# US 9,040,648 B2 · Polymer compositions containing mechanochromic polymers

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- Number: US 9,040,648 B2
- Document ID: US9040648B2
- Status: Granted
- Kind: B2
- Application number: 13/834,081
- Filed: 2013-03-15
- Published: 2013-10-17
- Granted: 2015-05-26
- Earliest claimed: 2012-04-16
- Assignees: PPG Industries Ohio, Inc.
- Applicants: PPG Industries Ohio, Inc.
- Inventors: Charles R. Hickenboth; Cynthia Kutchko; Matthew J. Kryger
- Web page: https://patentgrep.com/patent/US9040648B2

## CPC

- C08G 73/0688: {with only one nitrogen atom in the ring, e.g. polyquinolines}
- C08G 18/2081: {containing at least two non-condensed heterocyclic rings}
- C08G 18/227: {of antimony, bismuth or arsenic}
- C08G 18/381: {having bromine atoms}
- C08G 18/4063: {Mixtures of compounds of group C08G18/62 with other macromolecular compounds}
- C08G 18/44: Polycarbonates
- C08G 18/4854: {Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group}
- C08G 18/6254: {Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups}
- C08G 18/671: {Unsaturated compounds having only one group containing active hydrogen (takes precedence on groups C08G18/675 - C08G18/69)}
- C08G 18/722: {Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates}
- C08G 18/755: {and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate}
- C08G 18/758: {containing two or more cycloaliphatic rings}
- C08G 18/8125: {having two or more isocyanate or isothiocyanate groups}
- C09D 175/04: Polyurethanes
- C09D 175/14: Polyurethanes having carbon-to-carbon unsaturated bonds
- G03C 1/733: {with macromolecular compounds as photosensitive substances, e.g. photochromic (photodegradable or photocrosslinkable compositions G03F7/004)}
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- G03C: PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES (for photomechanical purposes G03F); PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY (photographic processes characterised by the use or manipulation of apparatus classifiable per se in subclass G03B, see G03B; photomechanical production of textured or patterned surfaces G03F; electrophotography, magnetography G03G)

## Abstract

The present invention relates to a polymer composition that includes a polymer having at least one polymer segment represented by the following Formula (I), With reference to Formula (I): M independently for each w is a residue of a monomer; φ is a residue of a mechanochromic compound having at least two reactive groups that are each independently bonded to one monomer residue M; w, independently for each z, is an integer of at least 1; and z is an integer of at least 2. The mechanochromic compound is selected from at least one of the following, (a) a spirooxazine compound represented by the following Formula (II), and (b) an indenonaphthopyran represented by the following Formula (III),

## Claims

### Claim 1

A polymer composition comprising a polymer, said polymer comprising at least one polymer chain segment represented by the following Formula (I),
wherein M independently for each w is a residue of a monomer,
Φ is a residue of a mechanochromic compound having at least two reactive groups that are each independently bonded to one monomer residue M,
w, independently for each z, is an integer of at least 1, and
z is 2,
further wherein said mechanochromic compound is selected from,
(a) a spirooxazine compound represented by the following Formula (II),
wherein n is from 1 to 4, p is from 1 to 2, q is from 1 to 4, and R1 independently for each n, R2 independently for each p, R3 independently for each q, R4, R5, and R6 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl each optionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO2—, —N(R11)—, and —Si(R11)(R12)— wherein R11 and R12 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more thereof,
provided that for the spirooxazine represented by Formula (II) two of, R1 independently for each n, R2 independently for each p, R3 independently for each q, R4, R5, and R6, each independently comprise said reactive group that is independently bonded to one monomer residue M,
wherein the spirooxazine represented by Formula (II) comprises one first reactive group, and one second reactive group,
further wherein for the spirooxazine represented by Formula (II) one of R1, and R2, independently comprise said first reactive group and one of R3, R4, R5 and R6 comprise said second reactive group,
(b) an indenonaphthopyran represented by the following Formula (III),
wherein x is from 1 to 4, y is from 1 to 4, R7 independently for each x, R8 independently for each y, R9, and R10 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl each optionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO2—, —N(R11)—, and —Si(R11)(R12)— wherein R11 and R12 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more thereof, and
B and B′ are each independently selected from unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, and polyalkoxy, or B and B′ taken together form a ring structure selected from unsubstituted fluoren-9-ylidene, substituted fluoren-9-ylidene, saturated spiro-monocyclic hydrocarbon ring, saturated Spiro-bicyclic hydrocarbon ring, and spiro-tricyclic hydrocarbon ring,
provided that for the indenonaphthopyran represented by Formula (III), two of, R7, R8, R9, R10, B, and B′ each independently comprise said reactive group that is independently bonded to one monomer residue M,
wherein the indenonaphthopyran represented by Formula (III) comprises one first reactive group, and one second reactive group,
further wherein for the indenonaphthopyran represented by Formula (III) one of B and B′ comprise said first reactive group, and one of R7, R8, R9 and R10 comprise said second reactive group.

