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Title:
POLYMER COMPOSITIONS CONTAINING MECHANOCHROMIC POLYMERS
Document Type and Number:
WIPO Patent Application WO/2014/152259
Kind Code:
A1
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 spirooxazine compound represented by the following Formula (II), and an indenonaphthopyran represented by the following Formula (III).

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Inventors:
HICKENBOTH, Charles R. (512 Luke Court, Cranberry Township, Pennsylvania, 16066, US)
KUTCHKO, Cynthia (1405 Greendale Drive, Pittsburgh, Pennsylvania, 15239, US)
KRYGER, Matthew J. (4 Shangri La Circle, Pittsburgh, Pennsylvania, 15239, US)
Application Number:
US2014/027132
Publication Date:
September 25, 2014
Filing Date:
March 14, 2014
Export Citation:
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Assignee:
PPG INDUSTRIES OHIO, INC. (3800 West 143rd Street, Cleveland, Ohio, 44111, US)
International Classes:
C09K9/02; C07D498/20; C09K11/06; G02B1/04; G03C1/685
Domestic Patent References:
WO2004041961A1
WO2006024099A1
WO2001019813A1
Foreign References:
US20010025948A1
EP1810982A1
US6555028B2
US6556028B1
US6113814A
US6019914A
US6296785B1
US7527754B2
US5645767A
US5777061A
Attorney, Agent or Firm:
FORTNEY, Lester, N. et al. (The Webb Law Firm, One Gateway Center420 Ft. Duquesne Blvd., Suite 120, Pittsburgh Pennsylvania, 15222, US)
Download PDF:
Claims:
WHAT IS CLAIMED iS:

1. A polymer composition comprising a polymer, said polymer comprising at least one polymer chain segment represented by the following Formula

(0,

wherein 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 spirooxazlne compound represented by the following Formula (If),

wherein n Is from 1 to 4, p is from 1 to 2, q is from 1 to 4, and Ri independently for each n, R2 independently for each p, R3 independently for each q, i, Rs, and R6 are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi each optionally interrupted with at least one of -0-, -S-, - C{0}-, -0(0)0-, -00(0)0-, -S(0>, -S02-, -N{R1 K and -Si(R11){R12}- wherein R 1 and R12 are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi, and combinations of two or more thereof,

provided that for the splrooxazine represented by Formula (I!) at least two of, Ri independently for each n, R2 independently for each p, R3 independently for each q, R4, R5) and e, each independently comprise said reactive group that is independently bonded to one monomer residue M,

(b) an indenonaphthopyran represented by the following Formula (Hi),

(ill)

wherein x is from 1 to 4, y is from 1 to 4, R7 independently for each > Re independently for each y, R8) and R10 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl each optionally interrupted with least one of -0-, -S-, -C{0)~, -C(0}0, ~OC(0)Ch -S(O)-, -S02-, -N(R 1)-, and

-SI{R1†)(R 2)~ wherein R1 ! and R12 are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations of two or more thereof, and

B and 8' are each independently selected from unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, and polyalkoxy, or and B' taken together form a ring structure selected from unsubstituted f!uoren~9- y!idene, substituted fiuoren-9-yiidene, saturated spiro-rnonocyclic hydrocarbon ring, saturated spiro-bicyclic hydrocarbon ring, and spiro-tricyciic hydrocarbon ring,

provided that for the indenonaphthopyran represented by Formula (III), at least two of, R7> Rg, Rg, Rio, B, and 8' each independently comprise said reactive group that is independently bonded to one monomer residue M.

2. The polymer composition of claim 1 ,

wherein the spirooxazine represented by Formula (I!) comprises at least one first reactive group, and ai least one second reactive group,

further wherein for the spirooxazine represented by Formula (I!) at least one of R< Independently for each n, and R2 independently for each p, independently comprise said first reactive group, and at least one of R3

independently for each q, R4, R5 and R6 Independently comprise said second reactive group, and

wherein the indenonaphthopyran represented by Formula (ill) comprises at least one first reactive group, and at least one second reactive group, further wherein for the indenonaphthopyran represented by Formula (HI) at feast one of B and B' independently comprise said first reactive group, and at feast one of R7 independently for each x, R8 independently for each y, Rg and R-¾0 independently comprise said second reactive group.

3, The polymer composition of claim 1 wherein, is 2,

the spirooxazine represented by Formula (II) comprises one first reactive group, and one second reactive group,

further wherein for the spirooxazine represented by Formula (H) one of i, and R2, independently comprise said first reactive group, and one of f¾, R , R5 and R6 comprise said second reactive group, and

the indenonaphthopyran represented by Formula (HI) comprises one first reactive group, and one second reactive group,

further wherein for the indenonaphthopyran represented by Formula (111) one of B and Bf comprise said first reactive group, and one of R7l R8, Rg and R10 comprise said second reactive group.

4. The polymer composition of claim 3 wherein, for the spirooxazine represented fay 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.

5. 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.

6. The polymer composition of claim 5 wherein,

the active hydrogen groups of said mechanochromic compound are each Independently selected from hydroxy!, thiol primary amine, secondary amine, and carboxyiic acid, and

the groups that, are reactive with active hydrogen groups, of said mechanochromic compound, are each independently selected from carboxyiic acid halides, cyclic carboxyiic acid anhydrides, oxiranes, thiooxsranes, isocyanates, fhioisocyanafes, cyclic carboxyiic acid esters, cyclic amides, and cyclic carbonates.

7. The polymer composition of claim 5 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,

8. The polymer composition of claim 7 wherein, each active hydrogen group of each monomer is independently selected from hydroxy!, 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 nalides, cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes, isocyanates, thioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates.

9. The polymer composition of claim 1 wherein, said polymer is selected from polyester polymers, po!yurethane polymers, polycarbonate polymers, poiyether polymers, poiyamide polymers, polyimide polymers, poiyamidelmide polymers, poiyurea polymers, polysulfone polymers, polyketone polymers, and combinations of two or more thereof.

10. The polymer composition of claim 1 wherein, for the spirooxazine compound represented by Formula (Si),

Ri independently for each n and R2 independently for each p are each independently selected from hydrogen, ary!, mono(Ci-C6)alkoxyaryi, di{Ci-C6)alkoxyaryi, mono{CrCe)a!ky!aryl, di(Ci-C6)a!kylaryi, bromoaryl, chloroaryf, fluoroary!, C3-C7 cyc!oalkyiaryl, C3-.C7 cycloaiky!, C3-C7 cycioafkyioxy, C3-C7 cyc!oalkyloxy(CrC6)aikyi, C3-C7 cycloa!kyioxy{Ci-C6)aikoxy, aryl(CrC6)a!ky1, aryi(C-i-C6)alkoxy, aryioxy, aryloxy Cr-CeJalkyl, ar/ x fC CeJaikoxy, mono- or df(C C6)aikyIaryi(CrCe)a!kyl, mono- or di{Ci-C6)aikoxyaryl{C C6}alkyi, mono- or di(CrC6)alkyiary!(CrC6)a!koxy, mono- or di(CrC6)aikoxyary!{CrC6)aikoxy, amino, mono(CrC6)aikylamino, d CrCeJa!kylamino, diaryiamino, N-(C Ce)aikylpiperazir\o, N-aryipiperazino, aziridino, indolino, piperidino, arylpiperidino, morpholsno,

thiomorphoiino, ietrahydroquinoiino, tetrahydroisoquino!ino, pyrryl, C Ce a!kyl, C Cs bromoalkyi, Crce chloroalkyi, C Ge fluoroaikyi, C C6 alkoxy, mono(C-!-C6)aikoxy(Ci- C4}a!k l, acryioxy, methacry!oxy, acy!oxyCC-t-Ce alkyl), acyloxy(C3-C7 cycioalkyl), acyfoxy(aryl), bromo, chloro or fluoro, f¾ is, independently for each q, chosen from hydrogen, C C5 alkyl, C C5 a!koxy, nitro, cyano, C C8 a!koxycarbonyl, acyloxy{CrC6 aikyi), acyloxy(C3-C7 cycioalkyi), acyioxy(aryl),, halo, C C monohaloalky! or C C4 po!yha!oaikyl; said halo substituents being chforo, fluoro, iodo or bromo,

