Stark trap, the product of Step 5 (26 g) was stirred in xylenes (520 mL). To this was added bismuth(ni)trifluoromethanesulfonate (3.4 g) and then the reaction mixture was heated to reflux for 3 hours. Example 1
Step 1
in an oven-dried flask {flask A) placed under a nitrogen atmosphere, a 1.0 solution of 3-methoxyphenylmagnes!um bromide in tetrahydroiuran (800 mL) and an additional 300 mL of tetrahydroiuran anhydrous were stirred. The flask was placed in an ice bath and to it. was added bisj (N,N-diethylamino)-ethyl) ether {152 ml) slowly drop-wise using an addition funnel over a 45 minute period. The mixture stirred for 1 hour during which time the solution partially solidified. In a separate oven-dried reaction fiask (flask 8), 4-bromobenzoyl chloride (160 g) was stirred in tetrahydroiuran anhydrous (740 ml). The flask was placed in an ice bath. The contents of fiask A was scooped out of if and added to ffask B portion-wise over 45 minutes. The reaction mixture was warmed to room temperature and stirred for an additional 2 hours. If was then slowly poured into a beaker containing a saturated aqueous solution of ammonium chloride (1.3 L) and ice. A separatory funnel was used to separate the layers. The aqueous layer was recovered and extracted with ethyl acetate (2x600 mL each time). The organic layers were combined and washed with a saturated aqueous solution of sodium bicarbonate {1 L), dried over sodium sulfate and concentrated by rotary evaporation to yield 231 grams of (4- bromophenyl)(3~methoxypheny!)methanone. The product was not purified and was used in the next reaction as is.
Step 2
In an oven-dried fiask placed under a nitrogen atmosphere, the product of Step 1 (90,6 g) and potassium tert-butoxide (56 g) were stirred in toluene (900 ml) using a mechanical stirrer. To this was added dimethyl succinate (70 mL) slowly drop-wise using an addition funnel over a 1 hour period. The exothermic reaction warmed to 40°C during the dimethyl succinate addition and became more viscous. Additional toluene (400 mL) was added. The reaction mixture was stirred for an additional 2 hours. The reaction mixture was slowly poured into a beaker containing deionized water (1 L) and ice. To this was added concentrated hydrochloric acid until a pH of 1 was reached. A separatory funnel was used to separate the organic and aqueous layers. The aqueous layer was extracted with with ethyl acetate 2 times (600 mL each). The organic layers were recovered, combined and washed with saturated aqueous solution of sodium chloride (700 mL), dried over sodium sulfate and concentrated by rotary evaporation to yield 150 grams of mixture of (E and Z) 4- (4-bromophenyi)-3-(rnethoxycarbonyi)-4-(3-methoxyphenyl)but-3~enoic acid. The product was used in the next reaction as is. Step 3
in a flask placed under a nitrogen atmosphere, the product of Step 3 (126 g) was stirred in acetic anhydride (500 mL). The reaction mixture was heated to reflux for 3 hours and then coofed to room temperature. It was concentrated by rotary evaporation and toluene was added (2x200 mL) and evaporated to remove residual water. The resulting residue was purified by column chromatography on silica gel (1000 g} eluting with a solution of 25% ethyl acetate / 75% hexanes. Fractions containing desired product were combined and concentrated by rotary evaporation. The resulting residue was recrystallized in methanol. The crystals were collected by vacuum filtration. Methyl 4-acetoxy- 1 -{4-bromophenyi)-7-methoxy-2-naphthoate (23 g) was isolated. This step was repeated to produce additional product for the next- step.
Step 4
In an oven-dried flask placed under a nitrogen atmosphere, the product of Step 3 (25 g), 2,4-dimethoxyphenyiboronic acid (11 .1 g) and sodium carbonate (1 .2 g) were stirred in 1 ,2-dimethoxyethane (125 mL) and deionized water (40 mL), A nitrogen purge fine was inserted directly into the reaction mixture for 10 minutes and then removed. Tetrakis(tripheny!phosphine)paliadium(0) (1.4 g) was added to the reaction mixture. Si was heated to reflux for 4 hours. After cooling to room temperature, the reaction mixture was poured into a beaker containing deionized water (1 L) and ice. Concentrated hydrochloric acid was added while stirring vigorousl until the pH reached 3. The mixture was transferred to a separator funnel and extracted with chloroform 3 times (400 ml each time). The organic layers were recovered, combined and then placed directly onto a silica gel column (600 g) eluting with a mixture of 30% ethyl acetate / 70% hexanes. Fractions containing product were combined and concentrated by rotary evaporation. The resulting residue was slurried in a minimal amount of a solution of 10% ethyl acetate / 90% hexanes, A solid precipitate was collected by vacuum filtration. 25.4 grams of methyl 4-acetoxy- 1 -{2\4'~dimethoxy~[ , 1 '-bsphenyi]-4-yi)-7-rnethoxy-2-naphthoate was isolated.
Step 5
Lanthanum(ill) chloride (44.2 g) and lithium chloride (13.2 g) were added to a reaction flask. The flask was placed in vacuum oven at 170°C for 4 hours, St was then removed from the oven and immediately placed under a nitrogen atmosphere. The product of Step 4 (25.3 g) was charged to the reaction flask and the mixture stirred in ietrahydrofuran anhydrous (500 mL). The reaction flask was cooled in a dry ice/acetone bath. To it was added a 2M solution of propylmagnesium chloride in diethyl ether (155 mL) slowly drop-wise using an addition funnel over the course of 40 minutes. The reaction mixture was heated to 40°C for 3 hours. It was then cooled to room temperature and slowly poured into a beaker containing deionized water (1 L) and ice. Concentrated hydrochloric ac d was added to the mixture while stirring vigorously until the pH reached 3. The mixture was transferred to a separator/ funnel and the organic layer and aqueous layer were separated. The aqueous layer was recovered, extracted with ethyl acetate 2 times (350 mL each time). The organic layers were recovered, combined and washed with a saturated aqueous solution of sodium bicarbonaie (500 ml), dried over sodium sulfate and concentrated by rotary evaporation. The resulting residue was purified by a chromatography column of silica gel (200 g) eiuting with a solution of 50% ethyl acetate / 50% hexanes. Fractions containing product were combined and concentrated by rotary evaporation. The resulting residue weighed 26 grams and was composed of 4-(2')4'«dimethoxy-[111 '-biphenyl}~4-y!)-3-(4-hydroxyheptan-4-yi)-6- methoxynaphtha!en-1-ol and several impurities, it was used In the next reaction as is.
Step 6
After cooling to room temperature the reaction mixture was added directly to a column of silica gel (400 g). It was eluted with a solution of 60% ethyl acetate / 40% hexanes. Fractions containing product were combined and concentrated by rotaty evaporation. The resulting residue was further purified with a second chromatography column of silica gel that was identical in conditions used to the first column. Fractions containing product were combined and concentrated by rotary evaporation. The resulting residue weighed 3.6 grams and was 2-methoxy-7,7- dipropyl-9-(2,4-dimethoxyphenyi)-7H-ben?o[C3fiuoren-5-oL
Step 7
in an oven-dried flask placed under a nitrogen atmosphere, the product of Step 6 (3.6 g) and 1-(4~(2-hydroxyethoxy)phenyi)-1-(4-methoxyphenyi)prop-2-yn-1~o! (2.9 g) were stirred in chloroform (72 mL). To this was added p-toluenesu!fonic acid (145 mg). The reaction mixture was stirred at room temperature for 2 hours. It was then placed directly on a colum of silica gel (300 g) eluting with a solution of 60% ethyl acetate / 40% hexanes. Fractions containing product were combined and concentrated by rotary evaporation. The resulting residue weighed 3.0 g. An NMR spectrum showed the product to have a structure consistent with 3-(4- hydroxyethoxyphenyi)~3-(4~methoxyphenyi)-7-me
13 3"dipropy! ^H 3H-!ndeno[2',3':3,4]naphtho[1 ,2-b]pyran.