### Claim 2 (depends on 1)

The polymer composition of claim 1 wherein,
for the spirooxazine represented by Formula (II) one R2 comprises said first reactive group, and one R3 comprises said second reactive group, and
for the indenonaphthopyran represented by Formula (III) one of B and B′ comprise said first reactive group, and one of R7 and R8 comprise said second reactive group.

### Claim 3 (depends on 1)

The polymer composition of claim 1 wherein, said reactive groups of said mechanochromic compound are each independently selected from active hydrogen groups, and groups that are reactive with active hydrogen groups.

### Claim 4 (depends on 3)

The polymer composition of claim 3 wherein,
the active hydrogen groups of said mechanochromic compound are each independently selected from hydroxyl, thiol, primary amine, secondary amine, and carboxylic acid, and
the groups that are reactive with active hydrogen groups, of said mechanochromic compound, are each independently selected from carboxylic acid halides, cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes, isocyanates, thioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates.

### Claim 5 (depends on 3)

The polymer composition of claim 3 wherein, each monomer independently comprises at least one monomer reactive group selected from active hydrogen groups, and groups that are reactive with active hydrogen groups.

### Claim 6 (depends on 5)

The polymer composition of claim 5 wherein,
each active hydrogen group of each monomer is independently selected from hydroxyl, thiol, primary amine, secondary amine, and carboxylic acid, and
each group that is reactive with active hydrogen groups, of each monomer, is independently selected from carboxylic acid halides, cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes, isocyanates, thioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates.

### Claim 7 (depends on 1)

The polymer composition of claim 1 wherein, said polymer is selected from polyester polymers, polyurethane polymers, polycarbonate polymers, polyether polymers, polyamide polymers, polyimide polymers, polyamideimide polymers, polyurea polymers, polysulfone polymers, polyketone polymers, and combinations of two or more thereof.