R4 is chosen from hydrogen, CrC8 aikyi, C3-C.7 cycioalkyi, phen(Ci-C4)a!kyl, naphth{Ci-C4}afkyi, ally!, acrylyloxy(C2-C6)alkyii m.ethacryfyloxy(C2- C6)alkyl, C2-Q 3cyloxy(C2-C6)alkyi; carboxy(CVC6)alkyl, cyano(C2-C6)aikyl! hydfoxy(C2-C6)alkyl, triaryisslyi, iriaryfsilyioxy, tri(Ci-C6)alkylsiiyi,

tri(Ci-G6)afkyisilyloxy, tri(CrC6)alkoxystly!, tri(CrC6)alkoxysiiy!pxy,

di(Ci-C6)alkyl(CrCe a!koxy)siiyl, di(C C6)aikyi(CrC6 alkoxy)silyloxy,

di(Ci-C6)aikoxy(CrC6 aikyl)siiyi, di(C¾ -C6)alkoxy{CrC6 aikyi Jsilyloxy, C C6 alkoxy(C2- C )aikyl or (C2 A0)& 3, wherein r is an integer from 1 to 6,

Rs and R6 are each independently selected from hydrogen, Cr C5 aikyi, acyloxy(C-rCe alkyl), acy!oxy(C3-C7 cycioalkyi), acyloxy(aryl), benzyl, phenyl, mono- or di-subststuted phenyl, said phenyl substituents being C C5 aikyi or C C5 a!koxy; 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 Rs independently for each y are each independently selected from,

hydrogen,

a compatibiizing substifuent;

halogen selected from fluoro and chloro;

C -C;.c alkyl;

C3-C10 cycioalkyi;

acyioxy(CrC6 alkyl), acyloxy(C3~C7 cycioalkyi), acyioxy(aryl);

substituted or unsubstituted phenyl, the pheny! substituents being selected from hydroxyl, halogen, carbonyi, C C2o alkoxycarbony!, cyano, halo(CrC2o)aikyis C:-C6:: aikyi or C G¾o aikoxy;

~0-Rio' or -C(O)-R10'or -C(O)-GR10', wherein R10' is hydrogen, CrC20 alkyl, phenyi(C1-C2o)alkyl, niono(C -C20)aikyl substituted phenyi(Cr Cao)alkyl, mono(C1-C2o)alkoxy substituted phenyl(CrC2o)aikyl:, (d- C2o)aikoxy(Ca-C2o)aiky{, C3-C10 cycioalkyi, or mono{Ci-C20)alkyi substituted C3-C {j cycioalkyi;

- iRn'JR^', wherein Rn' and R12' are each Independently hydrogen, C C2o alkyl, phenyl, naphthyl, furanyi, benzofuran-2-yl, benzofuran-3- yi, thienyl, benzothien-2-yi, benzothien~3~yl, dtbenzofuranyl, dibenzGthienyi, benzopyridyl, fluorenyl, C C2o alky!ary!, C3-C10 cycioaikyi, C -C2o bicycioaikyi, C5- C2o tricyc!oalkyi or C - C20 alkoxyalkyi, wherein said ary! group is phenyl or naphthyi, or R^' and

Rl2' come together with the nitrogen atom to form a C3-C20 hetero- bicyc!oaiky! ring or a C4-C20 hetero-tricycioalkyi ring;

a nitrogen containing ring represented by the following graphic formula

IVA,

wherein each -Y- is independently chosen for each occurrence from - CH2-, ~CH{Ri3!)-, -C(Ri3V- -CH(aryl)-, -C{aryl)2-, and -C(R13')<aryl)-, and Z is -Y-, -0-, -S-, -S(0}-, -S02-, -NH-, -N(R13 , or -N(aryl)-, wherein each R 3' is independently C1-C20 a!kyl, each aryl 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, 2 is -Y-;

a group represented by one of the following graphic formulas IVB or IVC,

wherein R1S, R16, and Rir are each independently hydrogen, C C6 alky}, phenyl, or naphthyi, or the groups R 5 and R16 together form a ring of 5 to 8 carbon atoms and each R° Is independently for each occurrence selected from Ci-C2D. alkyl, C C2o alkoxy, fluoro or chloro, and Q is an inieger 0, 1, 2, or 3; and

unsubstituted, mono-, or di-substituted C -Cig spirobicyciic amine, or unsubstituted, mono-, and di-substituted C4-C18 spirotricycfic amine, wherein said substituents are independently aryl, CrCj j alkyl, Ci-C20 alkoxy, or phenyl(Ci-C2o)alkyi; or two adjacent R? groups, or two adjacent R8 groups, independently together form a group represented by one of 1VD and

wherein T and T are each independently oxygen or the group where R ', R15l and R16 are as set forth above,

R9 and R¾ are each Independently selected from,

(i) hydrogen, CrC?.o alkyl, CrC20 haioalkyl, CrC,o cydoaikyi, acy oxy(Ci~Ce alkyl), acyioxy{C3-C7 cycloalkyi), a cy foxy (aryi), aliyl, benzyl, or mono-substituted benzyl, said benzyl substituents being chosen from halogen, C1-C20 alk l or C C2o alkoxy;

an unsubstituted, mono- di-or tri-subsiituted group chosen from phenyl, naphthyl, phenanihryi, pyreny!, quinoiyl, isoquinoiyi,

benzofuranyl, thienyl, benzothienyl, dihenzofuranyl, dibenzothienyl, carbazoiyl, or indoSyi, said group substituents in each case being independently chosen from halogen, CrC20 alkyl or C1-C20 alkoxy;

mono-substituted phenyl, said substituent located at the para position being ~(CH2)f- or ~0-{CH2)|~! wherein f. is the integer 1 , 2, 3, 4, 5 or