Step 8
The product of Step 7 (5.3 g), triethyiamine (2.0 g), and tetrahydrofuran (50 mL) were combined in a reaction flask, and the mixture was stirred at room temperature. Sebacoyi chloride (1.3 g) was added drop-wise to the solution and the mixture was further stirred at room temperature for 2 hours. The mixture was filtered through a short silica gel plug and concentrated. The product was isolated by silica gei chromatography (ethyl acetate/metby!ene chloride (v/v), 1/20). The recovered product was precipitated from methylene chioride/methanol (v/v: 1/4) and filtered off as a purple-tinted powder (3.5 g). The nuclear magnetic resonance (NMR) spectrum showed the product to have a structure consistent with bis(2-(4-(3-(4- methoxypheny{)-7-methoxy-1 1 -(2,4~dimethoxyphenyi)-13, 13-dipropyl-3H, 13H- indeno[2,,3':3l4]naphtho 1 ,2-blpyran-3-yl)phenoxy)ethyi) decanedioate shown in the following graphic formula:
Figure imgf000060_0001
Exam le 2
P -E, 3-{4-morphoiinophenyi)-3~(4~(2-hydroxy)ethoxy)phenyl-13 3-dirnet yl- 3H,13H-indeno[2',3':3,4]naphtho i !2-b]pyran (2.5 g), triethyiamine (1.27 g), and methylene chloride (50 ml) were combined in a reaction flask, and the mixture was stirred at room temperature. Sebacoyi chloride (0.65 g) was added drop-wise to the solution. The mixture was further stirred at room temperature for 1 hour and filtered. Water (50 mL) was added to the filtrate and the mixture was partitioned. The methylene chloride layer was recovered, concentrated and the residue was purified by silica gel chromatography using as the e!uant (ethyi acetate/hexanes (v/v), 1/1 ), The recovered product was precipitated from methylene chloride/methanoi (v/v: 1/4) and filtered off as a blue-tinted powder (1 g). An N R spectrum showed the product to have a structure consistent w th bis(2-(4-(3-(4-morpho!inophenyl)-13, 13-dimethyi-
SH.I SH-lndenoP'^'.'S^Jnapbtholl ^-bjpyran-S-y phenoxyJethy!) decanedioate shown in the following graphic formula:
Figure imgf000061_0001
Example 3
P -D, 3,3-bis-(4-methoxyphenyl)-6, 11 -dimethoxy-13-butyi-13 -(2- hyd oxy }■■ ethoxy-3H, 13H~indeno[2\3^3,4]naphtho{1 ,2-b]pyran (7 g), 4.3 grams (4 equivalents) of triethyl amine and dry tetrahydrofuran (150 ml) were combined in a 250 ml reaction flask. To this was added 1.91 grams (0,75 equivalents) of sebacoyi chloride dropwise at room temperature under a nitrogen atmosphere. The reaction mixture was heated to reflux for 90 minutes. The reaction mixture was cooled to room temperature, and then poured into 200 ml of ethyl acetate. This mixture was washed twice, each time with 250 mL of a 1 :1 mixture of saturated aqueous NaHC03 and water. The organic layer was recovered, dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting residue was purified by column chromatography. The pure fractions were combined, rotovaped and dried under vacuum to obtain 6.1 grams of a yeiiowish-greenish foam. Mass Spectrometry and N R analysis show the foamy product to have a structure consisient with bis{2- (3i3-bis(4-meihoxyphenyl)~6,1 1 -dimethoxy-13-bufyi-3H,13H- indeno[2, !3,:3,4Jnaphtho[1 ,2-bJpyran-13-yl-oxy)ethyi) decanedioate shown in the following graphic formula;
Figure imgf000062_0001
Example 4
Step 1
In an oven-dried flask placed under a nitrogen atmosphere, 4~f!uorophenyi-4- hydroxyphenyl methanone (100 g), 2~chioroeihanol (75g), potassium carbonate (134 g) and potassium iodide (11.5 g) were stirred sn anhydrous dimethyiiormamide (400 mL) using a mechanical stirrer. The reaction mixture was heated to reflux for 4 hours. It was cooled to room temperature and then poured into a beaker containing deionized water (1 L} and ice. Concentrated hydrochloric acid was added while stirring vigorously until the pH reached 3. The mixture was transferred to a separatory funnel and then extracted with chloroform (2x600 mL), The organic layers were combined and washed with a saturated aqueous solution of sodium bicarbonate (750 mL), dried over sodium sulfate and concentrated by rotary evaporation to yield a solid. The solid was slurried in a minimal amount of a solution of 10% ethyl acetate / 90% hexanes and collected by vacuum filtration. 120 grams of 4~fiuorophenyl-4-{2- hydroxyethoxy)phenyi methanone was Isolated,
Step 2
in an oven-dried flask placed under a nitrogen atmosphere, the product of Step 1 (121 g) and 3,4~dihydro-2H-pyran {106 mL) were stirred in dschloromethane (1100 mL). To this was added p-ioiuenesu!fonic acid (4.4 g). The reaction mixture was stirred at room temperature for 2 hours, it was then transferred to a separatory funnel and washed with a saturated aqueous solution of sodium bicarbonate (1 L), dried over sodium sulfate and concentrated by rotary evaporation to yield an oil. 160 grams of 4-fiuorophenyi-4-(2-((tetrahydro~2H-pyran-2-yf)oxy)eihoxy)pheny! methanone was isolated, it was used in the next reaction as is without further purification.
Step 3 In an oven-dried flask placed under a nitrogen atmosphere, the anhydrous product of Step 2 {160 g) was stirred in dimethylformamide that had been saturated with acetylene gas (640 mL). The reaction flask was placed in an ice bath and to the reaction fiask was added an 18wt% slurry of sodium acetyiide in xylenes and mineral oil (310 g) drop-wise using an addition funnel ove a 40 minute period. The reaction was warmed to room temperature and stirred for 2 hours, it was slowly poured into a beaker containing deionized water (2 L), ice and chloroform (1 L). The mixture was transferred to a separator/ funnel and then the aqueous layer and organic layer were separated. The aqueous layer was extracted with chloroform (750 mL), The organic- layers were combined and washed with a saturated aqueous solution of ammonium chloride (750 mL) followed by a saturated aqueous solution of sodium bicarbonate (750 ml). The recovered organic layer was dried over sodium sulfate and concentrated by rotary evaporation. The resulting residue was purified by column chromatography on silica gel (1000 g) eiuting with a solution of 35% ethyl acetate / 85% hexanes. Fractions containing product were combined and concentrated by rotary evaporation to yield an oil. 120 grams of 4-fluoropheny!-1-(4-(2-(tetrahydro- 2H-pyran~2-yi)oxy)ethoxy)phenyi-prop~2-yn-1 -ol was isolated.
Step 4
in an oven-dried flask placed under a nitrogen atmosphere, 2,3-dimefhoxy- 7,7-dimethyl-9-cyano-7H-benzo[C3fluoren-5-ol (100 g), prepared according to Steps 1 to 6 of Example 1 of U.S. Patent Publication 2006/0228557 A1 , which disclosure is incorporated herein by reference, and the product of Step 3 (130 g) were stirred in chloroform (2 L). To this was added bismuth(HI)frifiuoromethanesulfonate (2 g). The reaction mixture was stirred at room temperature for 3 hours. It was separated using a silica gel column (200 g) eiuting with a solution of 50% chloroform / 50% ethyl acetate. Fractions containing product were combined and concentrated by rotary evaporation. The resulting residue was dissolved in chloroform (300 mL) and methanol (700 mL) and transferred to a reaction flask. To it was added p- toluenesulfonic acid (5 g), The reaction mixture was heated to reflux for 4 hours. Upon cooling to room temperature, a solid precipitated out of solution which was collected by vacuum filtration. The product (105 grams) of 3-(4-(2- hydroxyethoxy)phenyi)-3-(4-fluorophenyl)-6,7~dimethoxy-11 -cyano-13,13-dimethyl- 3H 3H-indeno[2\3^3,4]naphtho[1 ,2-b]pyran was isolated.
Step 5
In an oven-dried reaction flask placed under a nitrogen atmosphere, the product of Step 4 (100,7 g) and triethylamine (50 g) were stirred In dichloromethane (1500 mL). Sebacoyl chloride (21.6 g) dissolved in dichioromethane (450 mL) was added to the reaction mixture drop-wise using an addition funnel over a 1 ,5 hour period, it was stirred at room temperature for 1 hour. The reaction mixture was poured into a beaker containing a saturated aqueous solution of ammonium chloride (2 L) and ice. The mixture was transferred to a separatory funnel and the organic and aqueous layers were separated. The recovered aqueous layer was extracted with dichioromet ane (600 mL). The organic layers were combined and washed with a saturated aqueous solution of sodium bicarbonate (1 L), dried over sodium sulfate and concentrated by rotary evaporation. The resulting residue was purified by column chromatography on silica gel (1300 g) eluting with a solution of 50% ethyl acetate / 50% hexanes. The fractions containing product were combined and concentrated by rotary evaporation. The resulting residue was further purified with a second silica gel column {1300 g) eluting with 25% ethyl acetate / 75% hexanes. Fractions containing product were combined and concentrated b rotary evaporation. The resulting residue was dissolved in a minimal amount of dichioromethane. It was s!ow!y dropped into a beaker containing vigorously stirring methanol (1.8 L). A solid precipitated out of solution. Product was collected by vacuum filtration and weighed 65 grams. NMR analysis indicated the product to have a structure consistent with bis(2-(4-(3«(4-ffuoroph.enyi)~6,7-cl}methoxy«11-cyano-13,13-dimethyl-3H,13H- indeno[2',3':3,4}naphtho[1 ,2-b]-3-y{)phenoxy)ethyi) decanedioate shown in the following graphic formula:
Figure imgf000064_0001
Example 5
Step 1
To a 1 L single-neck flask was added 3-methoxyphenyimagnesium bromide in tetrahydrofuran (1 , 560 ml). The flask was set up with a N2 blanket and magnetic stirring. The flask was seated in ice-salt-water bath (-5 to -8°C). 1 ,2-Dimethyiamino ethyl ether (106 ml) in tetrahydrofuran (100 ml) was dropped to the flask through an addition funnel over 10 minutes. The mixture was stirred for 1 hour. 4-Bromobenzoyl chloride in tetrahydrofuran (122 g in TOO nil) suspension was dropped info the flask using an addition funnel over 20 minutes. The cooling bath was removed 1 hour after the addition. The mixture was stirred at room temperature for 20 hours, The solution was poured into brine (1 L), Cone, hydrochloric acid (250 ml) was added to the mixture s!owfy. The top layer was separated and filtered through magnesium sulfate. The solution was concentrated to initially yield an orange-red oiiy residue ( 182g) that became a yellow waxy product. The residue was dried under high vacuum and used as is In next step.