### Claim 8 (depends on 1)

The polymer composition of claim 1 wherein,
for the spirooxazine compound represented by Formula (II),
R1 independently for each n and R2 independently for each p are each independently selected from hydrogen, aryl, mono(C1-C6)alkoxyaryl, di(C1-C6)alkoxyaryl, mono(C1-C6)alkylaryl , di(C1-C6)alkylaryl, bromoaryl, chloroaryl, fluoroaryl, C3-C7 cycloalkylaryl, C3-C7 cycloalkyl, C3-C7 cycloalkyloxy, C3-C7 cycloalkyloxy(C1-C6)alkyl, C3-C7 cycloalkyloxy(C1-C6)alkoxy, aryl(C1-C6)alkyl, aryl(C1-C6)alkoxy, aryloxy, aryloxy(C1-C6)alkyl, aryloxy(C1-C6)alkoxy, mono- or di(C1-C6)alkylaryl(C1-C6)alkyl, mono- or di(C1-C6)alkoxyaryl(C1-C6)alkyl, mono- or di(C1-C6)alkylaryl(C1-C6)alkoxy, mono- or di(C1-C6)alkoxyaryl(C1-C6)alkoxy, amino, mono(C1-C6)alkylamino, di(C1-C6)alkylamino, diarylamino, N—(C1-C6)alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, arylpiperidino, morpholine, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, C1-C6 alkyl, C1-C6 bromoalkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, C1-C6 alkoxy, mono(C1-C6)alkoxy(C1-C4)alkyl, acryloxy, methacryloxy, acyloxy(C1-C6 alkyl), acyloxy(C3-C7 cycloalkyl), acyloxy(aryl), bromo, chloro or fluoro,
R3 is, independently for each q, chosen from hydrogen, C1-C5 alkyl, C1-C5 alkoxy, nitro, cyano, C1-C8 alkoxycarbonyl, acyloxy(C1-C6 alkyl), acyloxy(C3-C7 cycloalkyl), acyloxy(aryl), halo, C1-C4 monohaloalkyl or C1-C4 polyhaloalkyl; said halo substituents being chloro, fluoro, iodo or bromo,
R4 is chosen from hydrogen, C1-C8 alkyl, C3-C7 cycloalkyl, phen(C1-C4)alkyl, naphth(C1-C4)alkyl, allyl, acrylyloxy(C2-C6)alkyl, methacrylyloxy(C2-C6)alkyl, C2-C4 acyloxy(C2-C6)alkyl, carboxy(C2-C6)alkyl, cyano(C2-C6)alkyl, hydroxy(C2-C6)alkyl, triarylsilyl, triarylsilyloxy, tri(C1-C6)alkylsilyloxy, tri(C1-C6)alkoxysilyl, tri(C1-C6)alkoxysilyloxy, di(C1-C6)alkyl(C1-C6 alkoxy)silyl, di(C1-C6)alkyl(C1-C6 alkoxy)silyloxy, di(C1-C6)alkoxy(C1-C6 alkyl)silyl, di(C1-C6)alkoxy(C1-C6 alkyl)silyloxy, C1-C6 alkoxy(C2-C4)alkyl or (C2H4O)rCH3, wherein r is an integer from 1 to 6,
R5 and R6 are each independently selected from hydrogen, C1-C5 alkyl, acyloxy(C1-C6 alkyl), acyloxy(C3-C7 cycloalkyl), acyloxy(aryl), benzyl, phenyl, mono- or di-substituted phenyl, said phenyl substituents being C1-C5 alkyl or C1-C5 alkoxy; or R5 and R6 taken together form a group chosen from a cyclic ring of from 5 to 8 carbon atoms which includes the Spiro carbon atom,
for the indenonaphthopyran represented by Formula (III),
R7 independently for each x and R8 independently for each y are each independently selected from,
hydrogen,
a compatiblizing substituent;
halogen selected from fluoro and chloro;
C1-C20 alkyl;
C3-C10 cycloalkyl;
acyloxy(C1-C6 alkyl), acyloxy(C3-C7 cycloalkyl), acyloxy(aryl);
substituted or unsubstituted phenyl, the phenyl substituents being selected from hydroxyl, halogen, carbonyl, C1-C20 alkoxycarbonyl, cyano, halo(C1-C20)alkyl, C1-C20 alkyl or C1-C20 alkoxy;
—O—R10′ or —C(O)—R10′ or —C(O)—OR10′, wherein R10′ is hydrogen, C1-C20 alkyl, phenyl(C1-C20)alkyl, mono(C1-C20)alkyl substituted phenyl(C1-C20)alkyl, mono(C1-C20)alkoxy substituted phenyl(C1-C20)alkyl, (C1-C20)alkoxy(C2-C20)alkyl, C3-C10 cycloalkyl, or mono(C1-C20)alkyl substituted C3-C10 cycloalkyl; —N(R11′)R12′, wherein R11′ and R12′ are each independently hydrogen, C1-C20 alkyl, phenyl, naphthyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl, fluorenyl, C1-C20 alkylaryl, C3-C10 cycloalkyl, C4-C20 bicycloalkyl, C5- C20 tricycloalkyl or C1-C20 alkoxyalkyl, wherein said aryl group is phenyl or naphthyl, or R11′ and R12′ come together with the nitrogen atom to form a C3-C20 hetero-bicycloalkyl ring or a C4-C20 hetero-tricycloalkyl ring;
a nitrogen containing ring represented by the following graphic formula IVA,
wherein each —Y— is independently chosen for each occurrence from —CH2—, —CH(R13′)—, —C(R13′)2—, —CH(aryl)-, —C(aryl)2-, and —C(R13′)(aryl)-, and Z is —Y—, —O—, —S—, —S(O)—, —SO2—, —NH—, —N(R13′)-, or —N(aryl)-, wherein each R13′ is independently C1-C20 alkyl, each aryl is independently phenyl or naphthyl, m is an integer 1, 2 or 3, and p is an integer 0, 1, 2, or 3 and provided that when p is 0, Z is —Y—;
a group represented by one of the following graphic formulas IVB or IVC,
wherein R15 is, R16, and R17 are each independently hydrogen, C1-C6 alkyl, phenyl, or naphthyl, or the groups R15 and R16 together form a ring of 5 to 8 carbon atoms and each Rd is independently for each occurrence selected from C1-C20 alkyl, C1-C20 alkoxy, fluoro or chloro, and Q is an integer 0, 1, 2, or 3; and
unsubstituted, mono-, or di-substituted C4-C18 spirobicyclic amine, or unsubstituted, mono-, and di-substituted C4-C18 spirotricyclic amine, wherein said substituents are independently aryl, C1-C20 alkyl, C1-C20 alkoxy, or phenyl(C1-C20)alkyl; or
two adjacent R7 groups, or two adjacent R8 groups, independently together form a group represented by one of IVD and IVE:
