WO2014152259A1 - Compositions de polymères contenant des polymères mécano-chromiques - Google Patents

Compositions de polymères contenant des polymères mécano-chromiques Download PDF

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WO2014152259A1
WO2014152259A1 PCT/US2014/027132 US2014027132W WO2014152259A1 WO 2014152259 A1 WO2014152259 A1 WO 2014152259A1 US 2014027132 W US2014027132 W US 2014027132W WO 2014152259 A1 WO2014152259 A1 WO 2014152259A1
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independently
substituted
mono
crc
group
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PCT/US2014/027132
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Charles R. Hickenboth
Cynthia Kutchko
Matthew J. Kryger
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Ppg Industries Ohio, Inc.
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Priority claimed from US13/834,081 external-priority patent/US9040648B2/en
Application filed by Ppg Industries Ohio, Inc. filed Critical Ppg Industries Ohio, Inc.
Publication of WO2014152259A1 publication Critical patent/WO2014152259A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/10—Spiro-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
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • G03C1/733—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds with macromolecular compounds as photosensitive substances, e.g. photochromic
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09K2211/1025—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
    • C09K2211/14—Macromolecular compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds

Definitions

  • the present invention relates polymer compositions that Include a polymer having at least one polymer chain segment that includes a residue of one or more spirooxazlne compounds and/or a residue of one or more indenonaphihopyran compounds, and mechanochromic articles that include such polyrrser compositions.
  • Various articles such as protective articles and support articles are typically fabricated at least in part from polymeric materials
  • Protective articles such as helmets, safety lenses, and protective housings
  • support articles such as beams
  • stresses and/or impacts that result in damage to the article, which could lead to catastrophic failure of the article at a point in time after the damage occurred, in some Instances, the occurrence or presence of such damage is not. accompanied by a visually observable Indication thereof in the article. In the absence of a visually observable indication of the damage, the damaged article would not likely be withdrawn from use, and an unexpected catastrophic failure of the article could occur.
  • Mechanochromic materials change color In response to a change In mechanical stress, such as Impacts. It Is known that mechanochromic materials can be incorporated info certain articles so as to provide a visual indication that the article has undergone a threshold mechanical stress event, which could result in catastrophic failure thereof. Some mechanochromic materials can undergo a reduction in stability over time, which can result in reduced mechanochromic properties. A reduction In mechanochromic properties can be accompanied by an undesirable reduction in a visually observable indication that the article in question has undergone a threshold mechanical stress event.
  • a polymer composition comprising a polymer, in which the polymer ' comprises at least one polymer chain segment represented by the following Formula (I),
  • W th reference to Formuia ⁇ ! W th reference to Formuia ⁇ !).: Svt independently for each w is a residue of a monomer; ⁇ is a residue of a mechanochromic compound having af least two reactive groups thai are each independently bonded to one monomer residue ; w, independently for each z, is an integer of at least 1 , and z is an Integer of at least 2.
  • the mechanochromic compound of which is a residue, is selected from, (a) a spirooxazine compound represented by the following Formula (ll),
  • R-i Independently for each n, R 2 Independently for each p, R 3 independently for each q, R4, Rg, and R 6 are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi each optionally interrupted with at least one of -0-, -S-, - C(OK -C(0)0 ⁇ , ⁇ GC(0)0- -S(O)-, -SOr, -N(R 11 )-, and -Si(R 11 )(R 12 )- wherein R 1 and R 12 are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi, and combinations of two or more thereof.
  • the mechanocbrornic compound, of which ⁇ is a residue is also selected from, (b) an indenonaphthopyran represented by the following Formula (III),
  • x is from 1 to 4
  • y is from 1 to 4
  • R 7 independently for each x, R 8 independently for each y, F3 ⁇ 4, and R 10 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyi each optionally interrupted with at least one of -0-, -S-, -C(O)-, -C ⁇ 0)0-, -OC(0)0-, -S(O)-, -SG 2 -, -N ⁇ R 11 )-. and -Si(R rl ) ⁇ R 12 ) ⁇ wherein R 1i and R 12 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyi, and combinations of two or more thereof.
  • 8 and B are each independently selected from unsubstituted aryl, substituted aryJ, unsubstituted heteroary!, substituted heteroaryl, and poiyalkoxy, or B and B' taken together form a ring structure selected from unsubstituted fluoren-9-ylidene, substituted ffuoren-9- ylidene, saturated spiro-monocyclic hydrocarbon ring, saturated spiro-bicyciic hydrocarbon ring, and spiro-tricyciic hydrocarbon ring.
  • a mechanochromic article comprising the polymer composition as described above.
  • the mechanochromic article can, with some embodiments of the present invention, be selected from films, sheets, and 3-dimensiortai articles.
  • left-to-right representations of linking groups are inclusive of other appropriate orientations, such as, but not limited to, right-to-left orientations.
  • left-to-right representation of the divalent linking group is inclusive of other appropriate orientations, such as, but not limited to, right-to-left orientations.
  • molecular weight values of polymers such as weight average molecular weights (Mw) and number average molecular weights ( n), are determined by gel permeation chromatography using appropriate standards, such as polystyrene standards.
  • polydispersity index (PDI) values represent a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mr?) of the polymer (i.e., Mw/Mn).
  • 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)acrylaie and similar terms, such as “(meih)acryiic acid ester” means methacrylates and/or acry!ates.
  • (meth)acrylic acid means meihacrySic acid and/or acrylic acid.
  • the terms “formed over,” “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.
  • 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.
  • ring position and related terms, such as “ring positions,” means a particular position in a ring structure, such as the fused ring structure, of a chemical compound, such as the spirooxazine compounds represented by Formula (I) and the indenonaphthopyran compounds represented by Formula (II). and which are depicted herein In accordance with some embodiments by numbers within the ring structures of the related representative chemical formulas.
  • hydrocarbyi and similar terms, such as “hydrocarbyi substituent,” means: linear or branched C C i5 alkyi (e.g., linear or branched Ci-C 10 a!kyl); linear or branched C 2 -C25 aikeny! (e.g., linear or branched C 2 - C 0 alkenyi); linea or branched C 2 ⁇ C 2 s aikynyl (e.g., linear or branched C 2 -C 10 alkynyi); C 3 -C ⁇ cycioalky!
  • C3-C10 cycloalkyi e.g., C3-C10 cycloalkyi
  • C3-C 12 heterocyc!oalkyi having at Ieast one hetero atom in the cyclic ring
  • C 5 --G-! 8 aryl including polycyclic ary! groups
  • C5-C 10 aryi e.g., C5 ⁇ C 18 heteroaryi
  • C 6 -C2 4 aralkyl e.g., C e ⁇ Cio aralkyl.
  • Representative alkyi groups include but are not fimited to methyl, ethyl, propyl, isopropy!, butyl, isobutyi, sec-butyl, tert-buty!, pentyl, neopenfyi, hexyi, heptyi, octyf, nonyi and deeyL
  • Representative a!kenyi groups include but are not limited to vinyl, ally! and propenyl.
  • Representative aikynyl groups Include but are not limited to ethynyj, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyi.
  • Representative cycloalkyi groups include but are not limited to cyciopropyl, cyciobutyl, cyclopentyl, cy ohexyf, and cycfoociyi substituents.
  • Representative heterocycloalkyi groups include but are not limited to tetrahydrofurany!, tetrahydropyranyi and piperidinyl.
  • Representative aryi groups Include but are not limited to phenyl, naphthyl, and triptycene.
  • Representative heteroaryi groups include but are not limited to furany!, pyranyl and pyridinyi.
  • Representative aralkyl groups include but are not limited to benzyl, and phenethy!.
  • cycloalkyi as used herein also Includes: bridged ring polycyc!oalkyi groups (or bridged ring polycyclic a!kyf groups), such as but not limited to, bicyclo[2.2.1 ⁇ hepiyi (or norbornyi) and bicyclo[2.2.2]octyl; and fused ring polycycloa!kyl groups (or fused ring polycyclic aikyl groups), such as, but not limited to, ociahydro-I H-indenyl, and decahydronaphthatenyi.
  • substituted hydrocarbyi as used herein means a hydrocarbyi group in which at least one hydrogen thereof has been substituted with a group that is other than hydrogen, such as, but not limited to, halo groups, hydroxy!
  • substituted hydrocarbyi is inclusive of haiohydrocarbyi (or halo substituted hydrocarbyi) substttuents.
  • haiohydrocarbyi as used herein, and similar terms, such as halo substituted hydrocarbyi, means that a! least one hydrogen atom of the hydrocarbyi (e.g., of the a!ky!, aikenyl, alkynyl, cycioaiky!, heterocycioa!ky!, ary!, heteroaryi, and aralkyi groups) is replaced with a halogen atom selected from chlorine, bromine, fluorine and Iodine.
  • the degree of halogenation can range from at least one hydrogen atom but less than all hydrogen atoms being replaced by a halogen atom (e.g., a tluoromethyl group), to full halogenation (perhaiogenaiion) in which all replaceable hydrogen atoms on the hydrocarbyi group have each been replaced by a halogen ato (e.g., trifluoromethyi or perfluoromethyi).
  • halogen ato e.g., trifluoromethyi or perfluoromethyi
  • perhaiohydrocarbyi group as used herein means a hydrocarbyi group in which all replaceable hydrogens have been replaced with a halogen. Examples of perhaiohydrocarbyi groups include, but are not limited to, perhalogenated phenyl groups and perhalogenated aikyl groups.
  • R R 10 , R 11 , and R 2 can in each case be independently and optionally interrupted with at least one of -0-, -S-, -0(0)-, -0(0)0-, -00(0)0-, -S(O)-, -S0 2 -, -N(R 11 )- and -Si(R , ? )(R 12 )-.
  • hydrocarbyi and substituted hydrocarbyi groups can be interrupted with two or more of the above recited linking groups, which can be adjacent to each other or separated by one or more carbons.
  • a combination of adjacent -C(O)- and - N(R 11 )- can provide a divalent amide linking or interrupting group, -C(0 ⁇ -N(R 11 )-.