8, said substituent being connected to an aryi group which is a member of a photochromic material;

the group -CH(R )G, wherein R is hydrogen, CrC6 alkyl or the unsubstituied, mono- or di-substituted aryi groups phenyl or naphthyl, and G is -CH2OR19, wherein R S is hydrogen, -C(O)R,0( C C20 alkyl, C C20

alkoxy(CrC2o)alkyl, pheny!(CrC2o)alkyl, mono(Ci-C20)alkoxy substituted phenyi(Ci- C2o)aikyit or the unsubstituied, mono- or di-substituted aryi groups phenyl or naphthyl, each of said phenyl and naphthyl group substituents being Cr-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 unsubstituied spiro-heterocyciic ring containing 1 or 2 oxygen atoms and 3 to 8 carbon atoms including the spirocarbon atom, said spiro- carbocyciic ring and spiro-heterocyciic ring being anneiia'ted with 0, 1 or 2 benzene rings, said substituents being hydrogen or C C2o alkyl; and B and B' are each independently;

an aryl group that is mono-substituted with a compatiblizlng substituent; a substituted phenyl; a substituted aryl; a substituted 9- juiolindinyl; a substituted heteroaromatic group chosen from pyridyi, furanyi, b.erszofuran-2-yi, henzofuran-3-yl, thienyi, benzothien-2-yl, benzothien-3-yl, dibenzofuranyi, dibenzothlenyl, carbazoyl, benzopyridyi, indoiinyi, and fluorenyl, wherein the phenyl, aryl, 9- juiolindinyi, or heteroaromatic substituent is a reactive substituent R; an unsubstituted, mono-, di-, or tri-substitu'ted phenyl or aryl group; 9- ju!olidiny!; or an unsubstituted, mono- or di-substituted heteroaromatic group chosen from pyridyi, furanyi, benzofuran-2-yl, benzofuran-3-yi, thienyi, benzothsen-2-yl, benzothien-3-yi, dibenzofuranyl,

dsbenzothienyl, carbazoyl, benzopyridyi, indoiinyi, and fluorenyl, wherein each of the phenyl, aryi and heteroaromatic substituents are each independently:

hydroxy!, a group -C(~0)R21, wherein R2i is -OR22, - (R23)R2 , piperidino, or morpho!inq, wherein R22 is aiiyl, Ci-C20 alkyl, phenyl, mono(C C2o)a[kyl substituted phenyl, mono(C

C20)alkoxy substituted phenyl, pheny!(C-rC2o)a!kyl, mono(C C2C)alky[ substituted phenyl(C C2o)aiky1, mono(C C20)alkoxy substituted phenyl(C C20)aikyl, C C20 alkoxy(C2-C2o)aikyl or C1-C20 haloafkyi, R23 and R24are each independently C1-C20 alkyl, C5~G10 cycioalkyi, phenyl or substituted phenyl, the phenyl substituents being C C20 aikyl or C C20 alkoxy, and said halo substituent is ch!oro or fiuoro, aryl, mono(Cr C2o)a!koxyaryiJ di(CrC20}aikoxyaryl, mono{CrC2o)alkylaryi, di{CrC20)aiky1aryl, haioaryt, C3-C10 cycloaikylaryi, C3~C 0 cycioalkyi, C3~C10 cyctoalkyioxy, C3-C10 cycioaikyioxy(C C2o)aikyi, C3-C 0 cycloaikyfoxy(CrC20)alkoxy, aryl(CrC20)a!kyi, aryl(Ci-C2o)a!koxy, aryloxy, aryioxy(C C2o)a!kyi, aryioxy(Cr C20)alkoxy, mono- or di(C1-C2o)alkylaryl{Cr-C2o)aikyl, mono- or di--(C C2o)alkoxyary!(Ci-C2o)aiky!, mono- or di-(C

C2o)a!kylary!(Ci-C2o)afkoxy, mono- or di-(Ci-C2o)alkoxyaryi{CV C2o)a!koxy, amino, mono- or di-(CrC20)a!kyiamino,

diarylamlno, plperazino, W-(G1-C20)aiky!piperazino, N~ arylpiperazino, aziridino, indolino, piperidino, morphoiino, thtomorpho!ino, tetrahydroquinoiino, tetrahydroisoquino!ino, pyrrolidyi, Cr-C20 aikyi, C C20 haioa!kyl, C,-C2o aikoxy, mono(CrC2o}aikoxy(Ci-C2o)alKyl, acryioxy, methacryioxy, acyloxy(CrC6 alkyi), acyioxy{C3-Cr cycioalkyf), acyioxy(aryi), or halogen;

an unsubstituted or mono-substituted group chosen from pyrazoiyi, imidazolyl, pyrazo!inyi, imidazoiinyi, pyrrolinyi, phenothiazinyi, phenoxazinyl, phenazinyi, and acridinyi, each of said substituents being CrC20 aikyi, C1-C20 aikoxy, phenyl, or halogen;

a group represented by one of:

wherein K is ~CH2- 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, C-i-Cjo alkyi, or C C20 acyl, each R25 being independently chosen for each occurrence from C1--C20 aikyi, C -C2o aikoxy, hydroxy, and halogen, f¾e and R27 each being independently hydrogen or C1-C20 aikyi, and u is an integer ranging from 0 to 2; or a group represented by:

wherein R28 is hydrogen or C1--C20 aikyi, and R2S is an unsubstituted, mono-, or di-substiiuted group chosen from naphthyl, phenyl, furanyl, and thienyl, wherein the substituents are C1-C20 alkyi, C1-C20 aikoxy, or halogen; or

B and B' taken together form one of a f!uoren-9-ylidene, mono- , or di-substituted fluoren-9-yiidene, each of said fluoren-9-ylidene substituents being independently chosen from C C2o alkyi, Ci-C20 aikoxy, and halogen.

11. The polymer composition of claim 10 wherein,

he spirooxazine compound represented by Formula (II), R-i independently for each n and R2 independently for each p are each independently selected from hydrogen, aryl, mono(CrC6)aikoxyaryl, di(C rCe)aikylamino, piperidino, morphoiino, C,~C6 alkoxy, or fiuoro,

R3 is, independently for each q, selected from hydrogen, Ci-C§ aikyi, Ci-G5 aikoxy, C C8 aSkoxycarbonyi, acyioxy{Ci-C6 alky!), acy!oxy{C3-C7 cycioaikyi), acyioxy(aryi)„ halo, C1-C4 monohaloaikyl or C1-C4 poiyha!oaiky!; and said halo substituerrts being chioro or fiuoro,

R4 is selected from hydrogen, Cr-C8 aikyi, phen{Ci-C4)aikyi, acryly!oxy(C2-Cg)a!kyl, methacryiy!oxy(G2-C6)alkyl, carboxy(C2-C6)a!kylt

tri{CrC6)alky!si!yl, tri(CrC6)alkyisi!yloxy, tri(CrC6)a!koxysflyi, iri(CrC6)a!koxysiiyioxy, dl(Ci -C3)alkyi(C C6 afkoxy)siiyi, di(CrC5}alkyl(C C6 aikox )siiyioxy,

di(Ci-C6)alkoxy(C Cs aikyi)siiyi or di(CrC6)alkoxy<CrC6 aikyl)silyloxy, and

R5 and R6 are each independently selected from hydrogen, Cr C5 aikyi, 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 (IN),

R7 independently for each x and Rs independently for each y are each independently selected from, hydrogen, C-rC6 a!ky!, C3-C7 cycioaikyi, morphoiino, morpho!ino substituted with C C8 linear or branched aikyi, Ci-C8 ha!oalkyl, fiuoro, chioro, and -O~Ri0',

Rg and R10 are each independently selected from hydrogen, Ci-C8 aikyi, C C8 haloaikyl, and C3-C7 cycioaikyi, or together form a spiro substituent selected from a substituted or unsubstituted spiro-carbocyciic ring containing 3 to 6 carbon atoms, and

B and B! are each independently selected from aryl, aryl substituted with CrC6 alkoxy, and aryl substituted with morphoiino.