Step 2
The crude product from Step 1 (182 gram) was dissolved In toluene (1 L) in a 2 L single-neck RB flask with Ma blanket and overhead stirring. Dimethyl succinate (72 ml) was added to the same flask. Potassium t-butoxide (68 gram) was added to the mixture in portions over 20 minutes. The reaction mixture stirred at room temperature for 20 hours. After 3 hours the dark slurry was poured into cold water (400 ml). The bottom water layer was separated and acidified by cone, HCI (200 ml). The slurry was extracted with ethyl acetate twice with (500 mL and 300 ml). The top solution was dried over sodium sulfate and concentrated. The residue was dried under high vacuum (170 g) and used as is in next step.
Step 3
The oiiy product from Step 2 (170 gram) and trace amount of 4- dimethyiaminopyridine (0.2 gram) were dissolved in acetic anhydride (250 mL) in 1 L single-neck RB flask equipped with a water condenser and magnetic stirring under N2 blanket. The reaction mixture was heated to 120°C for 3 hours. The mixture was then condensed down to less volume under reduced pressure. The recovered oily residue was dissolved in methanol. Solid product crystallized out and was recovered by filtration yielding (80 grams). HMR analysis showed the product to have a structure consistent with methyl 4-acetoxy~1-(4-bromophenyi)-7- ethoxy-2-naphihoate. Step 4
To a 1 L single-neck flask was added the product of Step 3 (63 g), phenylboronic acid (21 g), potassium carbonate (100g), toluene (240 mL), ethanol (120 mL) and water (120 mL). The mixture was bubbled with N2 for 15 minutes, Tetrakis(tripheny!phosphine)pal!adium(0) (1 ,5 g) was added to the mixture. The reaction mixture was heated to reflux for 4.5 hours. The mixture was cooled to room temperature and poured into water (500 mL), The resulting mixture was acidified with concentrated hydrochloric acid (12N, 200 mL). The top organic layer was recovered, filtered through magnesium sulfate and then concentrated. Solid product was obtained from the solution. The mother liquor was filtered through a short silica gel piug. Solid product was obtained from the major fraction. The combined product (64g) was dried in vacuum oven.
Step 5
To a 3 L one-neck RB flask was added dry solid lanthanum(l!l) chloride (130 g), lithium chloride (37 g), the product from Step 4 (80 g) and anhydrous THF (1 ,5 L). The white slurry was stirred at room temperature for 20 hours. The flask was cooled in a dry ice / acetone bath. N-Propy!magnesium chloride in tetrahydrofuran solution (2 , 425 mL) was dropped to the mix slowly. The cooling bath was removed upon completing the addition. The reaction mixture was stirred for 3 hours. The mixture was poured Into 30% aqueous hydrochloric acid (500 ml) and ice, The recovered top layer was filtered over magnesium sulfate and then concentrated. The resulting oily product (74g) was used as is in Step 9.
Step 6
The product from Step 5 was dissolved in xylene (400 mL) In a 2 L single- neck flask equipped with Dean-Stark trap and water condenser. Bismuth trif uoromethanesulionate (1 ,6 g) was added to the flask. The reaction mixture was heated to reflux for 4 hours. The resulting mixture was cooled to room temperature and filtered through a silica gel piug. The major fraction was collected and condensed to less volume. Solid product (6.5 g) was recrystaiized out from t-butyl methyl ether/hexane solution to yield an off-white solid, 9-phenyi-2-methoxy-7,7-dipropyi-7H- benzo[c]fluoren-5-ol.
Step ?
The products from Step 6 (65 g), pyridinium p-to!uenesulfonate (3 g) and 1-(4- methoxyphenyi)-1 '-(4~(2-hydroxy)ethoxypherjy!)prop-2-yn- -o! (45 g) were dissolved in 1 ,2-dichloroethane (400 mL) in a 1 L single-neck flask. The mixture was heated to 80°C for 2 hours. The mixture was cooled to room temperature and filtered through a short silica gei plug. The major fraction was further purified by silica gel chromatography eiuting with ethyl aeeiate/hexanes to afford an oi!y product f §-§). Solid product (55 g) was obtained by precipitation of the oily product in hexanes. Step 8
The product from Step 7 (50 g), dimethyfaminopy dine (0.1 g) and triethyiamine (13 ml) were dissolved in methylene chloride (300 mL) in a 2 L single- neck reaction, flask. To the flask was slowly added sebaeoyl chloride (9 mL) In methylene chloride (100 mL) using an addition funnel. The mixture was stirred at room temperature for 30 minutes. The reaction mixture was poured into water (500 ml). The bottom organic layer was recovered, filtered over magnesium sulfate and then condensed to less volume. The residue was purified by chromatography eiuting with a solution of ethyi acetate / hexanes. The major fraction was collected and condensed to less volume. Solid product (47 g) was precipitated out from methanol. N R analysis indicated that one of the products had a structure consistent with bis- {2-(4~(3~(4-methoxyphenyl)-7-methoxy-1 1 -phenyl-13, 13-dipropy!-3H, 13H- indenoi2',3':3,4]naphtho[1 ,2-b]pyran"3-yl)phenoxy)ethyi) decanedioate shown in the following graphic formula:
Figure imgf000067_0001
Example 6
Step 1
1 -{4-2-Hydroxyethoxyphenyi )- 1 -(4-methoxyphenyl)~2~propy n- 1 -ol was prepared according to the procedure of Steps 1 and 3 of Example 7 In U.S. 2006/0022176A1 , except that 4-hydroxy-4'-methoxy-benzophenone was substituted for 4~hydroxy-4 -fluoro-benzophenone. This disclosure is incorporated herein by reference.
Step 2:
1 -Phenyl-2-methoxycarbonyl-6~meihoxy-4-acetoxynaphtha!ene was prepared according to the procedures of Steps 1 and 2 of U.S. Pat. No.5, 645,767, except thai 4-methoxy benzopheno.oe was substituted for benzophenone. This disclosure is incorporated herein by reference.
Step 3
The product Step 2 (50 grams) was added to a reaction f!ask containing 500 ml. of tetrahydrofuran. The resulting mixture was cooled in a ice water bath and stirred under a nitrogen atmosphere. Methyl magnesium chloride solution (703 mL of a 1M in tetrahydrofuran) was added dropwise over forty-five minutes. The resulting yellow reaction mixture was stirred at 0°C for 2 hours and slowly warmed to room temperature. The reaction mixture was poured into 2 L of an Ice/water mixture. Ether (1 L) was added, and the layers separated. The aqueous layer was extracted with two 500 ml portions of ether, and the organic portions were combined and washed with 1 L of water. The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting oil was transferred into a reaction vessel (fitted with a Dean-Stark [rap) containing 500 mL of toluene to which ten drops of dodecylbenzene sulfonic acid were added. The reaction mixture was heated to reflux for 2 hours and cooled. The toluene was removed via rotary evaporation to yield 40.2 grams of an light yellow solid. An NMR spectrum showed the product to have a structure consistent with 7,7-dimethyi-5-hydroxy-3-methoxy-7H- benzofCjfiuorene.
Step 4
The product of Step 1 (4.0 grams), the product of Step 3 (4.0 grams), and 100 mL of chloroform were combined in a reaction flask and stirred at 40°C. Sufficient dodecylbenzenesu!fonic acid was added (3-5 drops) to produce a deep black coloration to the solution. After two hours, the reaction mixture was cooled and washed with 100 ml. of water. The organic layer was separated, dried over sodium sulfate, and concentrated by rotary evaporation to yield dark oil. Methanol (100ml) was added to the product. Upon warming and stirring, the product readily crystallized. The crystals were filtered, washed with fresh methanol and dried to yield 4.2 grams of an off-white solid. An NMR spectrum showed the product to have a structure consistent with 3-(4-methoxyphenyl)-3-(4-(2-hydroxy)eihoxyphenyi)-6- methoxy- 13, 13-dimethyl-3H, 13H~indenc^3¾4]naphtho[1 ,2-b]pyran.
Step 5
The product of Step 4 (4.16 g), succinic anhydride (2.2 g), 4- dimethy!aminopyridine (45 mg), and anhydrous tetrahydrofuran (80 mL) were combined in a reaction flask. The reaction mixture was heated at reflux for 4 hours and then stirred at 55CC overnight. The reaction mixture was concentrated. The product was crystallized from acetone/methanol (1/1 ), yielding 4.5 g of a green-tinted solid, 3-(4-methox phenyi)-3-(4-(2«{(3-cart>oxypropanoyl)oxy)ett oxy))phenyI-6- methoxy-13, 13-dimethyl-3Hi 13H-indenot2\3':3,4]naphthoi1 ,2-bjpyran.