  • a combination of adjacent -N(R 11 )-, -C(0) « and -O- can provide a divalent carbamate (or urethane) linking or interrupting group, - N(R 1 ! )-C(0)-0 ⁇ , where R 11 is hydrogen,
  • the term “fnechanochromie” and similar terms, such as “mechanochromic compound” means having an absorption spectrum for at least- visible radiation that varies in response to mechanical stress.
  • mechanochromic materia means any substance that is adapted to display mechanochromic properties (such as, adapted to have an absorption spectrum for at leas! visible radiation that varies in response to mechanicai stress) and which includes at least one mechanochromic compound, at ieast one polymer, and/or a polymer composition according to the present invention.
  • the mechanochromic compounds, materials, polymers, polymer compositions, and articles of the present Invention are, with some embodiments, capable of converting from a first state, for example a "clear state,” to a second state, for example a "colored state,” in response to mechanical stress.
  • a first state for example a "clear state”
  • a second state for example a "colored state”
  • the mechanochromic compounds, materials, polymers, polymer compositions, and articles of the present invention undergo minimal, or are substantially free of, reversion back to the previous state (such as a clear state) after exposure to and optional removal of the mechanical stress,
  • 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 mechanochromic compounds, polymers, polymer compositions, and articles of the present invention can differ with respect to at ieast one optical property, such as but not limited to the absorption of visible and/or UV radiation.
  • the mechanochromic compounds, polymers, polymer compositions, and articles of the present invention can have a different absorption spectrum In each of the first and second state.
  • a mechanochromic compounds, polymers, polymer compositions, and articles of the present invention can be clear in the first state and colored in the second state.
  • mechanochromic compounds, polymers, polymer compositions, and articles of the present invention can have a first color in the first state and a second color In the second state.
  • actinic radiation means electromagnetic radiation thai is capable of causing a response in a material, such as, but not limited to, transforming a photochrornic material from one form or state to another state, or initiating polymerization.
  • film means a pre-iormed layer having a generally uniform thickness that is not capable of self-support.
  • the term "sheet” means a pre-formed layer having a generally uniform thickness thai is capable of self-support.
  • coating means a supported film derived from a flowabie composition, which can have a uniform thickness or non-uniform thickness, and specifically excludes polymeric sheets and unsupported polymer films.
  • a coating that includes one or more mechanochromic polymers or compositions of the present invention can, with some embodiments, he a mechanochromic coating.
  • the polymers of the present invention can, with some embodiments, be selected from linear polymers, branched polymers, star polymers, graft polymers, and mixtures thereof.
  • Linear polymers are prepared, with some embodiments, from d (functional monomers and dlfunctionai mechanochromic compounds represented by Formula (II) and/or (lit).
  • Branched polymers can be prepared in accordance with art- recognized methods, in which monomers having a functionality of greater than 2, and/or mechanochromic compounds represented by Formula (II) and/or (IN) having a functionality of greater than 2 are used.
  • the polymers of the polymer compositions of the present invention include at least one polymer chain segment represented by Formula (I) as described above.
  • the polymer segment represented by Formula (I) can represent one or more segments that, comprise (or form / define) at least a portion of the chain, or backbone, architecture of the polymer.
  • the polymer chain segment represented by Formula (!) is located in ai least one of; the backbone of the polymer; one or more branches of the polymer (when the polymer is branched); and one or more arms of the polymer (when the polymer has star or comb architecture).
  • the polymer includes at least one polymer chain segment represented by Formula (I), such as 1 to 100, or 1 to 50, or 1 to 30, or 1 to 20, or 1 to 10, or 1 to 5, or 1 to 3 polymer chain segments represented by Formula (I).
  • the polymer in accordance with some embodiments, includes at least one residue of a mechanochromic compound represented by Formula (II) and/or (111), such as 1 to 100, or 1 to 50, or 1 to 30, or 1 to 20, or 1 to 10, or 1 to 5, or 1 to 3 residues of a mechanochromic compound represented by Formula (II) and/or (Hi).
  • the polymer includes 1 or 2 polymer chain segments represented by Formula (I), In further accordance with the some embodiments, the polymer includes 1 or 2 residues of a mechanochromic compound represented by Formula (II) and/or (111).
  • the polymer chain segment represented by Formula (I) substantially defines the polymer, and is represented by the following Formula (l-A), (!-A)
  • ⁇ , M, w, and z are each as defined with reference to Formula ⁇ 1 ⁇ herein, such as previously herein.
  • E independently tor each z is an end group or terminal group.
  • Each end group E of the polymer represented by Formula (l-A), with some embodiments, is a active hydrogen group independently selected from hydroxy!, thiol, carboxyiic acid, primary amine, and secondary amine.
  • each end group E is a group that is reactive with active hydrogen groups, such as, but not limited to, oxirane, thsooxtrane, isocyanate, tbioisocyanate, cyclic carbonate, cyclic carboxyiic acid ester, carboxyiic acid anhydride, cyclic carboxyiic acid anhydride, and cyclic amide.
  • Each end group E Independently is or includes a radically poiymerizable ethyienicai!y unsaturated group, such as, but not limited to, a (meth)acryioyl group and an aiiylic group.
  • the polymer compositions of the present invention can be cured b exposure to actinic radiation in the presence of a suitable initiator, such as a photopolymerizat!on initiator, and an optional crosslinking agent that has two or more radically poiymerizable ethyienical!y unsaturated groups, in accordance with art-recognized methods.
  • a suitable initiator such as a photopolymerizat!on initiator
  • an optional crosslinking agent that has two or more radically poiymerizable ethyienical!y unsaturated groups
  • the ai!yiic group, from which each E can be independently selected can be a substituted and/or unsubstituted allyiic group, such as one or more radicals represented by the following Formula (VII),
  • R ! is hydrogen, halogen or a Ci to C alky! group.
  • R 1 is hydrogen or methyl and Formula (VII) represents a (meth)aSlyl radical.
  • Each first reactive group and each second reactive group can be the same or different.
  • each first reactive group is positioned so as to be on one side of the spirooxazine relative to bond (a 1 ) (at least one R, and/or at least one R 2 each independently including a first reactive group)
  • each second reactive group is positioned so as to be on the other side of the spirooxazine relative to bond (a') (at least one R 3 , and/or R 4 , and/or R s , and/or Re each independently include a second reactive group).
  • the indenonaphthopyran represented by Formula (ill), with some embodiments includes at least one first reactive group, and at least one second reactive group.
  • at least one of B and B' independently include the first reactive group; and at least one of R 7 Independently for each x, R 8 independently for each y, R 9 and R 10 independently include the second reactive group.
  • each first reactive group is positioned so as to be on one side of the indenonaphthopyran relative to bond (a) (B and/or B' each independently including a first reactive group), and each second reactive group is positioned so as to be on the other side of the indenonaphthopyran relative to bond (a) (at least one Rr, and/o at least one R s , and/or R g , .and/or R 10 each independently include a second reactive group).
  • z of Formula (i) is 2, and the splrooxazine represented by Formula (II) includes one (a single) first reactive group, and one (a single ⁇ second reactive group.
  • the spiroo.xaz.ine represented by Formula (II) one of R , and R 2l independently include the first reactive group; and one of R 3 , R 4 , R 5 and F3 ⁇ 4 include the second reactive group.
  • Subscript z of Formula (i), with some further embodiments, is 2, and the splrooxazine represented by Formula (II) includes one (a single) first reactive group, and one (a single) second reactive group.
  • the splrooxazine represented by Formula (M) one R 2 includes the first reactive group.; and one R 3 includes the second reactive group.
  • the R 2 group of the splrooxazine represented by Formula (II) that, includes the one (or only) first reactive group is located at ring position 5' thereof
  • the R 3 group of the spirooxazlne represented by Formula (II) that includes the one (or only) second reactive group is located at ring position 5 thereof, with some embodiments.
  • Subscript z of Formula (I), with some further embodiments, Is 2, and the indenonaphthopyran represented by Formula (111) Includes one (a single) first reactive group, and one (a single) second reactive group.
  • one of B and 8' Include the first reactive group; and one of R 7 and R s include the second reactive group.
  • the B or 8' group of the Indenonaphthopyran represented by Formula (Hi) that includes the one (or only) first reactive group is located at ring position 3 thereof, and R 8 includes the one (or only) second reactive group, which is located at ring position 1 1 of the indenonaphthopyran represented by Formula (HI), with some embodiments,
  • each mechanochromic compound of the polymers of the present invention are each independently selected from active hydrogen groups, and groups that are reactive with active hydrogen groups, with some embodiments.
  • the reactive groups aflo the mechanochromic groups to react with two or more monomers, such that the mechanochromic compound becomes incorporated into a polymer chain segment of the polymer, such as represented by Formula (I).
  • the active hydrogen groups of each mechanochromic compound of the polymers of the present invention are each independently selected from hydroxy!, thiol, primary amine, secondary amine, and carboxylic acid, with some embodiments.
  • the groups that are reactive with active hydrogen groups, of each mechanochromic compound of the polymer of the present invention are each independently seiected from carboxylic acid haiides, cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes, isocyanates, thioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates, with some embodiments.
  • Each monomer from which the polymers of the present invention are prepared independently include at least one monomer reactive group selected from active hydrogen groups, and groups that are reactive with active hydrogen groups.
  • the monomer reactive groups allow the at least two monomers to react with and become eovaiently bonded with a mechanochromic compound, such as represented by Formulas (II) and ( ⁇ ).
  • the monomer reactive groups allow the monomers to react and polymerize with each other so as to form the polymers of the present invention.
  • each active hydrogen group of each monomer is independently selected from hydroxy!, thiol, primary amine, secondary amine, and carboxylic acid.
  • each group that is reactive with active hydrogen groups, of each monomer is independently selected from carboxylic acid haiides, cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes, isocyanates, thioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates.
  • the polymer of the present invention which can be part of a polymer composition with some embodiments, is selected from polyester polymers, polyurethane polymers, polycarbonate polymers, polyether polymers, po!yamide polymers, polyimide polymers, polyamideimide polymers, polyurea polymers, poiysulfone polymers, poiyketone polymers, and combinations of two or more thereof.