13. The polyme composition of claim 1 , wherein said polymer comprises at least one active hydrogen group selected from hydroxy!, thiol,

carboxylic acid, primary amine, and secondary amine, and

said polymer composition further comprises at least one crossiinking 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,

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

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

16. The mechanochromic article of claim 15 wherein said

3-dimensiona! articles are selected from ophthalmic articles, display articles, windows, mirrors, protective articles, and support articles.

17. The mechanochromic article of claim 18 wherein said mechanochromic article Is selected from ophthalmic articles, and said ophthalmic articles are selected from corrective lenses, non-corrective tenses, contact lenses, and magnifying lenses.

18. The mechanochromic article of claim 16 wherein said mechanochromic article is selected from display articles, and said display articles are selected from screens, monitors, and security elements,

19. The mechanochromic article of claim 16 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.

20. The mechanochromic article of claim 18 wherein said mechanochromic article is selected from support articles, and said support articles are selected from rods, beams, crossarms, and combinations thereof.

2 . The mechanochromic article of claim 15 wherein said mechanochromic article is selected from 3-dimensionai articles, and each

3-dimensionsai article comprises a coating residing over at least a portion of at least one surface of each 3-dimensiona! article, further wherein said coating comprises said polymer composition of claim 1 ,

22. 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, !ight stabilizers, and combinations thereof.

Description:
POLYMER COMPOSITIONS CONTAINING tWECHANOCHRG&HC POLYMERS

CROSS REFERENCE TO RELATED PATENT APPLICATIO

[001] The present patent application is a continuation in part of and claims priority to United States Patent Application No. 13/447,804, filed on April 16, 2012, the disclosure of which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

[002] 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.

BACKGROUND OF THE INVENTION

[003] 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, and support articles, such as beams can be subjected to 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.

[004] 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.

[005] It would be desirable to develop new mechanochromic materials that can be used to provide a visually observable indication that an article, which incorporates such mechanochromic materials, has undergone a threshold mechanical stress event, li would be additionally desirable thai such newly developed mechanochromic materials posses improved stability.

SUMMARY OF THE INVENTION

[006] In accordance with the present invention, there is provided 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 {!).: Svt independently for each w is a residue of a monomer; Φ 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.

[007] With further reference to Formula (I) the mechanochromic compound, of which is a residue, is selected from, (a) a spirooxazine compound represented by the following Formula (ll),

With reference to Formula (!!}, n is from 1 to 4, p is from 1 to 2, q is from 1 to 4, and 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.

|O08] With additional reference to the spirooxazine represented by Formuia (II), there is the proviso that at least two of, Ri independently for each n, R 2 independently for each p, R 3 independently for each q, R , R 5 , and R 6l each independently comprise the reactive group that is independently bonded to one monomer residue M.

[009] With further reference to Formula (I) the mechanocbrornic compound, of which φ is a residue, is also selected from, (b) an indenonaphthopyran represented by the following Formula (III),

With reference to Formuia (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, F¾, 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.

[010] With additional reference to Formula (III), 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.

[011] With regard to the indenonaphthopyran represented by Formula (Hi), there is the proviso that at least two of, R 7 , R s , R 9 , R 10( B, and B' each independently comprise the reactive group that is independently bonded to one monomer residue M.

|012] in accordance with the present invention, there is further provided 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.

[013] The features that characterize the present Invention are pointed out with particularity in the claims, which are annexed to and form a part of this disclosure. These and other features of the invention, its operating advantages and the specific objects obtained by its use will be more fully understood from the following detailed description in which non-limiting embodiments of the Invention are illustrated and described.

DETAILED DESCRIPTION OF THE INVENTION

014f As used herein, the articles "a," "an," and "the" include plural referents unless otherwise expressly and unequivocally limited to one referent,

[015] Unless otherwise indicated, all ranges or ratios disclosed herein are to be understood to encompass any and ail subranges or subratios subsumed therein. For example, a stated range or ratio of "1 to 10" should be considered to Include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, ail subranges or subratios beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, such as but not limited to, 1 to 6.1 , 3.5 to 7.8, and 5.5 to 10.

|016] As used herein, unless otherwise indicated, left-to-right representations of linking groups, such as divalent linking groups, are inclusive of other appropriate orientations, such as, but not limited to, right-to-left orientations. For purposes of non-limitin il r tion, the left-to-right representation of the divalent linking group

or equivalents ~C(Q)Q~, is inclusive of the right-to-left

representation thereof, -0(Q)C~ or -OC(O)-.

[017f Other than in the operating examples, or where otherwise indicated, ail numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified In all instances by the term "about." [018] As used herein, 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.

[019] As used herein, 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).

[020] As used herein, the term "polymer" means homopoiymers (e.g., prepared from a single monomer species), copolymers (e.g., prepared from at least two monomer species), and graft polymers.

[021] As used herein, the term "(meth)acrylaie" and similar terms, such as "(meih)acryiic acid ester" means methacrylates and/or acry!ates. As used herein, the term "(meth)acrylic acid" means meihacrySic acid and/or acrylic acid.

[022] As used herein, spatial or directional terms, such as "left", "right", "inner", "outer", "above", "below", and the like, relate to the invention as it is depicted in the drawing figures. However, It is to be understood that the invention can assume various alternative orientations and, accordingly, such terms are not to be considered as limiting,

[023] As used herein, 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. For example, a layer "positioned over" a substrate does not preclude the presence of one or more other layers, coatings, or films of the same or different composition located between the positioned or formed layer and the substrate.

[024] As used herein, the term "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.

|025] All documents, such as but not limited to issued patents and patent applications, referred to herein, and unless otherwise indicated, are to be considered to be "incorporated by reference" in their entirety. [026] As used herein, recitations of linear or branched" groups, such as linear or branched alkyi, are herein understood to snciude: a methylene group or a methyl group; groups that are linear, such as linear C 2 ~C 20 alky! groups; and groups that are appropriately branched, such as branched C3-C2 0 alkyi groups.

[02?] As used herein the term "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! (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) (e.g., C5-C 10 aryi); C 5 ~C 18 heteroaryi (having at ieast one hetero atom in the aromatic ring); and C 6 -C2 4 aralkyl (e.g., C e ~Cio aralkyl).

[028] 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!.

[029] The term "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.