wherein T and T′ are each independently oxygen or the group —NR11′-, where R11′, R15, and R16 are as set forth above,
R9 and R10 are each independently selected from,
(i) hydrogen, C1-C20 alkyl, C1-C20 haloalkyl, C3-C10 cycloalkyl, acyloxy(C1-C6 alkyl), acyloxy(C3-C7 cycloalkyl), acyloxy(aryl), allyl, benzyl, or mono-substituted benzyl, said benzyl substituents being chosen from halogen, C1-C20 alkyl or C1-C20 alkoxy;
(ii) an unsubstituted, mono- di- or tri-substituted group chosen from phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, or indolyl, said group substituents in each case being independently chosen from halogen, C1-C20 alkyl or C1-C20 alkoxy;
(iii) mono-substituted phenyl, said substituent located at the para position being —(CH2)t— or —O—(CH2)t—, wherein t is the integer 1, 2, 3, 4, 5 or 6, said substituent being connected to an aryl group which is a member of a photochromic material;
(iv) the group —CH(R18)G, wherein R18 is hydrogen, C1-C6 alkyl or the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl, and G is —CH2OR19, wherein R19 is hydrogen, —C(O)R10, C1-C20 alkyl, C1-C20 alkoxy(C1-C20)alkyl, phenyl(C1-C20)alkyl, mono(C1-C20)alkoxy substituted phenyl(C1-C20)alkyl, or the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl, each of said phenyl and naphthyl group substituents being C1-C20 alkyl or C1-C20 alkoxy; or
(v) R9 and R10 together form a Spiro substituent selected from a substituted or unsubstituted spiro-carbocyclic ring containing 3 to 6 carbon atoms, a substituted or unsubstituted spiro-heterocyclic ring containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, said Spiro-carbocyclic ring and spiro-heterocyclic ring being annellated with 0, 1 or 2 benzene rings, said substituents being hydrogen or C1-C20 alkyl; and
B and B′ are each independently:
an aryl group that is mono-substituted with a compatiblizing substituent; a substituted phenyl; a substituted aryl; a substituted 9-julolindinyl; a substituted heteroaromatic group chosen from pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl, and fluorenyl, wherein the phenyl, aryl, 9-julolindinyl, or heteroaromatic substituent is a reactive substituent R; an unsubstituted, mono-, di-, or tri-substituted phenyl or aryl group; 9-julolidinyl; or an unsubstituted, mono- or di-substituted heteroaromatic group chosen from pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl, and fluorenyl, wherein each of the phenyl, aryl and heteroaromatic substituents are each independently:
hydroxyl, a group —C(═O)R21, wherein R21 is −OR22, —N(R23)R24, piperidino, or morpholino, wherein R22 is allyl, C1-C20 alkyl, phenyl, mono(C1-C20)alkyl substituted phenyl, mono(C1-C20)alkoxy substituted phenyl, phenyl(C1-C20)alkyl, mono(C1-C20)alkyl substituted phenyl(C1-C20)alkyl, mono(C1-C20)alkoxy substituted phenyl(C1-C20)alkyl, C1-C20 alkoxy(C2-C20)alkyl or C1-C20 haloalkyl, R23 and R24 are each independently C1-C20 alkyl, C5-C10 cycloalkyl, phenyl or substituted phenyl, the phenyl substituents being C1-C20 alkyl or C1-C20 alkoxy, and said halo substituent is chloro or fluoro, aryl, mono(C1-C20)alkoxyaryl, di(C1-C20)alkoxyaryl, mono(C1-C20)alkylaryl, di(C1-C20)alkylaryl, haloaryl, C3-C10 cycloalkylaryl, C3-C10 cycloalkyl, C3-C10 cycloalkyloxy, C3-C10 cycloalkyloxy(C1-C20)alkyl, C3-C10 cycloalkyloxy(C1-C20)alkoxy, aryl(C1-C20)alkyl, aryl(C1-C20)alkoxy, aryloxy, aryloxy(C1-C20)alkyl, aryloxy(C1-C20)alkoxy, mono- or di(C1-C20)alkylaryl(C1-C20)alkyl, mono- or di-(C1-C20)alkoxyaryl(C1-C20)alkyl, mono- or di-(C1-C20)alkylaryl(C1-C20)alkoxy, mono- or di-(C1-C20)alkoxyaryl(C1-C20)alkoxy, amino, mono- or di-(C1-C20)alkylamino, diarylamino, piperazino, N—(C1-C20)alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl, C1-C20 alkyl, C1-C20 haloalkyl, C1-C20 alkoxy, mono(C1-C20)alkoxy(C1-C20)alkyl, acryloxy, methacryloxy, acyloxy(C1-C6 alkyl), acyloxy(C3-C7 cycloalkyl), acyloxy(aryl), or halogen;
an unsubstituted or mono-substituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl, and acridinyl, each of said substituents being C1-C20 alkyl, C1-C20 alkoxy, phenyl, or halogen;
a group represented by one of:
wherein K is —C1-12— or —O—, and M is —O— or substituted nitrogen, provided that when M is substituted nitrogen, K is —CH2—, the substituted nitrogen substituents being hydrogen, C1-C20 alkyl, or C1-C20 acyl, each R25 being independently chosen for each occurrence from C1-C20 alkyl, C1-C20 alkoxy, hydroxy, and halogen, R26 and R27 each being independently hydrogen or C1-C20 alkyl, and u is an integer ranging from 0 to 2; or a group represented by:
wherein R28 is hydrogen or C1-C20 alkyl, and R29 is an unsubstituted, mono-, or di-substituted group chosen from naphthyl, phenyl, furanyl, and thienyl, wherein the substituents are C1-C20 alkyl, C1-C20alkoxy, or halogen; or
B and B′ taken together form one of a fluoren-9-ylidene, mono-, or di-substituted fluoren-9-ylidene, each of said fluoren-9-ylidene substituents being independently chosen from C1-C20 alkyl, C1-C20 alkoxy, and halogen.