  • the polymers of the present invention can, with some embodiments, be prepared from art-recognized monomers and in accordance with art-recognized methods.
  • Polyesier polymers of the present invention can be prepared, with some embodiments, by art- recognized methods, which include reacting carboxylic acid functional materials (or their anhydrides) having acid functionalities of at least 2, and poiyols having hydroxy functionalities of at least 2, The molar equivalents ratio of carboxylic acid groups to hydroxy groups of the reactants is selected such that the resulting polyester has hydroxy! functionality and/or carboxyfic acid funcationlity, and a desired molecular weight.
  • Examples of multifunctional carboxylic acids useful in preparing polyester polymers include, but are not limited to, benzene- 1 ,2,4-tricarboxyiip acid, phthalsc acid, tetrahydrophtbalic acid, hexahydrophthalic acid, endobicyclo-2,2,1 ,5-heptyne- 2,3-dlcarboxylic acid, tetrachiorophthalic acid, cyeiohexanedioic acid, succinic acid, isophthafic acid, terephthailc acid, azelaic acid, maielc acid, trimesic acid, 3,6- dichlorophthalic acid, adipic acid, sebacic acid, and like multifunctional carboxylic acids.
  • polyester polymers include, but are not limited to, glycerin, irimethyioipropane, trimethylolethane, trishydroxyethyirsocyanurate, pentaerythriioi, ethylene glycol, propylene glycol, trimethylene glycol, 1 ,3-, 1 ,2- and 1,4-butanediols, heptanedioi, hexanediol, octanediol, 4,4'- ⁇ propane-2,2 ⁇ dlyi)dicyciohexanol, 4,4 , -methylenedtcyclohexanol, neopentyl glycol, 2,2,3 ⁇ trimethylpentane-1 ,3-dtoi, 1 ,4-dimet ylolcyciohexane, 2,2,4- trimethylpentane dloi,
  • Polyester polymers of the present invention that Include a residue of at least one mechanochromic compound, such as represented by Formula (II) and/or (II! have an Mn of less than or equal to 10,000, such as from 1 ,000 to 10,000, or from 2,000 to 7,000, with some embodiments.
  • the equivalent weight (such as hydroxy! or carboxylic acid equivalent weight) of the polyester polymers is, with some embodiments, less than or equal to 3000 grams ' /equivalent, such as from 300 to 2 , 000 gra ms equivalent .
  • Polyether polymers of the present invention can be prepared in accordance with art-recognized methods.
  • the polyether polymers can he prepared from poiyois having two or more hydroxy groups and poiyepoxides having two or more epoxide (or oxsrane) groups, which are reacted in proportions such that the resulting polyether has hydroxy functionality and/or oxsrane functionality.
  • the poiyois and poiyepoxides used in the preparation of the epoxide functional polyether can be selected from, for example, aliphatic, cycloafiphatic and aromatic poiyois and poiyepoxides, and mixtures thereof. Specific examples of poiyois include those recited previously herein.
  • Poiyepoxides useful in preparing polyether polymers include, with some embodiments, those resulting from the reaction of a polyol and epichlorohydrin. With some embodiments, one or more of the poiyois recited previously herein can be reacted with epichlorohydrin, so as to result in the formation of a poiyepoxide.
  • the polyether polymer can be prepared, with some embodiments, from; 4,4'- ⁇ propane ⁇ 2 ( 2-diyi)diphenoi and the dig!ycidy!
  • the polyether polymers of the present invention can have a n of less than 10,000,. such as from 1 ,000 and 7,000,
  • the equivalent weight (such as hydroxyi or epoxide equivalent weight) of the polyether polymers is, with some embodiments, less than or equal to 3,000 grams / equivalent, such as from 300 and 2,000 grams/equivalent.
  • the poiyurethane polymers of the present invention can be prepared in accordance with art-recognized methods, such as by reaction of a polyisocyanate having at least two isocyanate groups, with a polyol having at least two hydroxy groups, with: an appropriate molar excess of hydroxyi groups, so as to form a hydroxyi functional poiyurethane having at least 2 hydroxyi groups; or an appropriate molar excess of isocyanate groups so as to form a poiyurethane having at least 2 isocyanate groups.
  • polyisocyanates useful in the preparation of poiyurethane polymers include, with some embodiments;, aliphatic, aromatic, cycloaliphatic and heterocyclic polyisocyanates, and mixtures of such polyisocyanates,
  • polyisocyanates useful in the preparation of poiyurethane polymers include, but are not limited to, toiuene-2,4 ⁇ diisocyanate;
  • toluene-2,8"dlisGcyanate diphenyl methane-4,4'-diisocyanate; diphenyf methane- 2 ,4' -diisocyanate; para-phenyiene diisocyanate; biphenyi diisocyanate; 3,3'-dlmethyi- 4,4 -diphenyiene diisocyanate; tetramethylene-1 ,4-diisocyanate; hexameihylene-1 ,6- diisocyanafe; 2,2,4-thmethyi hexane-1 ,6-diisocyartate; lysine methyi ester
  • Examples to po!yols having at least two hydroxy! groups, from which the polyurethane polymers of the present invention can be prepared, include, but are not limited to those polyols recited previously herein.
  • the polyurethane polymers of the present invention can have a n of less than 10,000, such as from 100 and 7,000,
  • the equivalent weight (such as hydroxy! or isocyanate equivalent weight) of the polyurethane polymers of the present invention is, with some embodiments, less than or equal to 3,000 grams / equivalent, such as from 100 to 2,000 grams/equivalent.
  • the polycarbonate polymers of the present invention can be prepared in accordance with art- recognized methods.
  • the polycarbonate polymers are prepared from the reaction of a poiyol, such as a diol, with a carbonyi dihalide, such as carbonyi dich!oride, with removal of the resulting halide acid.
  • a poiyol such as a diol
  • a carbonyi dihalide such as carbonyi dich!oride
  • the polycarbonate polymers can have hydroxy! functionality, or can be further reacted in accordance with art- recognized methods, so as to have functionality other thane hydroxy! functionality, such as, but not limited to, oxirane functionality and cyclic carbonate funcafionality.
  • the polycarbonate polymers of the present invention can have a Mn of less than 10,000, such as from 1 ,000 and 7,000.
  • the equivalent weight (such as hydroxy! equivalent weight, or oxirane equivalent weight, or cyclic carbonate equivalent weight) of the polycarbonate polymers Is, with some embodiments, !ess than or equal to 3,000 grams / equivalent, such as from 300 and 2,000 grams/equivalent,
  • the po!yamide polymers of the present invention can be prepared In accordance with art-recognized methods. With some embodiments a material having two or more carboxyiic acid groups is reacted with a material having two or more primary amine groups, so as to form a polyamide polymer. With some further embodiments, a material having two or more primary amine groups is reacted with a material having two or more carbonyi halide groups. Examples of multifunctional carboxyiic acids from which the polyamide polymers can be prepared inciude, but are not limited to those recited previously herein. Examples of multifunctional carbonyi halides from which the polyamide polymers can be prepared include, but are not limited to those multifunctional carboxyiic acids recited previously herein, in which the carboxyiic acid groups are replaced with carbonyi halide groups.
  • Amines from which the polyamide polymers can be prepared include, hut are not limited to, aliphatic amines, cycioaliphatic amines, heterocycloaiiphatic amines, aromatic amines, and heteroaromatie amines. Additional examples of amines from which the polyamide polymers can be prepared include, but are not limited to, diaminocyciohexane, 4,4'-methylenedi ⁇ cyclQhexylamine), 4,4'-(propane- 2,2-diyl)dicyc!ohexanamine, 3 1 3 i -dimeihyi-methyier 3 ⁇ 4di(cyclohexyia:mine),
  • the polyamide polymers of the present invention can have a n of less than 10,000, such as from 1 ,000 and 7,000.
  • the equivalent weight (such as amine equivalent weight, or carboxyiic acid equivalent weight) of the polyamide polymers is, with some embodiments, less than or equal to 3,000 grams / equivalent, such as from 300 and 2,000 grams/equivalent,
  • the po!yimide polymers of the present invention can be prepared by art-recognized methods.
  • the poiyimide polymers are prepared by reaction of a multifunctional carboxyiic anhydride, such as a bis- anhydride, and a multifunctional amine, such as a diamine.
  • multifunctional anhydrides from which the poiyimide polymers can be prepared include, but are not limited to, pyrome!litic dianhydrlde and naphthalene tetracarboxy!ic dianhydrlde.
  • multifunctional amines from which the poiyimide polymers can be prepared include, but are not limited to, those amines recited previously herein.
  • the poiyimide polymers can have any suitable functionality, such as amine functionality or anhydride functionality.
  • the polyimide polymers of the present invention can have a n of less than 10,000, such as from 1 ,000 and 7,000.
  • the equivalent weight (such as amine equivalent weight, or anhydride equivalent weight) of the polyimide polymers is, with some embodiments, less than or equal to 3,000 grams / equivalent, such as from 300 and 2,000 grams/equivalent,
  • the poiyamideimide polymers of the present invention can be prepared by art-recognized methods.
  • the poiyamideimide polymers are prepared by reaction of a multifunctional amine with a materia! having both one or more carbonyl halide groups and one or more carboxyiic acid anhydride groups, such as, but not limited to a trimellitic acid halide.
  • Multifunctional amines from which the poiyamideimide polymers can be prepared include, but are not limited to, those recited previously herein.
  • the poiyamideimide polymers of the present invention can have a Mn of less than 10,000, such as from 1 ,000 and 7,000.
  • the equivalent weight (such as amine equivalent weight, or anhydride equivalent weight) of the poiyamideimide polymers is, with some embodiments, less than or equal to 3,000 grams / equsvaleni, such as from 300 and 2,000 grams/equivalent
  • the poiyurea polymers of the present invention can be prepared by art-recognized methods.
  • the poiyurea polymers are prepared by reaction of a multifunctional amine with a multifunctional isocyanate.