Step 6
The product of Step 5 (4.49 g), decanediol (0.58 g)s ,Ν'- dicyclohexylcarbodiimide (1.52 g), 4-dimethy!aminopyridine (0,49 g), dodecy! benzenesulfonic acid (1 .09 g), and methylene chloride (70 ml.) were combined in a reaction flask. The reaction mixture was stirred at room temperature overnight. The mixture was filtered and concentrated. The product was isolated by silica gel chromatography (methylene chloride and then ethyl acetate/methylene chloride (v/v), 1/6), yielding 3.0 g of a green-tinted solid. An N R spectrum showed the product to have a structure consistent with 0,0'-decane-1 , 10-diyl bis{2-(4-(3-(4- meihoxyphenyi)~6-methoxy-1 /13-dimethyi~3H 3HH'ndeno[2\3':3,4]naphtho[l2- b]pyran-3~yl)phenoxy)ethyl) disuccinate shown in the following graphic formula:
Figure imgf000069_0001
Exam le 7
Step 1
Into a 1 liter reaction (3 neck) flask was added 2,3-dimethoxy-7,7-dimethyl-9- bromo-7H-benzo[C]fiuorerv5-ol (25 grams), the product of Step 5 of Example 1 in U.S. Patent Publication 2006-0228557, which disclosure is incorporated herein by reference, 2,3,4-trtfluorophenyJ boranic acid (13.82 g), Na2C03 (13.32 g), 1 ,2- dimethoxyethane (300 mL), water (150 mL). Nitrogen was bubbled through the reaction mixture for 10 minutes, Tetrakis (triphenylphosphine) palladium (0) (3,63 g) was added to the reaction mixture and the resulting reaction mixture was heated to reflux and maintained at reflux for 6 hours. The reaction was cooled to room temperature and poured into 500 ml. of water / 50 mL of 10% HCi followed b extraction with ethyl acetate (2 x 300 mL each time). The organic (ethyl acetate) layers were recovered, combined and washed with saturated NaCI solution (400 ml). This organic layer was dried over anhydrous sodium sulfate and concentrated b rotary evaporation to obtain 27.5 g of material. This resulting material {2,3-dimethoxy- 7,7-dimethyl-9-(2,3!4-tnfiuorophenyi)-7H-benzo C]fluoren-5-ol} was used without further purification for Step 2.
Step 2
Into a 500 ml. reaction flask was added the product of Step 1 (6.0 g), 1-(4- methoxyphenyf)-1 '-(4-{ -hydrox )ethoxypheny!}-2~propyn-1-ol (4.4 g), and chloroform (250 mL). To the resulting reaction mixture was added 0.34 grams of PPTS (pyridinium p-toluene-suifonate). The reaction mixture was stirred at room iemperature for 4 hours and further additions of 1~(4-methoxyphenyl)-1 '-{4-(2- hydroxy)ethoxyphenyl)-2-propyn-1-ol (2.0 g), and PTSA (p-tciuene-su!fonic acid, 0.5 g) were made. The reaction mixture was stirred overnight and then washed with 400 ml of a 1 : 1 mixture of saturated aqueous NaHCG3 and wafer. The organic layer was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The resulting residue was purified by purified by chromatography to get 8.4 grams of a grayish solid. This solid was slurried in diethyl ether and filtered to obtain 7.22 grams of an off-white so!id product. NMR analysis showed the product to have a structure consistent with 3-(4~methoxyp enyi)-3-(4-(2-hydroxy)ethoxyphenyt)-6,7-dimeihoxy- 1 1 -(2>3>4-trif!uorophenyl)-13, 13-dimethy!-3H,13H-indeno[2\3':3,4]naphtho[1 ,2~ bjp ran.
Step 3
The product of Step 2 (3.90 g), succinic anhydride (1.6 g), 4- dtmethyiaminopyridine (33 mg), and anhydrous tetrahydrofuran (80 mL} were combined in a reaction flask. The reaction mixture was heated at reflux for 4 hours and then stirred at 55°C overnight. The reaction mixture was concentrated and the product was crystallized from methylene chioride/meihanol (1/2, v/v), yielding 4.1 g of a green-tinted solid, 3-{4-methoxy)pheny!-3-(4-(2-((3- carboxypropanoyl)oxy)ethoxy))phenyl-6,7-dirnethoxy-1 1-(2,3,4~trifiuoro)pheny!-13,13-
Figure imgf000070_0001
Step 4
The product of Step 3 (4.0 g), decanedlol (0.41 g), Ν,Ν'- dicyciohexy!carbodiimide (1 .09 g), 4-dirnethylaminopyridine (0.35 g), dodecy! benzenesuifonic acid (0.79 g), and methylene chloride (60 mL) were combined in a reaction flask. The reaction mixture was stirred at room temperature overnight. The mixture was filtered and concentrated. The product was isolated by silica gel chromatography using methylene chloride and then ethyl acetate/methylene chloride (v/v), 1/20, yielding 2.5 g of a green-tinted solid. An NMR spectrum showed the product to have a structure consistent with O,O'-decane-1,10~diyl bis-(2-(4-(3-(4- methoxyphenyl)-6 J-dimethoxy-11 -(2,3,4-trifluorophenyl)-13, 13-dimethyi-3H, 13H- i denop'.S^S^lnaphthofJ ,2-b]pyran-3-yi)phenoxy)ethyl) disuccinaie shown in the following graphic formula:
Figure imgf000071_0001
Example 8
Step 1
P -C, 3-{4~methoxyphenyl)-3"{4^2~hydroxy)ethoxyphenyl)--6:7-dimethoxy'11 - trif!uoromethyl-13, 13~dirnethyi~3H, 13H ndeno[2\3^3,4Jnaphthop ,2-bJpyran (3,5 g), succinic anhydride (1 ,05 g), 4-dimethylaminopyridine (32 mg), and anhydrous tetrahydrofuran (30 mL) were combined in a reaction flask. The reaction mixture was heated at reflux for 4 hours and then stirred at 55°C overnight. The reaction mixture was concentrated. The product was isolated by silica gel chromatography (ethyl acetate/hexanes (v/v): 1/1 ), yielding 3,7 g of a brown-tinted solid, 3~(4- methoxyphenyl)-3-(4-(2-(3-carboxypropanoyl)oxy)ethoxyphenyi)-6 -dirnethoxy-11- trifluorornethyl-13,13-dimethyl-3H,13H-indenoi2\3':3,4]naphthoi1 ,2-b]pyran.
Step 2
The product of Step 1 (3.6 g), decanediof (0.408 g), Ν,Ν'- dicyciohexylcarbodilmide (1,06 g), 4-dimethyiaminopyridine (0.343 g), dodecy! benzenesuifonic acid (0.764 g), and methylene chloride (120 mL) were combined in a reaction flask. The reaction mixture was stirred at room temperature overnight. The mixture was filtered and concentrated. The product was isolated by silica gel chromatography using as eiuant ethyl acetate/hexanes (v/v): 1/1, followed by a second short silica gel chromatography (ethyl acetate/hexanes (v/v): 2/1 ), yielding 2.4 g of a brown-tinted solid. An NMR spectrum showed the product to have a structure consistent wit O.O'-decane-I .I Q-diyl bis-(2-(4-(3-(4-rriethoxyphenyS)-6,7- dimethoxy-1 1 -trifiuoromethyl-13, 13-dimethyl~3H, 13H-indeno[2*,3":3,4]naphtho[1 ,2- b]pyran-3-yi)phenoxy)ethyl) disuccinaie shown in the following graphic formula:
Figure imgf000072_0001
Example 9
Step 1
2,3-Dimeihoxy-7,7-dimethyl-9-bromo-7H-benzo[CJ f!uoren-5-oi (50.0 g, the product of Step 5 of Example 1 of US2006/0 26402 A1 , which example is hereby specifically incorporated by reference herein), tetrakis(tripheny!phosph1ne)pa!iadium (5.0 g), (2-trifluoromethyi)phenyi boronsc acid (26.2 g), sodium carbonate (39.8 g), ethylene glycol dimethyl ether (400 mL), and water (300 mL) were combined in a reaction flask under a nitrogen atmosphere and stirred for 1 hour at room temperature. The mixture was then heated to reflux temperature for 24 hours. The reaction mixture was cooled to room temperature and poured into water (1 I) and extracted with ethyl acetate (three times with 500 mL). The organic extracts were combined and the solvent was removed by rotary evaporation to give 46.5 g of a light yellow solid. NMR spectra showed the product to have a structure consistent with 2,3-dimethoxy-7J-dimethyl-9"(2-trifluoromethy!pheny -7H-ber>zoiC] fiuoren-5-ol. Step 2 The product of Step 1 (4.0 g), 1 «(4~{2-hydroxyethoxy)pheny!-1~(4~ morpholiRophenyl)-2-propyn~1-ol (3.7 g, made as described in Step 3 of Example 7 of U.S. 2006/0022176A1), which disclosure is incorporated herein by reference, dodecylbenzene sulfonic acid (0.2 g) and chloroform (preserved with pentene, 250 mL) were combined in a reaction flask and stirred at room temperature for 5 hours. The reaction mixture was washed with 50 % saturated aqueous NaHCC (200 mL} and the organic layer was dried over anhydrous Na2S0 . The solvent was removed by rotary evaporation. Hot methanol was added to the resulting residue and the solution cooled to room temperature. The resulting precipitate was collected by vacuum filtration and washed with cold methanol yielding 4,7 g of
3-(4-morpholinophenyl)-3-(4-(2-hydra^^
!rifiuoromethyipheny))-13,13^
Ste 3
In a dried 250 mL two neck flask under nitrogen, piperidine (1.4 g) was added into THF (100 mL). The flask was placed in an ice bath and to it was added n-butyl lithium (nBuLi) (5 mL, 2,5 M) slowly dropwise over 10 min. The ice bath was removed and the reaction mixture was heated to 70X for 4 hrs. The mixture was cooled down to room temperature and the product of Step 2 (2.5 g) was added slowly. The reaction mixture was stirred for 1 hour at room temperature and poured into 200 ml water. The mixture was extracted with ethyl acetate (three times with 200 mL each time). The organic extracts were combined and the solvent was removed by rotary evaporation to give 2.9 g of 3-(4-morphoiinophenyl)-3-(4-(2-hydroxy)ethoxyphenyl)-6- methoxy-7-piperidino-1 1 -(2-trifluoromethy!phenyl)-13,13-dimethyl-3H,13H-
Figure imgf000073_0001
,2 3]pyran.