### Claim 9 (depends on 8)

The polymer composition of claim 8 wherein,
for the spirooxazine compound represented by Formula (II),
R1 independently for each n and R2 independently for each p are each independently selected from hydrogen, aryl, mono(C1-C6)alkoxyaryl, di(C1-C6)alkylamino, piperidino, morpholino, C1-C6 alkoxy, or fluoro,
R3 is, independently for each q, selected from hydrogen, C1-C5 alkyl, C1-C5 alkoxy, C1-C8 alkoxycarbonyl, acyloxy(C1-C6 alkyl), acyloxy(C3-C7 cycloalkyl), acyloxy(aryl), halo, C1-C4 monohaloalkyl or C1-C4 polyhaloalkyl; and said halo substituents being chloro or fluoro,
R4 is selected from hydrogen, C1-C8 alkyl, phen(C1-C4)alkyl, acrylyloxy(C2-C6)alkyl, methacrylyloxy(C2-C6)alkyl, carboxy(C2-C6)alkyl, tri(C1-C6)alkylsilyl, tri(C1-C6)alkylsilyloxy, tri(C1-C6)alkoxysilyl, tri(C1-C6)alkoxysilyloxy, di(C1-C6)alkyl(C1-C6 alkoxy)silyl, di(C1-C6)alkyl(C1-C6 alkoxy)silyloxy, di(C1-C6)alkoxy(C1-C6 alkyl)silyl or di(C1-C6)alkoxy(C1-C6 alkyl)silyloxy, and
R5 and R6 are each independently selected from hydrogen, C1-C5 alkyl, phenyl; or R5 and R6 taken together form a group chosen from a cyclic ring of from 5 to 8 carbon atoms which includes the Spiro carbon atom, and
for the indenonaphthopyran represented by Formula (III),
R7 independently for each x and R8 independently for each y are each independently selected from, hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, morpholino, morpholino substituted with C1-C8 linear or branched alkyl, C1-C8 haloalkyl, fluoro, chloro, and —O—R10′,
R9 and R10 are each independently selected from hydrogen, C1-C8 alkyl, C1-C8 haloalkyl, and C3-C7 cycloalkyl, or together form a spiro substituent selected from a substituted or unsubstituted spiro-carbocyclic ring containing 3 to 6 carbon atoms, and
B and B′ are each independently selected from aryl, aryl substituted with C1-C6 alkoxy, and aryl substituted with morpholino.