  • multifunctional amines from which the poiyurea polymers can be prepared include, but are not limited to, those recited previously herein.
  • multifunctional isocyanates from which the poiyurea polymers can be prepared include, but are not limited to, those recited previously herein.
  • the poiyurea polymers of the present invention can have a Mn of less than 10,000, such as from 1 ,000 and 7,000.
  • the equivalent weight (such as amine equivalent weight, or isocyanate equivalent weight) of the poiyurea polymers is, with some embodiments, less than or equal to 3,000 grams / equivalent, such as from 300 and 2,000 grams/equivalent
  • the polysulfone polymers of the present invention can be prepared by art-recognized methods.
  • the polysulfone polymers are prepared by reaction of a poiyoi, such as a dio!, with a bis( alo ⁇ hydrocarbyi)suifone, such as bfs(4 ⁇ halophenyi)suifone, such as bis(4-chlorophenyl)s lfone.
  • a poiyoi such as a dio!
  • a bis( alo ⁇ hydrocarbyi)suifone such as bfs(4 ⁇ halophenyi)suifone, such as bis(4-chlorophenyl)s lfone.
  • polyois from which the polysulfone polymers can be prepared include, but are not limited to, those polyois recited previously herein.
  • the polyol from which the poiysuifone polymers can he prepared is selected from 4 > 4
  • the poiysuifone polymers of the present invention can have a Mrs of less than 10,000, such as from 1 ,000 and 7,000.
  • the equivalent weight (such as hydroxy! equivalent weight) of the poiysuifone polymers is, with some embodiments, less than or equal to 3,000 grams / equivalent, such as from 300 and 2,000 grams/equivalent.
  • the poiyketone polymers of the present invention can be prepared by art-recognized methods.
  • the po!yketone polymers are prepared by reaction of an olefin, such as ethylene and optionally propylene, with carbon dioxide in the presence of a suitable catalyst, such as a palladium catalyst, such as pafladium(ll) ⁇ phenanthroline.
  • a suitable catalyst such as a palladium catalyst, such as pafladium(ll) ⁇ phenanthroline.
  • the poiyketone polymers of the present Invention wit some embodiments, can have a Mn of less than 10,000, such as from 1 ,000 and 7,000.
  • R- independently for each n and f3 ⁇ 4 independently for each p are each independently selected from hydrogen, aryi, rnono(C 1 -C6)alkoxyaryl > di(C C 6 )aikoxyaryl, mono(C r C 6 )alky1aryt di(C C 6 )alkyiaryl, bromoaryl, chloroaryl, fiuoroaryi, C 3 -C 7 cyeioalkylaryi, C3-C7 cycloa!ky!, C 3 -C 7 cycloalkyloxy, C3-C7 cycioalkyloxy(CrC6)alkyi, C3-C7
  • R 3 of the spirooxazine represented by Formula (II) is, independently for each q, chosen from hydrogen, C1-C5 alkyl, C r Cs aikoxy, nitro, cyano, C C 8 aikoxycarbonyl, acy!oxy(Cr C 6 alkyl), acyioxy(C 3 -C 7 cyeloalkyl), acyioxy(aryi) confront halo, C G 4 monohaioaikyl or d- C 4 polyhaloalkyl; said halo substifuents being chloro, fluoro, iodo or bromo.
  • F3 ⁇ 4 of the spirooxazine represented by Formula (H) is, chosen from hydrogen, C C 8 aikyl, C 3 ⁇ C 7 cycioalkyi, phen(C 1 -C )aikyi ⁇ naphth(Ci-C 4 ⁇ alkyi, ai!yl, acry!y ⁇ oxy(C Ce)a!kyi, methacry!y!oxy ⁇ C 2 -C 6 )alky!, C 2 -C 4 acyloxy(C 2 -C 6 ⁇ alkyl, carboxy(C 2 ⁇ C3 ⁇ 4)alkyl, cyano(C 2 - Ce)aikyi, hydroxy(C 2 -C 6 )a!kyi , triary!silyi, iriaryisilyloxy, tri ⁇ Ci-C 6 )a!ky!siiyi, tri
  • R 5 and R 6 of the spirooxazine represented by Formula (H) are each independently selected from hydrogen, C C 5 aikyl, acyloxyi ' d- C 6 aiky!), acyloxy(C 3 ⁇ C 7 cycioalkyi), acyloxy(aryi), benzyl, phenyl, mono- or di- substituted phenyl, said phenyl subsiituents being C r C 5 aikyl or Ci-C 5 aikoxy; or R 5 and R 6 taken together form a group chosen from a cyclic ring of from 5 to 8 carbon atoms which includes the spiro carbon atom.
  • Ri independently for each n and R 2 independently for each p are each independently selected from hydrogen, aryl, mono(CrCs)a!koxyaryl, di(Cr-C (5 )alkylamino, piperidino, morpholino, C r C 6 aikoxy, or fiuoro.
  • R 3 of the spirooxazine represented by Formula (11) is, independently for each q, selected from hydrogen, C1-C5 aikyl, C Q aikoxy, C ⁇ -C 8 alkoxycarbonyf, acytoxy(Ci-Ce aikyl), acyloxy(C 3 -C cycioalkyi), acyioxy ⁇ aryl),, halo, Cr-C 4 monohaloalkyi or C r C polyhaloalkyl; and said halo substifuents being chloro or fiuoro.
  • R 4 of the spirooxazine represented by Formula (II) is, is selected from hydrogen, C C 8 aikyl, phen(CrC 4 )a!kyi, acryiy!oxy(C 2 -Ce)alkyi, met.hacrylyfoxy(C 2 -Cs)aikyi,
  • R 5 and R e are each independently selected from hydrogen, C 1 -C5 alkyi, phenyl; or R 5 and R e taken together form a group chosen from a cyclic ring of from 5 to 8 carbon atoms which includes the spiro carbon atom.
  • R? independently for each x and 8 Independently for each y are each independently selected from; hydrogen; a compaiibllzing subsiituent halogen selected from iluoro and chioro; C1-C20 aikyi; C3 ⁇ 4 ⁇ C10 cycioalky!; acy!oxy ⁇ C r C s aikyi), acyioxy(C 3 -C7 cycioalkyi), acy!oxy(aryi); substituted or unsubstituted phenyl, the phenyl subslituents being selected from hydroxy!, halogen, carbonyi, Ci-C 20 aikoxycarhony!, cyano, haio(CrC2o)aikyi, C C i0 aikyi or C C 20 aikoxy; -
  • R t 1 ' and R 2 ' are each independently hydrogen, CrC 20 aikyi, phenyl, naphihyl, furany!, benzofuran-2-yl, benzofuran-3-yi, ihieny!, ben.zothien-2-yi, benzothien-3-yi, dibenzofuranyl, dibenzot ienyi, benzopyridyi, fiuorenyi, C r C 20 alkylaryi, C3-C 1 0 cycioalkyi, C A -C Z0 bicycioaikyl, C 5 ⁇ C 20 tricycioalkyi or C C 20 alkoxyalkyi, wherein said aryl group is phenyl or
  • R? independently for each x and R 8 independently for each y are each independently selected from a nitrogen containing ring represented by the following graphic Formula (IVA),
  • each -Y- is independently chosen for each occurrence from -CH 2 ⁇ , -CH(R 13 , -C(R 13 . -CH(aryl)-, ⁇ C(ary3 ⁇ 4-, and - CiRia'Xaryih and 2 is -- ⁇ --, -0-, -S-, -S(Oh -S0 2 -, -NH-, -N ⁇ R 13 ')-, or -N(aryf)-, wherein each Ri 3 ' is independently C C 2 o ai yi- each aryi is independently phenyl or naphthyi, 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-.
  • R 7 independently for each x and R s independently for each y are each independently selected from a group represented by one of the following graphic Formulas (IVB) or (IVC):
  • R 5 , R 16) and R 17 are each independently hydrogen, C C 6 alkyi, phenyl, or naphthyi, or the groups R 15 and R 6 together form a ring of 5 to 8 carbon atoms and each R d Is independently for each occurrence selected from C -C 20 alkyl, C1-C20 alkoxy, fluoro or chioro, and Q is an integer 0, 1 , 2, or 3.
  • R 7 independently for each x and R 8 independently for each y are each independently selected from unsubstituted, mono-, or di- substituted C 4 -Ci 8 spirobicyclic amine, or unsubstituted, mono-, and dt- substsiuted C4-C S spirotricyciic amine, wherein said substituents are independently aryl, C r C 20 alkyl, C C 2 o alkoxy, or phenyi(Ci-C2o)aikyl
  • T and T are each Independently oxygen or the group -NRn'-, where R ⁇ ', R 15> and R 16 are as set forth above,
  • R s and R 10 are each independently selected from the following classes of groups (i) through (v).
  • F3 ⁇ 4 and R 10 of Formula (HI) are each independently selected from, (i) hydrogen, C C 20 alkyl, C C 2 o haioa!ky!, C3-C10 cycioaikyl, acyioxy(Ci-C 6 alkyl), acyioxy ⁇ C 3 -Cr cycloalkyl), acyioxy(ary!), aliyi, benzyl, or mono-substituted benzyl, said benzyl substituents being chosen from halogen, C C 2 o alkyl or C C 20 alkoxy.
  • F1 ⁇ 2 and R 10 of Formula (ill) are each independently selected from, (ii) an unsubstituted, mono- di-or trhsubstifuted group chosen from phenyl, naphihyi, phenanthryl, pyrenyi, quinoiyl, isoquinolyl, benzofuranyi, thienyl, benzothienyl, dibenzofuranyi, dtbenzothienyi, carbazoiyl, or indoiyi, said group substituents in each case being independently chosen from halogen, C1-C20 a!kyl or C1-C20 alkoxy.