[030] The term "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! groups, ether groups, thiol groups, thio ether groups, carboxyiic acid groups, carboxyllc acid ester groups, phosphoric acid groups, phosphoric acid ester groups, sulfonic acid groups, sulfonic acid ester groups, nitro groups, cyano groups, hydrocarbyi groups (e.g., aikyl, aikenyl, alkynyi, cycioalkyi, heterocyc!oalkyl, aryl, heteroaryl, and aralkyi groups), and amine groups, such as -N Ru'XR^') where Rn ' and R 12 ' are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi,

[031] The term "substituted hydrocarbyi" is inclusive of haiohydrocarbyi (or halo substituted hydrocarbyi) substttuents. The term "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). Correspondingly, the term "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.

|032| The hydrocarbyi and substituted hydrocarbyi groups from which the various groups described herein can each be Independently selected, such as, but not limited to, 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 )-. As used herein, by interrupted with at least one of -0-, ~S~, -0(0)-, -0(0)0-, -00(0)0-, ~S(0h -SO .? -, -N(R 11 )-, and -Si(R r1 )(R 12 )--, means that at least one carbon of, but less than all of the carbons of, the hydrocarbyi group or substituted hydrocarbyi group, is In each case independently replaced with one of the recited divalent non-carbon linking groups. The 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. For purposes of non-limiting illustration, a combination of adjacent -C(O)- and - N(R 11 )- can provide a divalent amide linking or interrupting group, -C(0}-N(R 11 )-. For purposes of further non-!imiting illustration, 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,

[033] As used herein, 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. Further, as used herein the term "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.

[034] 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. With some embodiments of the present invention, 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,

[035] As used herein to modify the term "state," the terms "first" and "second" are not intended to refer to any particular order or chronology, but instead refer to two different conditions or properties. For purposes of non-limiting illustration, the first state and the second state of a 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. Thus, according to various non-limiting embodiments disclosed herein, 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. For example, while not limiting herein, 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. Alternatively, 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.

|G36] As used herein, the term "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.

£037] As used herein the term "film" means a pre-iormed layer having a generally uniform thickness that is not capable of self-support.

[038] As used herein the term "sheet" means a pre-formed layer having a generally uniform thickness thai is capable of self-support. £038] As used herein the term "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.

[040] 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.

[041 J The polymers of the polymer compositions of the present invention include at feast 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. With some embodiments 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).

|942J With some embodiments, 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). Correspondingly, 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). In accordance with some embodiments, 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).

[043] In accordance with some embodiments, the polymer chain segment represented by Formula (I) substantially defines the polymer, and is represented by the following Formula (l-A), (!-A)

With reference to Formula (i-A), φ, M, w, and z are each as defined with reference to Formula {1} herein, such as previously herein. With further reference to Formula (l~ A), E independently tor each z is an end group or terminal group. With some embodiments, E Is selected from hydrogen, a monomer residue , hydrocarbyi and substituted hydrocarbyi each optionally interrupted with at least one of -0-, -S-, - C(0)-, -C(0)0-, -OC(0}0-, -S(OK -SO r , -N(R 11 }~, and -Si(R 1 )(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,

[044] 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. With some additional embodiments, 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.

[045] Each end group E, with some further embodiments, 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. When the polymers of the present Invention include radically poiymerizable ethy!enicaily unsaturated groups, 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.

[046] With some embodiments, 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),

C(R 1 )~~CH 2 (VII) [04?] W th reference to Formula (VI !), R ! is hydrogen, halogen or a Ci to C alky! group. With some embodiments, R 1 is hydrogen or methyl and Formula (VII) represents a (meth)aSlyl radical.

[048] The spirooxazine represented by Formula (II), with some embodiments, includes at least one first reactive group, and at least one second reactive group. In further accordance with some embodiments, for the spirooxazine represented by Formula (II): at least one of R-i independently for each n, and R 2 independently for each p, independently include the first reactive group; and at feast one of R 3 Independently for each q, R 4l R 5 and R 6 independently include the second reactive group. Each first reactive group and each second reactive group can be the same or different.

[049] While not intending to be bound by any theory, and with reference to Formula (II), it Is believed based on the evidence at hand that the spirooxazine compound of the present invention, with some embodiments, Is converted from a first state (which can be visibly non-colored) to a second state (which can be visibly colored) when bond (a') between ring positions 3' and 4' is broken. As such, and with some embodiments, when the spirooxazine represented by Formula (!l) includes at least one first reactive group and at least one second reactive group, 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), and 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).

[050] The indenonaphthopyran represented by Formula (ill), with some embodiments includes at least one first reactive group, and at least one second reactive group. In further accordance with some embodiments, for the indenonaphthopyran represented by Formula (III); 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.

J0S1] While not intending to be bound by any theory, and with reference to Formula (III), it is believed based on the evidence at hand that the indenonaphthopyran compound of the present invention, with some embodiments, is converted from a first state (which can be visibly non-colored) to a second state (which can be visibly colored) when bond (a) between ring positions 3 and 4 is broken. As such, and with some embodiments, when the indenonaphthopyran represented by Formula (HI) includes at least one first reactive group and at least one 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).

[Θ52] In accordance with some embodiments, 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. In further accordance with some embodiments, for 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 F¾ include the second reactive group.

|053J Subscript z of Formula (I), with some embodiments, is 2, and the indenonaphthopyran represented by Formula (HI) includes one (a single) first reactive group, and one (a single} second reactive group, in further accordance with some embodiments, for the indenonaphthopyran represented by Formula (Hi); one of B and 8 ! include the first reactive group; and one of R 7 , R 8 , R 9 and R 10 include the second reactive group.

[054J 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. In further accordance with such non- limiting embodiments, for 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, and 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.

|055] 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. In further accordance with such non-limiting embodiments, for the Indenonaphthopyran represented by Formula (III); 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,

0563 The reactive groups of 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).

[057] 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.

[0581 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 (ΙΠ). In addition, the monomer reactive groups allow the monomers to react and polymerize with each other so as to form the polymers of the present invention.

[0591 With some embodiments, each active hydrogen group of each monomer is independently selected from hydroxy!, thiol, primary amine, secondary amine, and carboxylic acid. With some further embodiments, 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.

[060] 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.

[061] 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.

[062] 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.

[063} Examples of polyois useful in preparing 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, 4,4'~(propane~2,2-diy!)diphenQi, 4 ( 4'-methytenediphenol, and like polyois.

£084| 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 . [065] Polyether polymers of the present invention, can be prepared in accordance with art-recognized methods. With some embodiments 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. Fo purposes of non-limiting illustration, the polyether polymer can be prepared, with some embodiments, from; 4,4'-{propane~ 2 ( 2-diyi)diphenoi and the dig!ycidy! ether of 4,4'-(propane-2,2-dlyi)diphenol; or 4,4 - {propane-2,2-diyl)dlcy1cohexanoi and the diglycidy! ether of 4 ; 4'-(propane-2,2- diyf)dicylcohexanoi.

£086] The polyether polymers of the present invention, with some embodiments, 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.

[067] 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. Examples of polyisocyanates useful in the preparation of poiyurethane polymers include, with some embodiments;, aliphatic, aromatic, cycloaliphatic and heterocyclic polyisocyanates, and mixtures of such polyisocyanates,

[068] Further examples of 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

diisocyanate; bis(isocyanaio ethyl )fumarafe: isophorone diisocyanate; ethylene diisocyanate; dodecane-1 , 12-diisocyanate; cyclobutane-1 ,3-diisocyanate;

cyc!ohexane-1 ,3-diisocyaftate; cyc!ohexane-1 ,4-diisocyanate; methyi cyciohexyi diisocyanate; hexahydroto!uene~2,4-diisocyanaie; hexabydroto!uene-2,6- d i i socy a nate; hexahydropheny!ene-1 ,3-diisocyanaie; hexahydrophenyiene-1 ,4- diisocyanate; perhydrodiphenylmethane-2,4'-diisocyanaie;

perhydrodiphenylmethane~4 i 4 , -diisocyanate and mixtures thereof.