### Claim 10 (depends on 1)

The polymer composition of claim 1, wherein said polymer comprises at least one active hydrogen group selected from hydroxyl, thiol, carboxylic acid, primary amine, and secondary amine, and
said polymer composition further comprises at least one crosslinking agent comprising at least two functional groups selected from cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes, isocyanates, thioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates.

### Claim 11 (depends on 1)

The polymer composition of claim 1 further comprising an additive selected from heat stabilizers, light stabilizers, and combinations thereof.

### Claim 12 (depends on 1)

A mechanochromic article comprising the polymer composition of claim 1, wherein said mechanochromic article is selected from films, sheets, and 3-dimensional articles.

### Claim 13 (depends on 12)

The mechanochromic article of claim 12 wherein said 3-dimensional articles are selected from ophthalmic articles, display articles, windows, mirrors, protective articles, and support articles.

### Claim 14 (depends on 13)

The mechanochromic article of claim 13 wherein said mechanochromic article is selected from ophthalmic articles, and said ophthalmic articles are selected from corrective lenses, non-corrective lenses, contact lenses, and magnifying lenses.

### Claim 15 (depends on 13)

The mechanochromic article of claim 13 wherein said mechanochromic article is selected from display articles, and said display articles are selected from screens, monitors, and security elements.

### Claim 16 (depends on 13)

The mechanochromic article of claim 13 wherein said mechanochromic article is selected from protective articles, and said protective articles are selected from protective lenses, protective visors, protective headgear, and protective housings.

### Claim 17 (depends on 13)

The mechanochromic article of claim 13 wherein said mechanochromic article is selected from support articles, and said support articles are selected from rods, beams, crossarms, and combinations thereof.

### Claim 18 (depends on 1, 12)

The mechanochromic article of claim 12 wherein said mechanochromic article is selected from 3-dimensional articles, and each 3-dimensional article comprises a coating residing over at least a portion of at least one surface of each 3-dimensional article, further wherein said coating comprises said polymer composition of claim 1.

### Claim 19 (depends on 1)

A mechanochromic article comprising the polymer composition of claim 1 wherein said mechanochromic article further comprises a coating residing over at least a portion of at least one surface of said mechanochromic article, said coating being free of said polymer composition of claim 1, and said coating comprising an additive selected from heat stabilizers, light stabilizers, and combinations thereof.

### Claim 20

A polymer composition comprising a polymer, said polymer comprising at least one polymer chain segment represented by the following Formula (I),
wherein M independently for each w is a residue of a monomer,
Φ is a residue of a mechanochromic compound having at least two reactive groups that are each independently bonded to one monomer residue M,
w, independently for each z, is an integer of at least 1, and
z is an integer of at least 2,
further wherein said mechanochromic compound is selected from,
(a) a spirooxazine compound represented by the following Formula (II),
wherein n is from 1 to 4, p is from 1 to 2, q is from 1 to 4, and R1 independently for each n, R2 independently for each p, R3 independently for each q, R4, R5, and R6 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl each optionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO2—, —N(R11)—, and —Si(R11)(R12)— wherein R11 and R12 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more thereof,
provided that for the spirooxazine represented by Formula (II) at least two of, R1 independently for each n, R2 independently for each p, R3 independently for each q, R4, R5, and R6, each independently comprise said reactive group that is independently bonded to one monomer residue M,
(b) an indenonaphthopyran represented by the following Formula (III),
wherein x is from 1 to 4, y is from 1 to 4, R7 independently for each x, R8 independently for each y, R9, and R10 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl each optionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO2—, —N(R11)—, and —Si(R11)(R12)— wherein R11 and R12 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more thereof, and
B and B′ are each independently selected from unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, and polyalkoxy, or B and B′ taken together form a ring structure selected from unsubstituted fluoren-9-ylidene, substituted fluoren-9-ylidene, saturated spiro-monocyclic hydrocarbon ring, saturated spiro-bicyclic hydrocarbon ring, and spiro-tricyclic hydrocarbon ring,
provided that for the indenonaphthopyran represented by Formula (III), at least two of, R7, R8, R9, R10, B, and B′ each independently comprise said reactive group that is independently bonded to one monomer residue M,
wherein said polymer comprises at least one active hydrogen group selected from hydroxyl, thiol, carboxylic acid, primary amine, and secondary amine, and
said polymer composition further comprises at least one crosslinking agent comprising at least two functional groups selected from cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes, isocyanates, thioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates.