  • R 9 and R 0 of Formula (III) are each independently selected from, (iii) mono-substituted phenyl, said subsfituent located at the para position being - ⁇ CH 2 )f ⁇ or ⁇ 0-(CH 2 ) , wherein t is the integer 1 , 2, 3, 4, 5 or
  • said subsfituent being connected to an aryl group which Is a member of a photochromic material
  • R 9 and R 10 of Formula (III) are each independently selected from, (iv) the group -CH(R 18 )G, wherein R 8 is hydrogen, C C s aikyi or the unsubstituted, mono- or di-substituied aryl groups phenyl or naphihyi, and G is ⁇ CH 2 OR 19 , wherein R 19 is hydrogen, -C(0)R 10 , C r C 20 alkyl, C r C 20 alkoxy(C C 2 o)alkyi, phenyl(CrC 2 o)a kyi, mono(C -C 2 o)alkoxy substituted phenyl(C - C 2 o)a kyl, or the unsubstituted, mono- or di-subsiituted aryl groups phenyl or naphthyl, each of said phenyl and naphthyi group substituents being C C 20 alky
  • R s and R 10 together form a spiro subsfituent selected from a substituted or unsubstituted spiro-carbocyc!ic ring containing 3 to 8 carbon atoms, a substituted or unsubstituted spiro-heferocyc!ic ring containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, said spiro- carbocyciic ring and spiro-heterocyciic ring being anneiiaied with 0, 1 or 2 benzene rings, said substituents being hydrogen or C1-C20 alkyl
  • B and B' are each independently: an aryl group that is mono-substituted with a compatib!izing substiiuent; a substituted phenyl; a substituted aryl; a substituted 9-juloiindinyl; a substituted heteroaromalic group chosen from pyridyl, furanyi, benzofuran-2-yl, benzofuran ⁇ 3 ⁇ yl, thienyi, benzothien ⁇ 2-yl, benzoih1en ⁇ 3 ⁇ yl, dibenzofuranyi, dibenzot ienyi, carbazoy!, benzopyridyl, indo!inyi, and fiuorenyi, wherein the phenyl, ary!, 9-ju!oiindinyi, or heteroaromaiic substituent is a reactive
  • phenyl, aryl and heteroaromaiic substituents, from which B and B' can each be independently selected are n each case independently: hydroxy], a group -C ⁇ Q)R 21 , wherein R 2 is -OR22, -N(R 2 3)R2 » psperidtno, or rnorpholino, wherein R22 is ally], C1-C20 alkyl, phenyl, mono(Ci-C 20 )aiky1 substituted phenyl, mono ⁇ C C 2 o)atkoxy substituted phenyl, phenyl(CrC2o)a!kyf, mono(Gi-C2o)a!kyi substituted phenyl(CrC 20 )aikyl, mono(Ci-C2o)alkoxy substituted pheny!(Ci-C2o)a!kyl t C1-C20 aikoxy(C 2 -C 2
  • B and B' are each independently an unsubstituted or mono-substituted group chosen from pyrazolyl, imidazoiyi, pyrazollnyl, smidazoimyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyf, and acridinyl. Each of these substituents are, with some embodiments, C1-C20 alkyl, C C 2 o aikoxy, phenyl, or halogen.
  • B and B' are each independently a group represented by one of:
  • K is -CH 2 - or -0- classroom and M is ⁇ 0- or substituted nitrogen, provided that when is substituted nitrogen, K is - CH 2 -, the substituted nitrogen substiiuents being hydrogen, Ci ⁇ C 20 aikyf, or C C 2 o acyl, each R 2S being independently chosen for each occurrence from CrC 20 alkyj, d- C 2 o aikoxy, hydroxy, and halogen, R 26 and R 2 each being independently hydrogen or C1-C 2 0 alkyi, and u is an integer ranging from 0 to 2.
  • ⁇ 1 ⁇ 2 is hydrogen or C C 2 Q alkyi
  • R 29 is an unsubstiiuted, mono-, or dt-substituted group chosen from naphthy!, phenyl, furanyf, and thienyl, in which the substiiuents are C C 20 alkyi, C t - C 20 aikoxy, or haiogen.
  • R 7 Independently for each x and R 8 independently for each y, of the indenonaphthopyran represented by Formula ( ⁇ ), are each independently selected from, hydrogen, C -C 6 alkyi, C 3 -C 6 cycioaikyl, morpholino, morpholino substituted with C C 8 finear or branched alkyi, C r Cs haioalkyl, fluoro, chforo, and ⁇ O-Ri 0 '.
  • R 9 and R 10 of the indenonaphthopyran represented by Formula (ill), are each independently selected from hydrogen, C C 8 alkyi, C r C s haioalkyl, and C 3 -C 7 cycioaikyl, or together form a spiro substituent selected from a substituted or unsubstituied spiro-carbocyclic ring containing 3 to 6 carbon atoms,
  • B and B ⁇ of the indenonaphthopyran represented by Formula (ill) are each independently selected from aryl, ar f substituted with C r C 6 alkoxy, and aryl substituted with morpho!ino.
  • R 7 and R 8 can each be independently selected from a compatibiiizing substituent; and B and 8' can each be selected from an aryl group that is mono-substituted with a compatibiiizing substituent. If the indenonaphthopyran includes multiple compatibiiizing substituents, each compatibiiizing substituent can be independently chosen,
  • Each compatibiiizing substituent can independently be represented by one of the following:
  • 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 -A'-, 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 the amino alcohol residue can form a bond with -E-, -G- or -J, and the alcohol oxygen of the amino alcohol residue can form
  • diazacycioaikane residue an azacycio aliphatic amine residue, a diazacrown ether residue, and an aromatic diamine residue
  • diamine residues that can be used in conjunction with various non-iimtting 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 aicohol residue, a dlazacycio aliphatic alcohol residue and an aromatic amino alcohol residue. More particular, illustrative and non-limiting examples of amino alcohol residues thai can be used in conjunction with various non-limiting embodiments disclosed herein include the following:
  • -E- can represent a dicarboxylic acid residue or a derivative thereof, wherein a first carbonyi group of said dicarboxylic acid residue can form a bond with -G- or -D-, and a second carbonyi group of said dicarboxylic acid residue can form a bond with -G-.
  • suitable dicarboxylic acid residues that -E- can represent include an aliphatic dicarboxy!ic acid residue, a cycioaiiphatic dicarboxylic acid residue and an aromatic dicarboxylic acid residue. More particular, illustrative and non-iimiting examples of dicarboxylic acid residues that can be used in conjunction with various non-limiting embodiments disclosed herein include the following:
  • -G- can represent a group represented by the following general formula
  • x f 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'-, -0 ⁇ , -E- , or a substituent or an available position on the indeno-fused naphthopyran, and a second polyol oxygen of said polyol 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 H4) (OC 3 H 5 ⁇ y (OC 4 H 8 )J- (i.e., to form the group -[ ⁇ OC 2 H 4 ) !( (OC 3 H
  • poiyo!s from which the poiyol residues that -G- can represent can be formed according to various non-limiting embodiments disclosed herein include (a) sow molecular weight p lyols 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. 6, line 5, which disclosure is hereby specifically Incorporated by reference herein; (b) polyester polyols, 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 Iimited to, -CH 2 COOH, - CH(CH 3 )COOH, -C ⁇ 0)(CH 2 ) w COOH, -C 6 H 4 S0 3 H, -C 5 H 10 SO 3 H, -C*H 8 SQ 3 H, -C 3 H e S0 3 H, - ⁇ 1 ⁇ 4H 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 ⁇ o -G-, or a nitrogen of -D-.
  • -J can represent a group -L or residue thereof, wherein ⁇ L can represent a reactive moiety.
  • -L can represent a group such as, but not limited to, acryi, methacry!, crotyl, 2- (methacryioxy ⁇ ethyicarbamyl, 2- ⁇ methaeryloxy ⁇ ethoxycarbonyi, 4-viny!phenyl, vinyl, 1-chiorovinyi or epoxy.
  • acryi methacryi, crotyl, 2- (methacryioxy)eihyicarbamyi, 2-(methacryloxy)ethoxycarbonyi, 4-vinyiphenyi, vinyl, 1-chiorovinyl, and epoxy refer to the following structures: 4-vijiylpliei X
  • -G- can represent a residue of a po ' iyoi, which is defined herein to include ydroxy-containrng carbohydrates, such as those set forth in U.S. Patent No. 6,555,028 at coi. 7, line 56 to coi. 8, lines 17, which disclosure is hereby specifically incorporated by reference herein.
  • the polyo! residue can be formed, for example and without limitation herein, by the reaction of one or more of the polyol hydroxy!
  • the polyol can be represented by g-(OH)a and the residue of the polyol can be represented by the formula ⁇ Q ⁇ q ⁇ (OH) a . 3 ⁇ 4 , wherein q is the backbone or main chain of the polyhydroxy compound and "a" is at least 2.
  • one or more of the polyol 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 substliueni comprises the group -G-J
  • -G-J can be produced by reacting one or more polyoi hydroxy! groups to form the group -K (for example as discussed with respect to Reactions B and C ai col. 13, line 22 to col- 16, line 15 of U.S. Patent No.
  • -J represents a group ⁇ K that contains a sulfa or suifono terminating group
  • -G-J can be produced by acidic condensation of one or more of the polyoi hydroxy! groups with HOC 6 H 4 S0 3 H; HOC 5 H 10 SO 3 H; HOC 4 H 8 S0 3 H; HOC 3 HsS0 3 H; HOC 2 H 4 S0 3 H; or H 2 SO 4 , respectively.
  • -G ⁇ represents a polyoi residue and -J represents a group -L chosen fro acryi, methacryl, 2-(mefhacryloxy)ethylcarbamy! and epoxy
  • -L can be added by condensation of the polyoi residue with acryloy! chloride, mefhacryioyl chloride, 2 ⁇ isocyanatoethyl methacrylate or epichlorohydrin, respectively.
  • ⁇ 0131 J Further non-limiting examples of reactive and/or compatibiiizing subsiituents are set forth in U.S. Patent No. 6,555,028, at coi. 3, line 45 to col. 4, fine 26, and U.S. Patent No. 6,113,814 at col. 3, lines 30-64, which disclosures are hereby specifically incorporated by reference herein.