Step 4
The product of Step 3 (2.1 g), succinic anhydride (0.49 g), 4- dimethylaminopyridine (15 mg), and anhydrous tetrahydrofuran (30 mL) were combined in a reaction flask. The reaction mixture was heated at reflux for 4 hours and then stirred a! 55C overnight. The reaction mixture was concentrated. The product was isolated by silica gel chromatography (ethyl acetate/hexanes (v/v): 3/1 ), yielding 2.0 g of a purple-tinted solid, 3-(4-morpholinophenyt)-3-(4-(2-(3- carboxypropanoyi)oxy)ethoxyphenyl)-6-methoxy-7-piperidino~ 1-(2- trifluoromethylphen -I S S-dimeth l-SH.I
Figure imgf000073_0002
Step 5
The product of Step 4 (1.8 g), decanediol (0.165 g), ',Ν'- dicyciohexyicarbodiimide (0.43 g), 4-dimethyiaminopyridine (0,14 g), dodecyl benzenesulfonic acid {0.31 g), and methylene chloride (42 mL) were combined in a reaction fiask. The reaction mixture was stirred a! room temperature overnight, The mixture was filtered and concentrated. The product was isolated by silica gel chromatography (ethyl acetate/hexanes (v/v): 4/1 ), yielding 1.2 g of a purpfe-tinted solid. An NMR spectrum showed the product to have a structure consistent with 0,0'-decane-1 0-diyibis-(2-(4-(3-(4-morpho!inopheny )-6--methoxy-7~plperidino- - (24rifluoromethylphenyi)-13 ,13-dimethyi-3H ,13Hindeno[2\3':3,4]naphtho[1 ,2~b]pyran- 3-yl)phenoxy)ethyl} disuccinate shown in the following graphic formula:
Figure imgf000074_0001
Example 10
Step 1
P -D, 3,3-bis-(4-methoxyphenyl)~611 1 -dimethoxy-13-buiyM 3-{2- hydroxy)ethoxy-3H, 13H-indeno[2',3':3,4jnaphtho[1 ,2-b]pyran (3.5 g), succinic anhydride (1 .06 g), 4-dimethyiamlnopyndine (32 mg), and anhydrous tetrahydrofuran (30 ml) were combined in a reaction flask. The reaction mixture was heated at reflux for 4 hours and then stirred at 55 °C overnight. The reaction mixture was concentrated. The product was isolated by silica gel chromatography using as eiuant ethyl acetate/hexanes (v/v): 1/1 , yielding 3.6 g of a green-tinted solid, 3,3-bis-(4~ rnethcxypheny!)-6, 1 1 -dimeihoxy-13-buty!~13-(2-(3-carboxypropanoyl )oxy )ethoxy- SH. SH-inde oi^.S'^ ^ aphthoil ^-bj ran,
Step 2
The product of Step 1 (1.53 g), decanedio^ (0.176 g), Ν,Ν'- dicyclo exyicarbodiimlde (0.457 g), 4-dimethylamjnopyrtdine (0.148 g), dodecyl benzenesulfonic acid (0.33 g), and methylene chloride (52 mL) were combined in a reaction flask. The reaction mixture was stirred at room temperature overnight. The mixture was filtered and concentrated. The product was isolated by silica gel chromatography using as eiuant ethyl acetate/hexanes (v/v): 1/1 , followed by a second short silica gel chromatography using as e!uant ethyl acetate/hexanes (v/v): 2/1 , yielding 1.0 g of a green-tinted solid. An R spectrum showed the product to have a structure consistent with 0,0'~decane-1 , 10-diyl bis-(2-(3,3-bis-(4- methoxypheny})-6, 1 -dimethoxy-13-butyl-3H , 13H-indeno(2',3':3,4]naphtho[ ,2- b]pyran-13-yl-oxy)ethyl) disuccinate shown in the following graphic formu a:
Figure imgf000075_0001
Example 1 1
Step 1
PM-B, 3-(4-methoxyphenyl)-3~(4-(2-hydroxy)ethoxyphenyl)- 13,13-dimethyi- indeno[2\3':3,4]naphtho[1 ,2~b]pyran (5.0 g), pyridine (2.2 g), and anhydrous THF (80 mL) were combined in a reaction flask, and the mixture was stirred at room temperature, 1 ,6-Hexane bischioroformate (1.7 g) was added drop-wise to the solution. The mixture was further stirred at room temperature for 2 hours and filtered. The filtrate was concentrated and the residue was dissolved in ethyl acetate. Wate (50 mL) was added to the solution and the mixture was partitioned. The ethyl acetate layer was recovered, concentrated and the residue was purified by silica gel chromatography (ethyl acetate/hexanes (v/v), 1/2) and the product was precipitated from methylene chioride/methanol (v/v: 1/4). The product was recovered by filtration as a purple-tinted powder (1 .2 g). An NMR spectrum showed the product to have a structure consistent with hexane-1 ,6-diyj bis-(2-(4-(3-(4-melhoxyphenyl)-13, 13- dίmethyl·3Hi13H·-indeno[2 3':3!4]naphtho[1 ,2-bjpyra ~3- l)phe oxy)ethyί)
dicarbonate shown in the following graphic formula;
Figure imgf000076_0001
Example 12
Step 1
ΡΜ-Ε, 3^4-morphoiinophenyi)-3-(4-(2-hydroxy)ethoxyphenyl)-13,13-dimethyl- 3H, 1 SH-indenojS'.^S^naphthop ,2-b]pyran (3.5 g), succinic anhydride ( 1 .18 g), 4- dimethylaminopyridine (36 mg), and anhydrous tetrahydrofuran {30 mL) were combined in a reaction flask. The reaction mixture was heated at reflux for 4 hours and then stirred at 556C overnight. The reaction mixture was concentrated. The product was isoiated by silica gel chromatography using as e!uant ethyl
acetate/hexanes (v/v): 1/1 , yielding 3.6 g of a blue-tinted solid, 3~(4- morpholinopheny!)~3-(4-{2~(3-carboxypropanoyl)oxy)ethoxy)pheny!)- 3, 13-dimeihyi- 3H 3H ndenc[2 3^3,4]naphthop ,2-b]pyran.
Step 2
The product of Step 1 (1 .0 g), Methylene glycol (0.108 g), Ν,Ν'- dicyclohexyicarbodumide (0.325 g), 4-dimethylaminopyridine (0.105 g), dodecyl benzenesuifonic acid (0.235 g), and methylene chloride (40 mL) were combined in a reaction flask. The reaction mixture was stirred at room temperature overnight. The mixture was filtered and concentrated. The product was isolated by silica gel chromatography (ethyl acetate/hexanes (v/v): 2/1 ), yielding 0.5 g of a blue-tinted solid. An N R spectrum showed the product to have a structure consistent with 0,0'-((ethane-1 >2-diy!bis(oxy))bis(ethane-2, 1 -diyl)) bis~(2-(4-(3-(4-morpholinophenyl)- 13 3-dlmethyi-3H, 13H-indeno[2^3':3,4]naphtho[1 )2-b]pyran-3-yi)phenoxy}e hyl) disuccinate shown in the following graphic formula:
Figure imgf000077_0001
Example 13
Step 1
PM-E, 3H^narpholinophenyi)»3^
3H 3H-inderio[2\3^3,4]naphiho[1 ,2-bjpyran (3.5 g), succinic anhydride (1 .18 g), 4- dimethyiaminopyridine (38 mg), and anhydrous tetrahydrofuran (30 mL) were combined in a reaction fiask. The reaction mixture was heated at reflux for 4 hours and then stirred at 55°C overnight. The reaction mixture was concentrated. The product was isolated fay silica gel chromatography (ethyl acetate/hexanes (v/v): 1/1 ), yieiding 3.6 g of a blue-tinted solid, 3-(4-morphoiinophenyS)~3~(4~(2-(3- carboxypropanoyi)oxy)ethoxy)phenyl)-13, 13-dimethy!-3H, 13H~
indeno[2\3':3,4]naphiho[1 ,2-b3pyran.
Step 2
The product of Step 1 (0.58 g), tetraethyiene glycol (0.08 g), Ν,Ν'- dicyclohexyfcarbodfimide (0.19 g), 4-dfmethyiamlnopyridine (0.06 g), dodecyl benzenesulfonic acid (0.135 g), and methylene chioride (25 mL) were combined in a reaction flask. The reaction mixture was stirred at room temperature overnight. The mixture was filtered and concentrated. The product was isolated by silica gel chromatography (ethyl acetate/hexanes (v/v): 3/1 ), yielding 0.3 g of an expanded blue-tinted foam. An MR spectrum showed the product to have a structure consistent with 0,0'-{{(oxybis{eihane-2,1 -diy!))bis(oxy))bis{ethane-2,1 -diy!)) bis-(2-{4- (3-(4~morpho!inophenyf}-13,13-dime^3H,13H-indeno[2\3,:3,4]naphtho[1 >2- bjpyran-3-yi)phenoxy)ethyl) disuccinate shown in the following graphic formula;
Figure imgf000078_0001
Example 14
Step 1
2,3-Dimethoxy-7,7-dimethyl-9'bromO'7H-benzo[C] fluoren-5-o! {10.0, the product of Step 5 of Example 1 of US2006/0226402 A1 , which example Is hereby •specifically incorporated by reference herein), tetrakis(iripheny!phosphine)paliadium (1 .0 g), 4-{hydroxymethy!)pheny!.boronic acid (4.2 g), sodium carbonate (8.0 g), ethylene glycol dimethyl ether (100 mL), and water (100 mL) were combined in a reaction flask under a nitrogen atmosphere and stirred for 1 hour at room temperature, The mixture was then heated to reflux temperature for 24 hours. The reacison mixture was cooled to room temperature and poured into water (300 mL) and extracted with ethyl acetate (three times with 200 mL each time). The organic extracts were recovered, combined and the solvent was removed by rotary evaporation to give 9.1 g of a light yellow solid. NMR spectra showed the product to have a structure consistent with 2,3-dimethoxy~7,?~dimethyi~9~(4- hydroxymethyS)pheny!-7H~benzo[C] f!uoren-5-οί.