[D69J 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.

[070J 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.

[0711 The polycarbonate polymers of the present invention can be prepared in accordance with art- recognized methods. With some embodiments, 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. Examples to polyols having at least two hydroxy! groups, from which the polycarbonate polymers of the present Invention can be prepared, inciude, but are not limited to those polyols recited previously herein. 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.

[072] The polycarbonate polymers of the present invention, with some embodiments, 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,

[073] 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.

[074] 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 ¾di(cyclohexyia:mine),

4,4 , -{propane-2,2-diyl)diantline, 4,4-methyienedianiiine, piperazine, N-amlno ethyl piperazlne, 5-amino-1-aminomethyi-1 ,3 ( 3 rimethy1-cyciohexane, diamine ethane, diamine propane, diamlnobutane, diaminopentane, diamlnohexane, diaminoheptane, diamlnooctane, diaminodecane, diaminoundecane, diaminododecane, dicyanamtde, 4,4 i -diaminod!phenyi sulfone, and melamine.

[075] The polyamide polymers of the present invention, with some embodiments, 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,

[076] The po!yimide polymers of the present invention can be prepared by art-recognized methods. With some embodiments, 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. Examples of multifunctional anhydrides from which the poiyimide polymers can be prepared include, but are not limited to, pyrome!litic dianhydrlde and naphthalene tetracarboxy!ic dianhydrlde. Examples of 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. [077] The polyimide polymers of the present invention . with some embodiments, 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,

[078] The poiyamideimide polymers of the present invention can be prepared by art-recognized methods. With some embodiments, 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.

[079] The poiyamideimide polymers of the present invention, with some embodiments, 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

[080] The poiyurea polymers of the present invention can be prepared by art-recognized methods. With some embodiments, the poiyurea polymers are prepared by reaction of a multifunctional amine with a multifunctional isocyanate. Examples of multifunctional amines from which the poiyurea polymers can be prepared include, but are not limited to, those recited previously herein. Examples of multifunctional isocyanates from which the poiyurea polymers can be prepared include, but are not limited to, those recited previously herein.

[081] The poiyurea polymers of the present invention, with some embodiments, 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

[082] The polysulfone polymers of the present invention can be prepared by art-recognized methods. With some embodiments, 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. Examples of polyois from which the polysulfone polymers can be prepared include, but are not limited to, those polyois recited previously herein. With some embodiments, the polyol from which the poiysuifone polymers can he prepared is selected from 4 > 4 i ~(propane~2,2-diyl)diphenol and 4,4'-methyienediphenol.

[083] The poiysuifone polymers of the present invention, with some embodiments, 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.

[084] The poiyketone polymers of the present invention can be prepared by art-recognized methods. With some embodiments, 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. 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.

[085] With the spirooxazine compound of the present invention as represented by Formula (II), and in accordance with some embodiments, R-, independently for each n and f¾ 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

cydoalky!oxy(CrCe)aikoxy, aryi(CrC 6 )alkyl, aryi(C 1 -C 6 )aikoxy, ary!oxy,

aryloxy(CrC 6 )alkyl, aryioxy(Ci-C 6 )a!koxy, mono- or d!(C 1 -C 6 )alkyiary!{Ci-C6)alky!, mono- o di(CrCe)a!koxyaryl(CrCe)aikyl, mono- or di(Ci-C 6 )aikylaryl(CrC 6 ).a!koxy, mono- or di(Ci-C 6 )alkoxyaryi(C C 6 }ajkoxy, amino, monofCr-CeJaikyiamino,

df{CrC e )alkyiamino, diaryiarfiino, N-(CrC q )a!ky!piperazirtQ, N-arylpiperazino, aziridino, indolit o, piperidino, arylpiperidino, morpholino, thiornorphoiino,

tetrahydroquinolino, tetrahydroisoquinoiino, pyrryi, Ci~C e alkyl, Ci-C 3 bromoalkyi, C,- C6 chioroa!kyj, C r C 6 fluoroaikyi, C r C g aikoxy, mono{CrC 6 )a!koxy(CrC4)alky!, acryloxy, methacryioxy, acyioxy(C C 6 alkyl), acyloxy(C 3 -C 7 cyc!oalkyl), acyioxy(ary!), bromo, ch!oro or fluoro.

[086] In accordance with some embodiments of the present invention, 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)„ halo, C G 4 monohaioaikyl or d- C 4 polyhaloalkyl; said halo substifuents being chloro, fluoro, iodo or bromo. [087J i n accordance with some embodiments of the present invention, F¾ 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 ~C¾)alkyl, cyano(C 2 - Ce)aikyi, hydroxy(C 2 -C 6 )a!kyi , triary!silyi, iriaryisilyloxy, tri{Ci-C 6 )a!ky!siiyi, tri(CrCe)alky!silyIoxy, tri(C C 6 }a[koxysiiyl, tri(Ct -C e )af koxysilyloxy, di(CrC 6 )aSkyl(CrC 6 alkoxy)siiyl, di(C r C 6 )a!kyl(CrC 6 alkoxy)siiyioxy, di(CrC 6 )aikoxy(CrC 6 alkyi)siiyi, di(CrC 8 }aikoxy(Ci -C 6 aiky!)siiyfoxy, Ci-C 6 alkoxy{C 2 - C 4 )alkyi or (C 2 H 4 0) r CH 3 , wherein r is an integer from 1 to 6.

[088] With some embodiments, 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.

[089] With the spirooxazine compound of the present invention as represented by Formua! ( I), and in accordance with some embodiments, 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.

[090] In accordance with some embodiments of the present invention, 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.

[091] in accordance with some further embodiments of the present invention, 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,

carboxy(C 2 -C 6 )alkyi, tri(C r C 6 )alkylsilyl, tri(CrCe}alkylsilyloxy, in(Ci-C 3 )aIkoxysiiyi, iri(Ci-C 6 )afkoxysilyloxy, ai(CrC e )alkyl{CrC 6 aikoxy )silyl, aXCVC 6 )alkyl(C C e aikoxy)siiyioxy, d i(C -C 6 )alkoxy(Ci -C 6 alkyi)silyS or dlfC-i-CejaikoxyiCi-Cg

alkyl)silyloxy.

[092] I accordance with some additional embodiments of the present Invention, 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.

[093] For the indenonaphthopyran represented by Formula (IN), and In accordance with some embodiments, 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; C¾~ 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; -O-R, 0 ' or -C(O)-R 0 Or -C(O)-OR, 0 ', wherein R 10 ' is hydrogen, C -C2 0 aikyi, phenyl(C r C2o)aikyi, mono{C C 2 o)alkyl substituted pheny!(C C 20 }aikyi, mono(C C 2 o)aikoxy substituted pheny CrCzoJaikyi, {C 1 -G 20 )aikoxy(C2-C2 0 )aikyl ! C 3 - C 10 cycioalkyi, or mono(C C 2 o)aikyi substituted C 3 -C 10 cycioalkyi; wherein 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 naphthyi, or R„' and R 2 ' come together with the nitrogen atom to form a C 3 ~C 20 hetero-bicycioalkyl ring: or a C4-C20 hetero-tricyc!oa!kyi ring.