  • the spirooxazlne compounds of the present invention can be prepared by art-recognized methods. With some embodiments, the spirooxazlne compounds of the present invention can be synthesized in general accordance with the description provided in United States Patent No. 6,019,914 at column 9, fines 7-48, which disclosure Is incorporated herein by reference.
  • the indenonaphthopyran compounds of the present invention can be prepared by art-recognized methods. With some embodiments, the indenonaphthopyran compounds of the present invention can be synthesized In general accordance with the description provided in United States Patent No. 6,296,785, at column 10, line 52 through column 29, line 18, which disclosure is incorporated herein by reference. With some further embodiments, the indenonaphthopyran compounds of the present invention can be synthesized in general 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.
  • the indenonaphthopyran compounds of the present Invention can be synthesized in general accordance with the description provided in United States Patent No, 5,645,767, at column 5, line 6 through column 11 , line 31 , which disclosure is incorporated herei by reference.
  • Each polymer of the polymer composition of the present invention can independently be a thermoplastic polymer or a curable polymer.
  • the polymer is a curable polymer i has, with some embodiments, one or more functional groups thai are reactive with the (i) functional groups of another material, such as a cross!inking agent, and/or (si) other functional groups on the same polymer.
  • the polymer includes at least one first reactive group; and the polymer composition further includes at least one crossiinking agent that Includes at least two second reactive groups that are reactive with and form covai .
  • the polymer includes at ieast one active hydrogen group selected from hydroxy!, thiol, carboxylic acid, primary amine, and secondary amine; and the polymer composition further Includes at least one crossiinklng agent that includes at least two functional groups selected from cyclic carboxyilc acid anhydrides, oxiranes, thiooxiranes, isacyanates, thioisocyanates, cyclic carboxyilc acid esters, cyclic amides, and cyclic carbonates.
  • the crosslinking agent includes at least two functional groups selected from oxiranes, thiooxiranes, isocyanaies, thioisocyanates.
  • the crossiinklng agent in accordance with some additional embodiments, includes at least two functional groups selected from oxiranes and isocyanaies.
  • the crosslinking agent includes a separate polymer according to the present invention, which includes at least two functional groups selected from cyclic carboxyilc acid anhydrides, oxiranes, thiooxiranes, isocyanaies, thioisocyanates, cyclic carboxy!ic acid esters, cyclic amides, and cyclic carbonates,
  • the crosslinking agent polymer can be prepared In accordance with the description and methods provided previously herein, using a spirooxazine represented by Formula (il) and/or an indenonaphthopyran represented by Formula (Hi).
  • the crosslinking agent is a polymer, but is not prepared using a spirooxazine represented by Formula (H) or an indenonaphthopyran represented by Formula (111), With some embodiments, the crosslinking agent is a polymer thai does not include residues of a spirooxazine represented by Formula (II) or an indenonaphthopyran represented by Formula (ill), Is free of one or more polymer segments represented by Formula (I), and is selected from polyester polymers, polyurethane polymers, polycarbonate polymers, polyeiher polymers, polyamide polymers, polyimkie polymers, po!yamideimide polymers, poiyurea polymers, polysuifone polymers, poiyketone polymers, and combinations of two or more thereof.
  • isocyanate functional materials from which the crosslinking agent ca be selected include but are not limited to, toiuene-2,4 ⁇ dilsocyanate; toluene-2,6 ⁇ diisocyanate; diphenyl methane-4,4'- diisocyanate; diphenyl methane-2,4 ! -di!socyanate; para-phenylene diisocyanate;
  • hiphenyi diisocyanate 3,3' ⁇ dimefhyi-4,4'-diphenyiene diisocyanate; tetramethyiene- 1 ,4-diisocyanate; hexamethyiene-1 ,6-dsisocyartate; 2,2,4-trimethyi hexane-1 ,6- diisocyanate; lysine methyl ester djisocyanate; bis(isocyanaio ethy!)fumarate;
  • the poiyisocyanate crossiinking agent can, with some embodiments, be seiected from polyisocyanates prepared from dimers and trimers of dtisocyante monomers. Dimers and trimers of diisocyanate monomers can be prepared by art- recognized methods, such as described in U.S. Pat. No. 5,777,061 at column 3, line 44 through column 4, line 40, Dimers and trimers of the above recited diisocyanate monomers can contain linkages seiected from the group consisting of isocyanurate, uretdione, biuret, ailophanate and combinations thereof.
  • the isocyanate functional crosslinking agent can also be selected from (i) poiyisocyanate functionai polymer having at least two isocyanate groups, (ii) oiigomeric poiyisocyanate functional adduct and mixtures thereof.
  • the poiyisocyanate functionai polymer and oiigomeric poiyisocyanate functionai adduct can each contain structural linkages selected from urethane, i.e., ⁇ NH-C(0)-0-, thiourethane, i.e., ⁇ NH ⁇ C(G)-S-, urea, e.g., ⁇ H ⁇ C(0)- H ⁇ , and combinations of these structural linkages.
  • the poiyisocyanate polymer can be prepared, by art-recognized methods, from one or more monomers having at least two reactive hydrogen groups, such as thiol, hydroxy, primary amine and secondary amine groups, and one or more monomers having two or more isocyanate groups.
  • the molar equivalent ratio of reactive hydrogen groups to isocyanate groups Is selected such that the resulting polymer has the desired end groups, i.e., isocyanate groups.
  • the number average molecular weight ( n) of the po!yisocyanate-functional polymer is less than 20,000, such as from 1 ,000 and 10,00.0, with some embodiments.
  • the poiyisocyanate functionai polymer is a poiyisocyanate functional poiyurefhane prepared from aliphatic diols and aliphatic diisocyanates.
  • the poiyisocyanate functionai poiyurethane may be prepared using relatively small amounts of monomers having three or more functional groups, such as triols and/or triisocyanates, to increase the functionality and branching of the poiyurethane, in accordance with art-recognized methods.
  • oligomeric polyisocyanate functional adduct is meant a material thai is substantially free of polymeric chain extension.
  • Oligomeric po!yisocyanate functional adducts can be prepared by art-recognized methods from, for example, a compound containing three or more active hydrogen groups, such as trtmethyioipropane (IMP), and an isocyanate monorrser, such as l ⁇ isocyanato-3,3,5 ⁇ trimethyi-5-isocyanatomethylcyciohexane (iPDi), in a molar ratio of 1 :3, respectively.
  • active hydrogen groups such as trtmethyioipropane (IMP)
  • an isocyanate monorrser such as l ⁇ isocyanato-3,3,5 ⁇ trimethyi-5-isocyanatomethylcyciohexane (iPDi)
  • 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 ("T P-3IPDI").
  • the oligomeric po!yisocyanate functional adduct can contain structural linkages selected from the urethane, thiourethane, urea and combinations thereof, as described previously herein.
  • the active hydrogen group containing compound Is aliphatic with some embodiments, such as TMP, trishydroxyisocyanurate, pentaerythritoi and trimethyioipropane tris ⁇ mercaptoaeeiate).
  • the isocyanate monomer is, with some embodiments, a ditsocyanate monomer and can be selected from those described previously herein.
  • the isocyanate groups of the isocyanate functional crossiinking agent can, with some embodiments, be capped or blocked with a capping / blocking agent. After exposure to elevated temperature, the capping / ' blocking agent separates from the isocyanate functional material, allowing the free / unblocked isocyanate groups thereof to react and form covafent bonds with the active hydrogen groups of the polymer prepared by controlled radical polymerization according to the present invention. After unblocking or decapping from the po!yisocyanate, the capping agent can voiatize out of the composition (prior to the composition becoming vitrified) and/or remain in the composition, such as a piastici er. With some embodiments, it is desirable that the capping agent not form bubbles in the composition and/or overly piasticize the composition after decapping.
  • the capping groups of the capped polyisocyanate crossiinking agent can be selected from, with some embodiments hydroxy functional compounds, 1 H- azoles, lactams, ketoxtmes and mixtures thereof.
  • Classes of hydroxy functional compounds include, but are not limited to, aliphatic, cycioa!iphatic, or aromatic alkyi monoalcohols or pheno!ics.
  • hydroxy functional compounds useful as capping agents include, but are not limited to: lower aliphatic alcohols such as methanol, ethanoi, and n-butanol; cycloaliphatic alcohols such as cyclohexanol and tetrahydrofuran; aromaile-alkyl alcohols, such as phenyl carbinol and methyiphenyi carbinol; and glycol ethers, e.g., ethylene giycol butyl ether, dielhylene glycol butyl ether, ethylene glycol methyl ether and propylene giycol methyl ether.
  • lower aliphatic alcohols such as methanol, ethanoi, and n-butanol
  • cycloaliphatic alcohols such as cyclohexanol and tetrahydrofuran
  • aromaile-alkyl alcohols such as phenyl carbinol and methyiphenyi carbin
  • the hydroxy functional capping groups include the phenoiics, examples of which include, but are not limited to, phenol itself and substituted phenols, such as cresoi, nltrophenol and p-hydroxy methyl benzoate.
  • Examples of 1H ⁇ azoles that are useful as capping groups include, but are not limited to I HMmidazole, I H-pyrazo!e, 1 H ⁇ 3,5-dhmethyl pyrazole, 1 H-2,5 ⁇ dimethyi pyrazofe, 1 H- 1 ,2,3 riazoie, 1 H - 1 ,2,3-benzotrlazoie, I H-l ⁇ -triazoie, 1 H «5-methyl- 1 ,2,4-triazoie, and 1 H-3-amino-1 ,2,4-triazole.
  • Ketoximes useful as capping groups include those prepared from aliphatic or cycloaliphatic ketones.
  • ketoxime capping groups include, but are limited to, 2-propanone oxime (acetone oxlme), 2-butanone oxime, 2-pentanone oxime, 3-pentanone oxime, 3-methyl-2-butanone oxime, 4-methyl ⁇ 2 ⁇ pentanone oxime, 3,3-dimethyi-2-butanone oxime, 2 ⁇ heptanone oxime, 3-heptanone oxime, 4- heptanone oxime, 5 ⁇ methyi-3-heptanone oxime, 2,6--dimethyi-4-heptanone oxime, cyclopentanone oxime, eyclohexanone oxime, 3-meihy!cyclohexanone oxime, 3,3,5- trimethylcyclohexanone oxime and 3 i 5 i 5-t
  • lactam capping groups include, but are not limited to, e- caprolactam and 2-pyroiidinone.