Step 2
The product of Step 1 (3.0 g), 1 -(4-methoxyphenyi)~1 -(4-morphoiinophenyl)-2- propyn-1-oi (3.0 g, made as described in Step 1 of Example 1 of U.S. Patent No. 5,458,814, which disclosure is incorporated herein by reference, dodecyibenzene sulfonic acid (0.2 g) and chloroform (preserved with pentene, 250 mL) were combined in a reaction flask and stirred at room temperature for 5 hours. The reaction mixture was washed with 50 % saturated aqueous NaHC03 (200 mL) and the organic layer was dried ove anhydrous Na2S04. The solvent was removed by rotary evaporation. Hot methanol was added to the resulting residue and the solution cooled to room temperature, The resulting precipitate was collected by vacuum filtration and washed with cold methanol yielding 3.4 g of
3-(4~methoxyphenyl)-3-'{4--morphoiinophenyl)-6s7-d!rnethoxy-1 ~(4- hydroxymethy!)phersy!-13, 13-dimethyi-3H,
Figure imgf000079_0001
,2-bJpyran.
Step 3
The product of Step 2 (3.0 g), succinic anhydride (0,82 g), 4- dimeihyiaminopyridine (25 mg)r and anhydrous tetrahydrofuran (30 mL) were combined in a reaction flask. The reaction mixture was heated at reflux for 4 hours and then stirred at 55°C overnight, The reaction mixture was concentrated. The product was crystallized from acetone, yielding 2.8 g of an off-white solid, 3-(4- methoxypheny!)-3-(4-morpho!inophenyi)-6,7-dirnethoxy-1 1-(4-(3- carboxypropanoyl)oxymethyl)pheny1-13, 13~dimethyl~3H , 13H- indeno[2',3':3,4]naphtho[t ,2-bjpyran,
Step 4
The product of Step 3 (1 .0 g), decanediol (0, 10 g), , '- dicyclohexylcarbodiimide (0.27 g}, 4-d!methyiaminopyridine (0,09 g), dodecyl benzenesulfonic acid (0.20 g), and methylene chloride (30 mL) were combined in a reaction flask. The reaction mixture was stirred at room temperature overnight. The mixture was filtered and concentrated. The product was Isolated by silica gel chromatography (ethyl acetate/hexanes (v/v); 2/1 ), yielding 0.6 g of a green-tinted solid. An NMR spectrum showed the product to have a structure consistent with 0,0'-decane-1 , 10-diyl bis-(4-(3~(4-methoxyphenyl)-3-{4-rnorpho!inophenyi}-8!7- dimethoxy-13 3-d.imethyl-3H> 13H-indeno[2\3^3i4]naphtho[1 ,2-b]pyran-1 1-yi)benzyl) disuccinate shown in the following graphic formula:
Figure imgf000079_0002
Example 15
PM-B (5.0 g), meia-ietramethyfxy!y!ene diisocyanate (1 .13 g), butyiated hydroxytoiuene (33 mg), dibutyitin di!aurate (33 mg), and ethyl acetate (30 rnL) were combined in a reaction f!ask, and the mixture was heated at reflux for 2 hours. Methanol (5 ml) was added to the mixture to quench excess meta- tetrameihylxy!ylene diisocyanate. The mixture was concentrated and the residue was purified by silica gei chromatography (ethyl acetate/hexanes (v/v): 2/3). The product was obtained as a purple-tinted solid (4.0 g). An NMR spectrum showed the product to have a structure consistent with 1 ,3-phenylene bis-(propane-2,2-diy!) bis- (a-i^S-f^metho henyiVi a S-dimeihyi-SHJ SH-indenop'.S'^^jna hthof ^- bjpyran-3-yl)phenoxy)ethyl) dicarbamate shown in the foiiowing graphic formula:
Figure imgf000080_0001
Exampie 16
PM-B, 3-(4-methoxyp enyS)-3-(4-(2-hydroxy)ethoxyp.henyi)-13(13-dimethyl»
SH.I SH-indenop'.S^S^jnaphfhoil ^-bjpyrars (3.5 g), 1 ,6-hexane diisocyanate (0,56 g), butyiated hydroxytoluene (23 mg), dibutyitin di!aurate (23 mg), and ethyl acetate (30 mL) were combined in a reaction flask, and the mixture was heated at reflux for 2. hours. Methanol (5 ml) was added to the mixture to quench excess 1 ,6-hexane diisocyanate. The mixture was concentrated and the residue was purified by siiica gel chromatography (ethyl acetate/hexanes (v/v): 1/1 ). The product was obtained as a purple-tinted solid (1.8 g). An NMR spectrum showed the product to have a structure consistent with hexane-1 ,6-diyl bis-(2-(4-(3-{4-methoxyphenyl)- 3,13- dimethyl~3Hl13H-indenoi2',3':3,4Jnaphtho[1 ,2-b)pyran-3-yl)phenoxy)ethyi}
dicarbamate shown in the following graphic formula:
Figure imgf000081_0001
Example 17
PM-B, 3-(4-methoxyphenyl)-3-(4-{2-hydroxy)eihoxypheny!)-13, 13-dimethyl-
3HI13H-snden:0[2',3,:3,43naphiho[1 ,2-b]pyran (5.0 g), 4,4'- diisocyanatodicyclohexylmethane (1.21 g), butyiated hydroxytoluene {33 mg), dibutyiiin dila urate (33 mg), and ethyl acetate (30 imL) were combined in a reaction flask, and the mixture was heated at. reflux for 2 hours. Methanol (5 mL) was added to the mixture to quench excess 4,4>-diisocyanatodicyclohexyimethane. The mixture was concentrated and the residue was purified by silica get chromatography (ethyl acetate/ftexanes (v/v): 1/2). The product was obtained as a purp!e-tinied solid (4,3 g). An NMR spectrum showed the product to have a structure consistent with methylene bis(cyciohexane~4, 1 -dry! ) bis-(2-(4-(3-(4-methoxyphenyl)~13, 13-dimethyl- 3H,13H-indeno[2\3':3,4]naphtho[1 ,2-b]pyran~3~yl)phenoxy)ethyl) dicarbamate shown in the following graphic formula:
Figure imgf000081_0002
Exampie 18
PM-B, 3-(4-methoxyphenyi)-3-{4-(2-hydroxy)ethoxyphenyi)-13,13-dimethyS- 3H,13H-indeno[2',3':3f4]naphiho[1 ,2-b]pyran (5.0 g), isophorone diisocyanate (1.03 g), butyiated hydroxytoluene (33 mg), dibu yltin difaurate (33 mg), and ethyl acetate (30 mL) were combined in a reaction flask, and the mixture was heated at reflux for 2 hours. Methanol {5 ml..) was added to the mixture to quench excess isophorone diisocyanate. The mixture was concentrated and the residue was purified by silica gel chromatography (ethyl acetate/hexanes (v/v); 1/2). The product was obtained as a purple-tinted solid (4.2 g). An N R spectrum showed the product to have a structure consistent with 5-{2-(4-(3-(4-meihoxypheny!)-13, 13-dimethyl3H( 13H- indeno[2!,3':3,4]naphtho[1 ;2-b]pyran-3-yl)phenoxy)ethyfoxycarbonylamino)-1~(2-(4~(3- (4-methoxyphen l)-13, 13-dimethyl-3H, 13H-indenoi2,,3,:3,4]naphtho[1 ,2-blpyran-3- yl)phenoxy)ethyloxycarbony!aminomethyl)-1 ,3,3-trimethyicyclohexane shown in the following graphic formula:
Figure imgf000082_0001
Example 10
Step 1
P -B, 3-(4-methoxyphenyl)-3-(4-(2-hydroxy)ethoxypheny!)- 3, 13-dimethyi- 3H,13H-indeno[2',3':3,4]naphtho[1 ,2-b3pyran (2.0 g), e-caproiactone (3.7 g), and toiuene (24 g) were combined in a reaction flask, and the mixture was stirred at room temperature for 30 minutes. Triisopropoxyaiuminum (0.23 g) was added drop-wise to the solution. The mixture was further stirred at room temperature for 7 hours.
Diluted hydrochloric acid (50 mL) was added to the solution and the mixture was partitioned. The recovered toluene layer was concentrated and the residue was purified by silica gel chromatography (ethy! acetate/hexanes (v/v), 1/2, 1/1 , 4/1 ), yielding 4,9 g of a purple-tinted oil, 4~(3-(4-methoxyphenyl)-13, 13-dimethyi~3H , 13H- i.ndeno[2i i3I;3,4]naphiho[1 i2-b]pyran-3-yi)phenoxy)-poly(caprOlactone-1000)
hydroxyiate.