[004] For the indenonaphthopyran represented by Formula (HI), and in accordance with some further embodiments, 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),

[095] With reference to Formula (IVA), each -Y- is independently chosen for each occurrence from -CH 2 ~, -CH(R 13 , -C(R 13 . -CH(aryl)-, ~C(ary¾-, and - CiRia'Xaryih and 2 is --Υ--, -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-. [09β] For the indenonapht opyran represented by Formula (Iff), and in accordance with some furthe embodiments, 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):

[097] With reference to Formulas (IVB) and (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.

[098] For the indenonaphthopyran represented by Formula (III), and in accordance with some additional embodiments, 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

[099] in accordance with some embodiments, and with further reference to the indenonaphthopyran represented by Formula (ill), two adjacent R 7 groups, or two adjacent R 8 groups, Independently together form a group represented by one of the following Formulas (IVD) and (IVE):

}j With reference to Formulas (IVD) and (IVE), T and T are each Independently oxygen or the group -NRn'-, where R^', R 15> and R 16 are as set forth above,

[0101 In accordance with some further embodiments, and with further reference to the indenonaphthopyran represented by Formula (III), R s and R 10 are each independently selected from the following classes of groups (i) through (v). [0102] With some embodiments, F¾ 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.

[0103] With some embodiments, F½ 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.

[0104] With some embodiments, 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

8, said subsfituent being connected to an aryl group which Is a member of a photochromic material

[0105] With some embodiments, 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 alkyl or C C 2 o alkoxy,

[0106] With some embodiments, (v) 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

[0107] In accordance with some additional embodiments, and with further reference to the indenonaphthopyran represented by Formula (Hi), 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 substitueni R; an unsubstituted, mono-, di-, or t i-subsiituted phenyl or aryi group; 9-jubiidinyl; or an unsubstituted, mono- or di-substituted heteroaromatic group chosen from pyridyi, furany!, benzofuran-2-yl, benzofuran-3-yi, thieny!, benzothien-2-yi, benzothien-3-yl, dibenzofuranyi, dibenzothienyi, carbazoyl, benzopyridyl, indofinyl, and fluorenyi.

[0108J The 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 o)alkyi or C C 20 habaikyl, R 23 and R 24 are each independently C C 20 alkyl, G 5 -C 10 cycloaikyl, phenyl or substituted phenyl, the phenyl substituents being CrC 20 aikyl or C C 2 o aikoxy, and said halo substituent is chloro or f!uoro, aryl, mono(CrC 2 o)alkoxyaryl, di{CrC 20 )a!koxyaryl, monQ(CrC 20 )alkylaryi, di(C r - C 20 )alkylaryi, haloaryl, C 3 -C 10 cycioalkylaryi, C3-C10 cycloaikyl, C3-C10 eycloaikyioxy, C 3 -C 0 cycloalkyioxy{CrC 2 o)aiky!, C 3 -C 10 cyc!oalkyloxy{CrC2c)alkoxy, aryi(C C 20 )alkyl, aryl(Cr-C 2 o)alkoxy, aryloxy, ary!oxy{C r C 20 )alkyi, aryloxy(C C 2 o)a!koxy, mono- or di{Ci ½o)alkyiary!(CrC2o)a!kyl, mono- or di~(GrC2o)alkoxyary!{Ci-C2 0 )aikyl ( mono- or di~(CrC 2 o)aikyiary!{C 1 -C 2 o)aikoxy, mono- or di~(CrC 2 o)a!koxyary!(Cr C 2 o)aikoxy, amino, mono- or di~{C r C 20 )alky1amino, diarylamino, piperazino, N-(Cr C2o)alkylpiperazino, N-ary!piperazino, aziridino, indoiino, piperldino, rnorpholino, thiomorphoiino, tetrahydroquinoiino, tetrahydroisoquinoiino, pyrroiidyi, Ci-C 20 alkyl, C1-C20 habaikyl, C Cj. 0 aikoxy, mono(C C2o)aikoxy(CrC2o)aikyl, acryloxy, methacry xy, acy!oxy(Ci-C 6 alkyl), acybxy(C 3 -C 7 cycloaikyl), acyloxy(aryl), or halogen,

[0109] in accordance with some alternative embodiments, and with further reference to the indenonaphthopyran represented by Formula (HI), 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. [0110] In accordance with some alternative embodiments, and with further reference to the indenonaphthopyran represented by Formula (HI), B and B' are each independently a group represented by one of:

[0111] With reference to the formulas immediately above, K is -CH 2 - or -0-„ 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.

[0112] in accordance with some alternative embodiments, and with further reference to the indenonaphthopyran represented by Formula {III}, B and B' are each Independently, a group represented by:

[0113] With reference to the formula Immediately above, ί½ is hydrogen or C C 2 Q alkyi, and 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.

[0114] In accordance with some embodiments, B and 8', of Formula (lii), taken together form one of a fiuoren-9-yiidene, mono-, or di-substituted fluorerv-9-yiidene, each of said fiuoren-9-y!idene, in which the substiiuents are each independently chosen from C r -C 20 alkyi, C C 2 o aikoxy, and halogen.

[0115] With some embodiments, R 7 Independently for each x and R 8 independently for each y, of the indenonaphthopyran represented by Formula (ΠΙ), 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 '.

[0116] With some further embodiments, 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,

[0117] With some additional embodiments, 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.

[0118] As previously discussed with regard to the indenonaphthopyran represented by Formula (ill): 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,

[0119] Each compatibiiizing substituent can independently be represented by one of the following:

-A'-D-E-G-J (XIII); -G-E-G-J (XVI}; -D-E-G-J (XIX);

-A'-D-J (XIV); -D-G-J (XVII); ~D~J {.XX};

.A'-G-J (XV); -G-J (XVill); and -A'-J (XXI). 012O] With formulas (Xlii) through (XXI), non-!imiting examples of groups that - A'- can represent according to various non-limiting embodiments disclosed herein include -0-, -C{=0)-, ~CH 2 ~, -OC{~0)- and -NHCi 0)-, provided that if -A ' -- represents -0-, -A'- forms at least one bond with -J.

[0121] 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 a bond with -A'-, or a substituent or an available position on the indenonaphthopyran. [0122] Non-limiting examples of suitable diamine residues that -D-- can represent include an aliphatic diamine residue, a cyclo aliphatic diamine residue, a

diazacycioaikane residue, an azacycio aliphatic amine residue, a diazacrown ether residue, and an aromatic diamine residue, More particular, illustrative and non- limiting examples of diamine residues that can be used in conjunction with various non-iimtting embodiments disclosed herein include the following:

[0123] 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:

[0124] With continued reference to formulas (XI !i) through (XXI) above, according to various non-limiting embodiments disclosed herein, -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-. Non-limiting examples of 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:

'

[0126] According to various non-limiting embodiments disclosed herein, -G- can represent a group represented by the following general formula,

-i(OC 2 H 4 ) x (OC 3 He) y (OC 4 H 8 )j-0- in which 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 8 5 y (OC 4 H 8 }j~{ }, and the second polyol oxygen forms a bond with -E- or -J, Non- limiting examples of suitable polyol residues that -G- can represent include an aliphatic polyol residue, a cycio aliphatic polyol residue and an aromatic polyol residue.