  • Other suitable capping groups include, morpholine, 3-aminopropy; morpholine and N-hydroxy phtha!tmide.
  • Oxirane functional crosslinking agents can be prepared by reacting a hydroxy! functional material having at least two hydroxy! groups with a
  • polyols that can be used to prepare oxirane functional cross!inking agents include, but are not limited io, glycerin, irimethylolpropane, trimethy!olethane, trishydroxyethy!isocyanurate, pentaerythritoi, ethylene glycol, propylene glycol, trimeihylene glycol, butanediol, heptanediol, hexanediol, octanediol, 4,4'-(propane-2,2-diyi)dicyclohexano ⁇ 1 4,4 , -methyfen.edicyclohexanoi 1 neopeniyl glycol, 2,2,3 ⁇ trimethylpentane-1 ,3-
  • the oxirane functional crosslinking agent can be a polymeric material.
  • the polymeric oxirane functional crosslinking agent can he prepared from an oxirane functional material having at least two oxirane groups and an active hydrogen functional material having at least two active hydrogen groups, such as at Ieast two hydroxy! groups.
  • active hydrogen functional material having at least two active hydrogen groups, such as at Ieast two hydroxy! groups.
  • pofyols that can be used to prepare polymeric oxirane functional cross!inking agents include, but are not limited to those classes and examples recited previously herein with regard to preparing the oxirane functional crosslinking agent,
  • the polymer is present in the polymer composition of the present invenison In an amount of at least 2 percent by weight, or at least 10 percent by weight, or at Ieast 20 percent by weight, or at ieast 30 percent by weight, or at ieast 50 percent by weight, or at ieast 70 percent by weight, or at Ieast 80 percent by weight, based on total weight of resin solids of the polymer composition.
  • the polymer composition also, with some embodiments, contains the polymer in an amount of less than or equal to 98 percent by weight, or less than or equal to 95 by weight, or less than or equal to 90 percent by weight, based on total weight of resin solids of the polymer composition.
  • the polymer can, with some embodiments, be present in the polymer composition of the present invention In an amount ranging between any combination of these values, inclusive of the recited values, such as from 2 to 98 percent by weight, or from 10 to 98 percent by weight, or from 20 to 98 percent by weight, or from 30 to 98 percent by weight, or from 50 to 98 percent by weight, or from 70 to 95 percent by weight, or from 80 to 90 percent by weight, in each case based on total weight of resin solids of the polymer composition.
  • the polymer is present in the polymer composition of the present invention in an amount of from 2 to 50 percent by weight, or from 5 to 30 percent by weight, or from 10 to 25 percent by weight, in each case based on total weight of resin solids of the polymer composition.
  • the crosslinking agent is present, with some embodiments, in the polymer composition of the present invention in an amount of at feast 2 percent by weight, or at least 5 percent by weight, or at ieast 10 percent by weight, based on total weight of resin solids of the polymer composition.
  • the crosslinking agent can also, with some embodiments be present in the polymer composition in an amount of less than or equal to 70 percent by weight, or an amount of less than or equal to 50 percent by weight, or iess than or equal to 30 percent by weight, or less than or equal to 20 percent by weight, based on total weight of resin solids of the polymer composition.
  • the crosslinking agent can be present in the polymer composition of the present invention in an amount ranging between any combination of these values, inclusive of the recited values, such as from 2 to 70 percent by weight, or from 2 to 50 percent by weight, or from 5 to 30 percent by weight, or from 10 to 20 percent by weight, based on iota; weight of resin solids of the curable particulate composition, and , inclusive of the recited values.
  • the polymer Is present in the polymer composition with some embodiments, in an amount of from 30 to 98 percent by weight, based on total resin solids weight of the polymer composition; and the crossfinking agent Is present in the polymer composition, with some embodiments, in an amount of from 2 to 70 percent by weight, based on total resin solids weight of the polymer composition.
  • the polymer compositions of the present invention include one or more additional polymers that do not include (and are free of) a residue of a mechanochromic compound, such as represented by Formulas (ii) and (HI), which can be referred to as non-mechanochromic polymers.
  • a mechanochromic compound such as represented by Formulas (ii) and (HI)
  • non-mechanochromic polymers include, but are not limited to, polyester polymers, po!yurethane polymers, polycarbonate polymers, polyether polymers, poiyamide polymers, polyimide polymers, poSyamideimide polymers, polyurea polymers, po!ysu!fone polymers, polyketone polymers, polyvinyl polymers, polyo!efins, poiy(metb)acrylate$, and combinations of two or more thereof.
  • Each non-mechanochromic polymer can include, with some embodiments: one or more (such as two or more) active hydrogen groups, such as hydroxy], thiol, carboxylic acid, primary amine, and secondary amine; and/or one or more (such as two or more) functional groups that are reactive with active hydrogen groups, such as, cyclic carboxylic acid anhydrides, oxiranes, thlooxiranes, isocyanates, ihioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates.
  • the non-mechanochromic polymer is present in an amount of from 2 to 98 percent by weight, or from 10 to 80 percent by weight, or from 20 to 70 percent by weight, or from 30 to 60 percent by weight, or from 30 to 50 percent by weight, where the percent by weights are in each case based on the total weight of the polymer of the present invention (which Includes a residue, of a mechanochromic compound such as represented by Formulas (ii) and (III)) and the non-mechanochromic polymer,
  • the equivalent ratio of active hydrogen equivalents of the polymer, to active hydrogen reactive equivalents (such as Isocyanate or oxirane equivalents) of the crossiinking agent is, with some embodiments, from 0.7:1 to 2:1 , or from 0.8:1 to 1.3:1.
  • the polymer composition of the present invention can be cured by any suitable methods. With some embodiments, the polymer composition is thermosetting, and is curable by exposure to elevated temperature.
  • thermosetting polymer composition of the present Invention is meant a three dimensional crosslink network formed by cova!ent bond formation, such as between the active hydrogen groups of the polymer and the isocyanate or oxsrane groups of the crossiinking agent
  • the temperature at which the thermosetting polymer composition of the present Invention Is cured is variable and depends in part on the amount of time during which curing is conducted. With some embodiments, the thermosetting polymer composition is cured at a temperature within the range of 90°C to 204°C, or from 149°C to 204X, or from 154°C to 177 e C., for a period of 20 to 60 minutes.
  • the polymer compositions of the present Invention can also, with some embodiments, include pigments and fillers.
  • pigments include, but are not limited to: inorganic pigments, such as titanium dioxide and iron oxides; organic pigments, such as phihaiocyanines, anthraquinones, qiiinacridones and thioindigos; and carbon blacks.
  • fillers include, but are not limited to: silica, such as precipitated silicas; clay; and barium sulfate.
  • pigments and fillers can, with some embodiments, be present in amounts of from 0.1 percent to 70 percent by weight, based on the total solids weight of the polymer composition (excluding solvent).
  • the polymer compositions of the present invention can, with some embodiemtns, optionally contain additives such as, but not limited to: waxes for flow and wetting; fiow control agents, such as poiy(2-ethy!hexyi)acfyiaie; antioxidants; and ultraviolet (UV) light absorbers.
  • additives such as, but not limited to: waxes for flow and wetting; fiow control agents, such as poiy(2-ethy!hexyi)acfyiaie; antioxidants; and ultraviolet (UV) light absorbers.
  • useful antioxidants and UV light absorbers include, but are not limited to, those available commercially from BASF under the trademarks IRGA OX and Ti UVI .
  • These optional additives, when used, can be present in amounts up to 20 percent by weight, based on totai solids weight of the polymer composition (excluding solvent).
  • the polymer compositions of the present can, with some embodiments, include solvents, selected from water, organic solvents, and combinations thereof,
  • Classes of organic solvents that can be present in the polymer compositions of the present invention include, but are not limited to: alcohols, e.g., methanol, ethanol, n-propanoi, iso-propanoi, n-butanoi, sec-butyl alcohol, tert-buty! alcohol, isc-butyi alcohol, furfuryl alcohol and tetrahydrofurfuryf alcohol; ketones or ketoa!coho!s, e.g., acetone, methyl ethyl ketone, and diacetone alcohol; ethers, e.g., dimethyl ether and methyl ethyi ether; cyclic ethers, e.g.
  • esters e.g., ethyl acetate, ethyl lactate, ethylene carbonate and propylene carbonate; po!yhydric alcohols, e.g., ethylene glycol, diefhylene glycol, Methylene glycol, propylene glycol, ietraethySerse glycol, polyethylene glycol, glycerol, 2-methyi- 2,4-pentanedlol and 1 ,2,6-hexantri.oi; hydroxy functional ethers of aikylene glycols, e.g., butyl 2-hydroxyethyl ether, hexyi 2-hydroxyethyi ether, methyl 2-hydroxypropy1 ether and phenyl 2-hydroxypropyi ether; nitrogen containing cyclic compounds, e.g., pyrrolidone, N-methy! ⁇ 2 ⁇ pyrrolidone and 1
  • Solvent(s) cars he present in the polymer compositions of the present invention, in an amount of at least 5 percent by weight, or at least 15 percent by weight, or at least 30 percent by weight, based on the total weight of the polymer composition.
  • the solvent(s) can also be present in the polymer composition in an amount of less than 95 percent by weight, or less than 80 percent by weight, o less than 60 percent fay weight, based on the total weight of the pigment dispersion.
  • the amount of solvent present in the polymer composition can range between any combination of these values, inclusive of the recited values, with some embodiments, such as from 5 to 95 percent by weight, or from 15 to 80 percent by weight, or from 30 to 60 percent by 'weight, In each case based on the total weight of the polymer composition,
  • the polymer composition includes an additive- selected from heat stabilizers, light stabilizers, and combinations thereof.