Step 2
The product of Step 1 (4.9 g), meta-ietramethylxylySene diisocyanate (0.388 g), butyiated hydroxyto!uene (1 1 mg), dibutyltin di la urate (1 1 mg), and ethyl acetate (30 mL) were combined in a reaction flask, and the mixture was heated at reflux for 2 hours. Methanol (5 ml) was added to the mixture to quench excess meta- tetramethylxyiylene diisocyanate. The mixture was concentrated and the residue was purified fay silica gel chromatography (ethyl acetate/hexanes (v/V): 1/1 , 2/1). The product was obtained as a purple-tinted oil (2.2 g), An NMR spectrum showed the product to have a structure consistent with 1.3-phenylene bis(propane-2,2-diyj) bis- (1-(4-(3-(4-methoxyphenyiJ-13 3-dimethyl-3H,13H-indeno[2\3^3^3naphtho[1 l2- b]pyran-3-yl)phenoxy)-poiy(caprotactone-1000) dicarbamate shown in the following graphic formula in which the calculated capro!acfone unit # is 9.5, but ~9 units of caprolacione were drawn for structure simplicity:
Figure imgf000083_0001
Example 20
P -B, 3'(4-methoxyphenyi)-3-(4-(2-hydroxy)ethoxyphenyi)-13, 13-dimethyl- 3H,13H-indenoi2l,3':3l4]naphtho[1,2-b3pyran (5.0 g), DESMODUR® 3600 po!yfeocyanate (1 .69 g), buiylaied hydroxytoluene {33 mg), dibutyliin dilaurate (33 mg), and ethyl acetate (40 ml) were combined in a reaction flask, and the mixture was heated at reflux for 2 hours. Methanol (5 mL) was added to the mixture to quench excess DESMODUR® N 3600 poiyisocyanate. The mixture was concentrated and the residue was purified by silica gel chromatography (ethyl acetate/hexanes (v/v): 1/1 ). The product was obtained as a purpfe-tinted solid (3.5 g). An NMR spectrum showed the product to have a structure consistent with (2,4,6- trioxo-1,3,5-tna2inane-1 ,3,5 rtyi)tris(hexane-6,1-diyi) tris(2-(4-(3-(4-methoxypheny! )- 13, 13-dtmethyl-3H, 13H~indenoi2\3':3,4}naphtho 1 ,2-bJpyran-3-yi)phenoxy)ethyi) tricarbamate shown in the following graphic formula:
Figure imgf000084_0001
Example 21
PM-B, 3-{4-methoxyphenyi)-3-(4-(2-hydroxy)ethoxypheny!)-13, 13-dinriethyi- SH
Figure imgf000084_0002
(5.0 g), DESMODUR® 3200 polyisocyanaie (1.69 g), butyiated hydroxytoluene (33 mg), dibutyltin di!aurate (33 rng), and ethyl acetate (35 ml) were combined in a reaction flask, and the mixture was heated at reflux for 2.5 hours. Methanol (5 ml) was added to the mixture to quench excess DESMODUR® N 3200 polyisocyanaie. The mixture was
concentrated and the residue was purified by silica gel chromatography (ethyl acetate/hexanes (v/v); 2/1 ). The product was obtained as a purple-tinted solid (2.0 g). An NMR spectrum showed the product to have a structure consistent with 3«(4- (bis-((2^4-(3-(4-methoxy)phenyl-13,13-dimethyl-3H,13H- indeno[2\3^3,4]naphtho[1 ,2-b]pyran-3- yl)phenoxy)ethyioxycarbonylamino)hexy!aminocarbonyl)aminohexylarninocarbonylox yethoxy)phenyi)-3-(4-methoxyphenyl)-13, 13-dimethyl-3H,13H- indeno[2',3':3,4]naphtho[1 ,2-bjpyran shown in the following graphic formula:
Figure imgf000085_0001
Example 22
Step 1
P -8, 3-(4-methoxyphenyi)-3-{4-(2-hydroxy)ethoxyphenyl)-13, 13-dimethyl-
3H, 13H-indeno{2, J3':3,4]naphtho 1 ,2- ]pyran (2.0 g), e-caproiactone (3.7 g), and toluene (25 g) were combined in a reaction flask, and the mixture was stirred at room temperature for 30 minutes. Triisopropoxyaiuminum (0.23 g) was added drop-wise to the solution. The mixture was stirred at room temperature for 5 hours. Diluted hydrochloric acid (50 mL) was added to the solution and the mixture was partitioned. The toluene layer was recovered, concentrated and the residue was purified by silica gel chromatography (ethyl acefate/hexanes (v/v), 1/2, 1/1 ), yielding 4.4 g of a purple- tinted oil, 1 -(4-(3-(4-meihoxyphenyi)-13,13-dimethy!-3H,13H- indeno{2',3,:3>4]naphtho[1 ,2~b]pyran-3-y!)phenoxy)-poly(caprolactone-1000) hydroxyiate.
Step 2
The product of Step 1 (3.2 g), DESMODUR® N 3600 poiyisocyanate (0,379 g), butyiated hydroxyto!uene {7 mg), dibutyltin dilaurate (7 mg). and ethyl acetate (30 g) were combined in a reaction flask, and the mixture was heated at reflux for 2 hours. Methanol (5 mL) was added to the mixture to quench excess DESMODUR® N 3800 poiyisocyanate. The mixture was concentrated and the residue was purified by silica gel chromatography (ethyl acetate/hexanes (v/v): 1/1 , 2/1 ). The product was obtained as a purple-tinted oil (1.5 g). An NMR spectrum showed the product to have a structure consistent with ((2,4,6-trioxo-l ,3,5-triazinane-l ,3,5-triyl)tris(hexane- 6, 1 -diyl)) tris(1-(4-(3-(4-methoxy)phenyl-13,13-dimethyl-3H,13H- indeno[2\3^3,4jnaphtho[1 ,2-b3pyran~3-yi)phenoxy! poly(caprolactone-IOOO)
tricarbamate shown in the following graphic formula:
Figure imgf000086_0001
PART 2: PHOTOCHROMIC PERFORMANCE TESTING
The photochromic performance of the photochromic materials of Examples 1- 22 were tested as follows, A quantity of the photochromic material to be tested, calculated to yield a 1 .5 x 10~3 M solution, was added to a fiask containing 50 grams of a monomer blend of 4 parts ethoxyiaied bispheno! A dimethacrylate (BRA 2EO DMA), 1 part po!y(ethylene giycoi) 600 dimethacrylate, and 0.033 weight percent 2,2'- azobis(2-meihyi propionitrt!e) (AIBN). The photochromic material was dissolved into the monomer blend by stirring and gentle heating. After a clear solution was obtained, it was vacuum degassed before being poured Into a flat sheet moid having the interior dimensions of 2.2 mm x 6 inches (15.24 cm) x 6 inches (15.24 cm). The moid was seated and placed in a horizontal air flow, programmable oven programmed to Increase the temperature from 40°C to 95°C over a 5 hour interval, hold the temperature at 95°C for 3 hours and then lower it to 60°C for at least 2 hours. After the mold was opened, the polymer sheet was cut using a utility knife to score the surface and snap info 2 inch (5.1 cm) test squares.
The photochromic test squares prepared as described above were tested for photochromic response o an optical bench. Prior to testing on the optica! bench, the photochromic test squares were exposed to 365 nm ultraviolet light for about 15 minutes to cause the photochrornrc material to transform from the ground state-form to an activated-state form, and then placed In a 75°C oven for about 15 minutes to allow the photochrome material to revert back to the ground state-form. The test squares were then cooled to room temperature, exposed to fluorescent room lighting for at least 2 hours, and then kept covered (that is, in a dark environment} for at least 2 hours prior to testing on an optical bench maintained at 73°F (23°C). The bench was fitted with a 300-watt xenon arc lamp, a remote controlled shutter, a Melles Griot KG2 filter that modifies the UV and IR wavelengths and acts as a heat-sink, neutral density filter(s) and a sample holder, situated within a water bath, in which the square to be tested was inserted, A coliimated beam of light from a tungsten lamp was passed through the square at a small angle (approximately 30°) normal to the square. After passing through the square, the light from the tungsten lamp was directed to a collection sphere, where the light was blended, and on to an Ocean Optics S2000 spectrometer where the spectrum of the measuring beam was collected and analyzed. The Amax.vjs Is the wavelength in the visible spectrum at which the maximum absorption of the activated-state form of the phoiochromic compound in a test square occurs. The Aroax-V|S wavelength was determined by testing the phoiochromic test squares in a Varian Cary 300 UV-Visible spectrophotometer, it may also be calculated from the spectrum obtained by the S2000 spectrometer on the optical bench,
The saturated optica! density ("Sat'd OD") for each test square was determined by opening the shutter from the xenon lamp and measuring the transmittance after exposing the test chip to 3W/m2 UVA radiation for 30 minutes. The Amax.yis at the Sat'd OD was calculated from the activated data measured by the S2000 spectrometer on the optical bench. The First Fade Half Life {'Τ,/2"} or Bleach Rate is the time interval in seconds for the absorbance of the activated -state form of the phoiochromic materia! In the test squares to reach one half the Sat'd OD absorbance value at room temperature (23°C), after removal of the source of activating fight.