### Claim 21

A mechanochromic article comprising a polymer composition,
wherein said mechanochromic article is selected from 3-dimensional articles, and each 3-dimensional article comprises a coating residing over at least a portion of at least one surface of each 3-dimensional article, further wherein said coating comprises said polymer composition,
wherein said polymer composition comprises a polymer, and said polymer comprises at least one polymer chain segment represented by the following Formula (I),
wherein M independently for each w is a residue of a monomer,
Φ is a residue of a mechanochromic compound having at least two reactive groups that are each independently bonded to one monomer residue M,
w, independently for each z, is an integer of at least 1, and
z is an integer of at least 2,
further wherein said mechanochromic compound is selected from,
(a) a spirooxazine compound represented by the following Formula (II),
wherein n is from 1 to 4, p is from 1 to 2, q is from 1 to 4, and R1 independently for each n, R2 independently for each p, R3 independently for each q, R4, R5, and R6 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl each optionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO2—, —N(R11)—, and —Si(R11)(R12)— wherein R11 and R12 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more thereof,
provided that for the spirooxazine represented by Formula (II) at least two of, R1 independently for each n, R2 independently for each p, R3 independently for each q, R4, R5, and R6, each independently comprise said reactive group that is independently bonded to one monomer residue M,
(b) an indenonaphthopyran represented by the following Formula (III),
wherein x is from 1 to 4, y is from 1 to 4, R7 independently for each x, R8 independently for each y, R9, and R10 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl each optionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO2—, —N(R11)—, and —Si(R11)(R12)— wherein R11 and R12 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more thereof, and
B and B′ are each independently selected from unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, and polyalkoxy, or B and B′ taken together form a ring structure selected from unsubstituted fluoren-9-ylidene, substituted fluoren-9-ylidene, saturated spiro-monocyclic hydrocarbon ring, saturated spiro-bicyclic hydrocarbon ring, and spiro-tricyclic hydrocarbon ring,
provided that for the indenonaphthopyran represented by Formula (III), at least two of, R7, R8, R9, R10, B, and B′ each independently comprise said reactive group that is independently bonded to one monomer residue M.

### Claim 22

A mechanochromic article comprising a polymer composition,
wherein said mechanochromic article further comprises a coating residing over at least a portion of at least one surface of said mechanochromic article, said coating being free of said polymer composition, and said coating comprising an additive selected from heat stabilizers, light stabilizers, and combinations thereof,
wherein said polymer composition comprises a polymer, and said polymer comprises at least one polymer chain segment represented by the following Formula (I),
wherein M independently for each w is a residue of a monomer,
Φ is a residue of a mechanochromic compound having at least two reactive groups that are each independently bonded to one monomer residue M,
w, independently for each z, is an integer of at least 1, and
z is an integer of at least 2,
further wherein said mechanochromic compound is selected from,
(a) a spirooxazine compound represented by the following Formula (II),
wherein n is from 1 to 4, p is from 1 to 2, q is from 1 to 4, and R1 independently for each n, R2 independently for each p, R3 independently for each q, R4, R5, and R6 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl each optionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO2—, —N(R11)—, and —Si(R11)(R12)— wherein R11 and R12 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more thereof,
provided that for the spirooxazine represented by Formula (II) at least two of, R1 independently for each n, R2 independently for each p, R3 independently for each q, R4, R5, and R6, each independently comprise said reactive group that is independently bonded to one monomer residue M,
(b) an indenonaphthopyran represented by the following Formula (III),
wherein x is from 1 to 4, y is from 1 to 4, R7 independently for each x, R8 independently for each y, R9, and R10 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl each optionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—, —OC(O)O—, —S(O)—, —SO2—, —N(R11)—, and —Si(R11)(R12)— wherein R11 and R12 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more thereof, and
B and B′ are each independently selected from unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, and polyalkoxy, or B and B′ taken together form a ring structure selected from unsubstituted fluoren-9-ylidene, substituted fluoren-9-ylidene, saturated spiro-monocyclic hydrocarbon ring, saturated spiro-bicyclic hydrocarbon ring, and spiro-tricyclic hydrocarbon ring,
provided that for the indenonaphthopyran represented by Formula (III), at least two of, R7, R8, R9, R10, B, and B′ each independently comprise said reactive group that is independently bonded to one monomer residue M.