  • useful heat stabilizers and light absorbers include, but are not limited to, those available commercially from BASF under the trademarks IRGANOX and TfNUV!N.
  • the optional heat stabilizers and light stabilizers, when used, can be present in amounts up to 20 percent by weight, based on total solids weight of the polymer composition (excluding solvent).
  • the present invention also relates to meehanocbromie articles that include the polymer composition of the present invention as described previously herein.
  • the mechanochromic article is selected from films, sheets, and 3-dimenslonal articles.
  • the 3-dimensiona! articles from which the mechanochromic articles of the present invention can be selecte include, but are not limited to, ophthalmic articles, display articles, windows, mirrors, protective articles and support articles.
  • the mechanochromic articles of the present Invention are selected from ophthalmic articles, and the ophthalmic articles are selected from corrective lenses, non-corrective lenses, contact lenses, and magnifying lenses.
  • 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 mufti- vision lenses, which can be either segmented or non-segmented multi-vision lenses (such as, but not limited to, blfocai 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, intraocular lenses, magnifying lenses, and protective lenses or visors.
  • corrective and non-corrective lenses including single vision or mufti- vision lenses, which can be either segmented or non-segmented multi-vision lenses (such as, but not limited to, blfocai 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, intraocular lenses, magnifying lenses, and protective lenses or visors.
  • the mechanochromic articles of the present invention are selected from display articles, and the display articles are selected from screens, monitors, and security elements.
  • display' 1 means the visible or 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.
  • the mechanochromic articles of the present invention are selected from protective articles, and the protective articles are selected from protective lenses, protective visors, protective headgear, and protective housings.
  • protective lenses include, but are not limited to, safety glasses and safety goggles, such as used in a laboratory and/or a work shop, such as a metal shop, welding shop, wood-working shop, automotive shop/garage, and the like.
  • protective visors include, but are not limited to, those used with racing helmets (such as automotive, motorcycle, and boat racing helmets), aircraft helmets, hockey helmets, metal working helmets, and helmets used by- ground military personnel.
  • protective headgear examples include, but are not limited to, motorcycle helmets, aircraft helmets, speed boat helmets, automotive race helmets, baseball helmets, hockey helmets, equestrian helmets, helmets used b ground military personnel, construction helmets, oil filed helmets, and helmets used by metal workers.
  • protective housings include, but are not limited to, housings for sensitive equipment, such as, analytical equipment, guidance systems (such as missile guidance systems), and medical equipment (such as insuiin pumps).
  • the mechanochromic articles of the present invention are, with some embodiments, selected from support articles, and the support articles are seiected from rods, beams, crossarms, and combinations thereof.
  • the rods, beams, and crossarms can be substantially unitary articles, or composed of a plurality of components, in which at least some of the components are the mechanochromic articles of the present invention,
  • the mechanochromic article of the present invention is selected from a 3-dimensional article, and the 3-dimensionsa! article includes a layer residing over at least a portion of at least one surface of the 3-dimensionai article, in which the layer Includes the poiymer composition of the present invention as described previously herein, and is a mechanochromic layer.
  • the mechanochromic layer can be selected from films, sheets, and/or coatings.
  • the mechanochromic article of the present invention is selected from a 3-dimensiona! article, and the 3-dimensionsa! article includes a coating residing over at least a portion of at least one surface of the 3-dimensionai article, in which the coating includes the polymer composition of the present invention as described previously herein, and is a mechanochromic coating.
  • the coating is the polymer composition of the present invention, and the coating is a mechanochromic coating.
  • the coating can be a single layer coating or a multiple layer coating, in which each layer thereof can have the same or a different composition.
  • the coating is a multiple layer coating that includes a primer over at least a portion of a surface of the 3-dimensionai article, a mechanochromic layer formed over the primer layer (In which the mechanochromic layer includes the poiymer composition of the present invention), and an optional clear layer formed over the mechanochromic layer.
  • the mechanochromic layer can be pigmented or unpigmented, with some embodiments.
  • the optional clear layer which resides over the mechanochromic layer, can include an additive selected from heat stabilizers and/or light stabilizers.
  • the heat stabilizers and light stabilizers can be present in amount(s) and the thickness of the clear layer can be selected such that phoiochromic activation of the residue of the mechanochromic compounds) (represented by Formula (II) and/or (ill), which resides within the polymer backbone of the polymer of the present invention) by actinic radiation is at least minimized, or substantially eliminated.
  • the heat stabilizers and light stabilizers can be present in the clear layer in a total amount of up to 40% by weight, based on the total solids weight of the clear layer.
  • a mechanochromic article that includes the polymer composition of the present Invention, in which the mechanochromic article further includes a coating residing over at least a portion of at least one surface of the mechanochromic article.
  • the coating is free of the polymer composition of the present invention, and the coating includes an additive selected from heat stabilizers, light stabilizers, and combinations thereof.
  • the coating residing ove the mechanochromic article can be referred to as an overcoating.
  • the overcoating, which resides over the mechanochromic article can be a clear overcoating, with some embodiments of the present invention.
  • the heat stabilizers and light stabilizers can be present in amount(s) and the thickness of the clear overcoating can be selected such that photochrome activation of the residue of the mechanochromic compound (represented by Formula (II) and/or (111), which resides within the polymer backbone of the polymer of the present invention) by actinic radiation is at least minimized, or substantially eliminated.
  • the heat stabilizers and light stabilizers can be present in the clear overcoating in a total amount of up to 40% by weight, based on the total solids weight of the clear overcoat.
  • Part 1 describe the synthesis of controlled radical polymerization initiators.
  • Part 2 describes the preparation of polymers made by controlled radical polymerization using the initiators of Part 1.
  • Part 3 describes the preparation of film and coatings, and testing results for mechanochromic properties. Part 1. Preparation of controlled radical polymerization initiators
  • Example 3 (Q.03Q5g) was subjected to the conditions described in Example 6 except that 0.008g Cu, 0.029g trls(2- dsmethylamtnoethyj)amlne, 4.32g of methyl acrylate, and 2.8g of D SO was used.
  • Gel Permeation Chromatography in THF indicated a peak MW of 128,614 (theory 140,000) relative to a linear polystyrene standard.
  • the initiator 1 ,3,3-trimethyispiro[indoline-2,3'-naphiho[2, 1 -b] 1 ,4]oxazine]-5,5' ⁇ diyl bis(2-bromo ⁇ 2 ⁇ me ⁇ hylpropionate) of Example 2 (24,4 mg) was subjected to the polymerization conditions described in Example 6 except that 0.0094g Cu s 0.034g tris(2-dim8thyiaminoethyl)amine 1 5,19g of methyi acrylate, and 3.4g of DMSO was used, Gel Permeation Chromatography in THF indicated a peak MW of 183811 ⁇ theory 140,000 ⁇ relative to a linear polystyrene standard.
  • the polymer from Example 7 and DABCO were soiubiiized In the anhydrous THF then heated at 60°C for 30 minutes.
  • the DESMODUR W was added dropwlse to the solution, and the resulting mixture was stirred at 60°C for 2 hours.
  • This mixture was removed from the heat and po!yTHF 250 was added dropwlse while stirring, then the mixture was piaced under a stream of Nitrogen for 4 hours to evaporate solvent.
  • the HDI was then mixed in, and the resulting polymer was then piaced In a vacuum oven for 2 hours, it was then poured into a TEFLON ⁇ mold and baked at 60°C for 36 hours.
  • the resulting cast film was found to be mechanochromic.
  • Coating formulations were prepared according to Table 2 in the following manner: Charge 1 was added to the vessel with mixing and heated to 60°C for approximately 30 minutes to dissolve the solids. Charge 2 was added to the solution and the resuming mixture heated at 60C for an additional 80 minutes. The materials of Charge 3 and Charge 4 were added in the order listed. The resulting mixture was placed in a 120 mL container and placed on a mechanical stir device for 18 hours.
  • NMP N- ethyl-2-pyrroiidone
  • Piedmont Plastics ⁇ were treated with a corona discharge from a TANTEC® EST- Electrical Service Treatment unit operated at 500 Watts and 54kVA for 45 seconds.
  • the coating compositions were then spin coated to the prepared substrate and
  • Example 18 demonstrates that it is possible to have combined mechanochromic-photochromsc activation,

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  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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Abstract

La présente invention concerne une composition de polymères comportant un polymère ayant au moins un segment de polymère représenté par la formule (I), dans laquelle : M indépendamment pour chaque w est un résidu d'un monomère; Φ est un résidu d'un composé mécano-chromique ayant au moins deux groupes réactifs qui sont indépendamment liés à un résidu de monomère M; w, indépendamment pour chaque z est un nombre entier au moins égal à 1; et z est un nombre entier au moins égal à 2. Le composé mécano-chromique est choisi parmi au moins un des éléments suivants : un composé de spiro-oxazine représenté par la formule (II), et un indénonaphtopyrane représenté par la formule (III).
PCT/US2014/027132 2013-03-15 2014-03-14 Compositions de polymères contenant des polymères mécano-chromiques WO2014152259A1 (fr)

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CN110831992A (zh) * 2017-07-03 2020-02-21 三井化学株式会社 光学材料用聚合性组合物及成型体
EP3783084A4 (fr) * 2018-04-17 2021-11-03 Tokuyama Corporation Composé photochromique, composition durcissable contenant ledit composé photochromique et article optique
US11963868B2 (en) 2020-06-01 2024-04-23 Ast Products, Inc. Double-sided aspheric diffractive multifocal lens, manufacture, and uses thereof

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CN110831992A (zh) * 2017-07-03 2020-02-21 三井化学株式会社 光学材料用聚合性组合物及成型体
CN110831992B (zh) * 2017-07-03 2022-08-23 三井化学株式会社 光学材料用聚合性组合物及成型体
EP3783084A4 (fr) * 2018-04-17 2021-11-03 Tokuyama Corporation Composé photochromique, composition durcissable contenant ledit composé photochromique et article optique
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US11963868B2 (en) 2020-06-01 2024-04-23 Ast Products, Inc. Double-sided aspheric diffractive multifocal lens, manufacture, and uses thereof

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