The compounds of Examples 4, 7, 8 and 14 exhibited dual peak absorptions in the visible spectrum (lambda max visible) in distinct color regions. For each lambda max visible, the corresponding optical density (Δ OD/ in, and A OD at saturation) as we!f as fade half life are tabulated in Table 1 for the two bands (A and B) of peak absorption. PART 3: TEST RESULTS
Results for the phoiochromic materials tested are listed below in Table 1. Table 1 Phoiochromic Performance Results
[01731 The present invention has been described with reference to specific details of particular embodiments thereof, !t is not intended that such details be regarded as limitations upon the scope of the invention except Insofar as and to the extent that they are included in the accompanying claims,

Claims

We claim;
1. A photochromic compound represented by the following
Formula (I),
Formula (I)
Figure imgf000089_0001
n
wherein L is a multivalent linking group selected from multivalent amine, multivalent linear or branched optionally substituted C1-C20 a!kyl, multivalent optionally substituted C3-C12 cyc!oaikyl, multivalent optionally substituted C3~C12 heterocycloalky!, multivalent optionally substituted aryi, multivalent optionally substituted heteroaryi, -(R^-O where R4 for each q is independently selected from divalent linear or branched Cr-Ci2 alky! and q is from 1 to 50, and combinations of two or more thereof,
n is at least 2,
R1 for each n is independently selected from a bond, divaieni linear or branched optionally substituted Cr~C20 alkyi, divalent optionally substituted C3-C12 cycloalky!, divalent optionally substituted C3-C2 heterocyc!oaikyi, divalent optionally substituted aryi, divalent optionally substituted heteroaryi and combinations of two or more thereof,
X1 for each n and X2 for each n are each independently selected from O, NH, and a bond,
provided that when R1 is a bond and X1 is a bond, R1 and X1 together define a bond,
L2 for each n is independently selected from a group represented by the following Formula (II),
Formula (II)
Figure imgf000089_0002
wherein R2 for each t is independently selected from a bond, divalent linear or branched C C20 alkyi, divalent optionally substituted C3-C12 cycloalkyl, divalent optionally substituted aryi, divalent optionally substituted heteroaryi, and combinations of two or more thereof, R3 for each p is independently selected from divalent linear or branched C C20 a!kyi, divalent optionally substituted C3-C12 cycioalkyl, divalent optionally substituted aryl, divalent optionally substituted heteroaryl, and combinations of two or more thereof,
Xs for each t and X4 for each t are each independently selected from O, NH, and a bond,
provided thai when R2 is a bond and X3 is a bond, R2 and X3 together define a bond, and provided thai when X2 is a bond, R2 is a bond, X3 is a bond, and t is greater than 0, X2, R2 and X3 together define a bond,
I, for each n, is 0 to 100, and
p, for each n, is 0 to 20,
provided that the sum of t and p is greater than 0, and
PC for each n Is independently a photochromic moiety.
2. The photochromic compound of claim 1 wherein, n is 2,
L1 is a divalent linking group selected from divalent linear or branched optionally substituted C1-C20, divalent optionally substituted C3-C12 cycioalkyl, divalent optionally substituted aryl. divalent optionally substituted heteroaryL and
combinations of two or more thereof,
R is a bond,
X' is NH, and
X2 is O.
3. The photochromic compound of claim 2. wherein, t is 0,
p is from 1 to 5, and
R3 for each p is Independently divalent linear or branched C2-C10 alkyl.
4. The photochromic compound of claim 2 wherein, t Is from 1 to 10,
R2 for each t Is independently selected from divalent linear or branched C C10 alkyl,
X3 is a bond,
X is O,
p is from 1 to 5, and R for each p is independently divalent linear or branched C2-Cio alky!.
5. The photochromic compound of claim 2 wherein, „1 is selected from,
divalent linear or branched Ci-C2C, alkyi,
a structure repre Formula (III),
Figure imgf000091_0001
structure represented by the following Formula (IV),
Figure imgf000091_0002
ure represented by the following Formula (V),
(V)
Figure imgf000091_0003
6. The photochromic compound of claim 1 wherein, n is 3, and
L1 Is represented by the following Formula (Vi),
(VI)
Figure imgf000092_0001
7. The photochromic compound of claim 6 wherein, R for each n is independently selected from linear or branched CrC10 aikyi.
8. The photochromic compound of claim 7 wherein t is 0,
p is from 1 to 5, and
R3 for each p is independently divalent linear or branched C2-C10 a! kyL
9. The photochromic compound of claim 7 wherein, t is from 1 to 10,
R2 for each t is independentiy selected from divaient linear or branched C--C- ; aikyi,
Xs is a bond,
X4 is O,
p is from 1 to 5, and
R3 for each p is independentiy selected from divalent linear or branched C6-
Cie aikyi.
10. The photochromic compound of claim 1 wherein, n is 3, and said photochromic compound has a first n-segment, a second n-segment, and a third n-segment, and
L1 is .
1 1. The photochromic compound of ciaim 10 wherein, for said first n-segment,
R Is divaient linear or branched optionally substituted CI-C2Q aikyi, X1 is NH, and
X2 is 0,
for each of said second n-segment and said third n-segment,
R and X1 together define a bond, and
X2 is NH.
12. The photochromic compound of claim 11 wherein,
for said first n-segment, said second n-segment, and said third n-segment, t is 0,
p is from 1 to 5, and
R3 for each p is Independently divalent linear or branched C2-C10 a!kyl
13. The photochromic compound of claim 1 wherein, n is 2,
L1 for each n is Independently divalent linear or branched optionally substituted C1-C20 alkyi,
R ss a bond,
X1 is O, and
X2 is a bond.
14. The photochromic compound of claim 13 wherein,
t is 1 ,
R2 is divalent linear or branched CrCi0 a!kyi,
X3 Is a bond, and
X4 Is O.
15. The photochromic compound of claim wherein, p is 1 to 5, and
R3 for each p is independently divalent linear or branched C2-Gi0 aikyl.
16. The photochromic compound of claim 1 wherein, n is 2,
L1 is divalent linear or branched optionally substituted C1-C20 aikyl,
R1 is a bond,
X1 is O, and
X2 is O.
17. The photochromic compound of claim 16 wherein, t is 0,
p is from 1 to 5, and
R3 for each p is independently divalent linear or branched C2-C10 aSky!.
18. The photochromic compound of claim 1 wherein,
n is 2,
V for each n is independently selected from divalent linear or branched optionally substituted C C2o a!ky!, divalent optionally substituted C3-C 2 cycloalkyi, divalent optionally substituted C3-C12 heterocyc!oa!kyi, divalent optionally substituted aryi, divalent optionally substituted heteroaryl, and combinations of two or more thereof,
R1 and X1 together define a bond, and
X2 is O.
9. The photochromic compound of claim 8 wherein,
L for each n is independently selected from divalent linear or branched C C10 aikyl,
t is 0,
p is from 1 to 5, and
R3 for each p is independently divalent linear or branched C2-C10 aikyl,
20. The photochromic compound of claim 1 wherein, n is 2, and said photochromic compound has a first n-segment and a second n-segment,
L1 is -(R4-0)a-,
for said first n-segment,
R1 and X1 together define a bond,
for said second n-segment,
R1 Is a bond, and
X1 is O, and
for said first n-segment and said second n-segment,
X2 is a bond.
21. The photochromic compound of claim 20 wherein, for said first n-segment and said second n-segment,
t is 1 ,
R2 is linear or branched CrCio afkyl,
X3 is a bond,
X4 is O,
p is from 1 to 5, and
R3 for each p is independently selected from divalent linear or branched C2-C IQ alkyl.
22. The photochromic compound of claim 1 wherein each PC is independently sefected from, indeno-iused naphthopyrans, naph o[1 ,2-b]pyrans, naphtho[2,1~b]pyrans( spirofluoroeno[1 ,2-bjpyrans, phenanthropyrans:
quino!irtopyrans, fiuoroanthenopyrans, spiropyrans, benzoxazines, naphthoxazines, spiro(indoline)naphthoxaztnes, sptroiindolsnejpyridobenzoxazines,
spiro(indoline)fluoranthenoxazines, spiro(indoline)quinoxazines, fuigides, fuigimides, diarylethenes, diary!alkytethenes, diarytalkenyiethenes, thermally reversible photochromic compounds, and non-iherma!iy reversible photochromic compounds, and mixtures thereof.
23. The photochromic compound of claim 22 wherein each PC is independently selected from an indeno[2!,3!:3,4]naphtho{1 ,2-b]pyran.
24. The photochromic compound of claim 23 wherein each PC is independently bonded to L2 at a ring position selected from ring position 3, ring position 6, ring position 7, ring posilion 1 1 , and ring position 13.
25. The photochromic compound of claim 23 wherein each PC is independently bonded to L2 at a ring position selected from ring position 3, ring position 1 1 , and ring position 13,
26. The photochromic compound of claim 1 wherein each PC has an activated visible light absorbance spectra, and the activated visible light absorbance spectra of each PC is substantially the same.
27. A photochromic articfe comprising the photochromic compound of claim
28. The photochromic article of claim 27 wherein said photochromic article Is selected from ophthalmic articles, display articles, windows, mirrors, and active iiquid crystal cell articles, and passive liquid crystal cell articles.
29. The photochromic article of claim 28, wherein said photochromic article Is selected from ophthalmic articles, and said ophthalmic articles are selected from corrective lenses, non-corrective lenses, contact Senses, intraocular lenses, magnifying lenses, protective lenses, and visors.
30. The photochromic article of claim 28, wherein said photochromic article is selected from display articles, and said display articles are selected from screens, monitors, and security elements.
31. A photochromic composition comprising the photochromic compound of claim 1 ,
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