[0126] More particular, illustrative and non-limiting examples of 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. 5, lines 7-33, which disclosure is hereby specifically incorporated by reference herein; (c) poiyefher polyols, such as but not limited to those sel forth in U.S. Patent No. 6,555,028 at col. 5, lines 34-50, which disclosure is hereby specifically incorporated by reference herein; (d) amide-containing polyols, such as, but not limited to, those set forth in U.S. Patent No. 8,555,028 at coL 5, lines 51-62, which disclosure is hereby specifically incorporated by reference; (e) epoxy polyols, such as, hut not limited to, those set forth in U.S. Patent No. 6,555,028 at col. 5 line 83 to col. 6, line 3, which disciosure is hereby specifically incorporated by reference herein; (f) polyhydric polyvinyl alcohols, such as, but not limited to, those set forth in U.S. Patent No, 6,555,028 at col. 6, lines 4-12, which disciosure ts hereby specifically ncorporated by reference herein; (g) urethane polyols, such as, but not limited to those set forth in U.S. Patent No. 6,555,028 at col. 8, lines 13-43, which disclosure is hereby specifically incorporated by reference herein; (h) polyacrylic po!yois, such as, but not iimited to those set forth In U.S. Patent No,. 6,555,028 at col, 6, lines 43 to col. 7, line 40, which disciosure is hereby specifically incorporated by reference herein; (1) polycarbonate poiyoSs, such as, but not Iimited to, those set forth in U.S. Patent No. 6,555,028 at col. 7, lines 41 -55, which disclosure Is hereby specifically incorporated by reference herein; and (j) mixtures of such poiyols.

[01273 With further reference to formulas (X!l!) through (XXI), according to various non-limiting embodiments disclosed herein, -j can represent a group ~K, wherein -K represents a group such as, but not 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, -<¼H 4 S0 3 H and ~S0 3 H, wherein "w" ranges from 1 to 18. According to other non-limiting embodiments -J can represent hydrogen that forms a bond with an oxygen or a nitrogen of linking group to form a reactive moiety such as -OH or -NH. For example, according to various non-limiting embodiments disclosed herein, -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-.

[0128] According to still further non-limiting embodiments, -J can represent a group -L or residue thereof, wherein ~L can represent a reactive moiety. For example, according to various non-iimittng embodiments disclosed herein -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. As used herein, the terms acryi, methacryi, crotyl, 2- (methacryioxy)eihyicarbamyi, 2-(methacryloxy)ethoxycarbonyi, 4-vinyiphenyi, vinyl, 1-chiorovinyl, and epoxy refer to the following structures: 4-vijiylpliei X

i epoxy

0129] As previously discussed, -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! groups with a precursor of -A'-, such as a carboxylic acid or a methylene halide, a precursor of poiyaikoxyiated group, such as polyalkyiene glycol, or a hydroxyl subsstituent of the indenonaphthopyran. 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 . ¾ , wherein q is the backbone or main chain of the polyhydroxy compound and "a" is at least 2.

)] Further, as discussed above, one or more of the polyol oxygens of -G- can form a bond with -J (i.e., forming the group -G~J). For example, although not limiting herein, wherein the reactive and/or compatib!izing substliueni comprises the group -G-J, if -G- represents a polyol residue and ~j represents a group -K that contains a carboxyl terminating group, -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. 6,555,028, which disclosure is hereby specifically incorporated by reference herein) to produce a carboxy!ated polyoi residue. Alternatively, if -J represents a group ~K that contains a sulfa or suifono terminating group, although not limiting herein, -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. Further, although not limiting herein, If -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.

{0132] 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.

[0133] 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. With some additional further embodiments, 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.

{0134] Each polymer of the polymer composition of the present invention can independently be a thermoplastic polymer or a curable polymer. When 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.

{01353 in accordance with some embodiments of the polymer composition of the present invention: 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 . ent bonds with the first reactive group(s) of the polymer, [0136] In accordance with some embodiments of the polymer composition of the present invention: 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. With some further embodiments, 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.

[0137] The crosslinking agent, with some embodiments, 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).

10138] With some embodiments, 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.

[0139] Examples of isocyanate functional materials from which the crosslinking agent ca be selected, with some embodiments, 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;

tsophorone diisocyanate; ethylene diisocyanate; dodecane-1 , 12~diisocyanaie;

cyclobutane-1 ,3-diisocyanate; cyciohexane-1 ,3-diisocyanate; cyc!ohexane-1 ,4- diisocyanate; methyl cyciohexyf diisocyanate; hexahydrotoluene-2,4-diisocyanate; hexahydrdtoluene-2,6-ditsocyanate hexahydrophenyiene-1 ,3-diisocyanate;

hexahydrophenylene- 1 ,4-diisocyanate; perhydrodiphenyirnethane-2,4'"diisocyanate; perhydrodiphenylmethane~4,4'-diisocyanate and mixtures thereof.

[0140] 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.

[0141] 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.

|01421 With some embodiments of the present invention, the poiyisocyanate functionai polymer is a poiyisocyanate functional poiyurefhane prepared from aliphatic diols and aliphatic diisocyanates. Optionally, 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. [0143] As used herein, by "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. In the case of TMP and IPDI, by employing art-recognized starved feed and/or dilute solution synthesis techniques, an oligomeric adduct having an average isocyanate functionality of 3 can be prepared ("T P-3IPDI").

[0144] Depending on the type of active hydrogen group containing compound(s) used (e.g., polyois, poiyamines and pofythiols) 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.

[0145] 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.

[0146] 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. Specific examples of 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. W th some embodiments, 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.

[0147] 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.

[0148] Ketoximes useful as capping groups Include those prepared from aliphatic or cycloaliphatic ketones. Examples of 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-tnmetbyi~2-cyc!ohexene~5~one oxime.

[0149] Examples of 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.

[0150J Oxirane functional crosslinking agents can be prepared by reacting a hydroxy! functional material having at least two hydroxy! groups with a

2-(hafomethyl)oxfrane, such as 2-{ch!oromeihy!)oxirane, which is also referred to as epich!orohydrin. Examples of 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-diol, 1 ,4-dimethy!olcyclohexane, 2,2,4- trimethylpeniane dio!, 4,4'-{propane-2 1 2-diyl)dsphenol, and 4 s 4 , -methylenediphenol.

[01S1J The oxirane functional crosslinking agent can be a polymeric material. With some embodiments, 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 feast two active hydrogen groups, such as at Ieast two hydroxy! groups. Examples of 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,

[0152] The polymer, with some embodiments, 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. With some further embodiments, 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.

[01531 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.

[0154] 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.

[0155] in accordance with some embodiments, 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. Examples of such 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. With some embodiments, 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,

[0156] To achieve a suitable level of cure with the polymer composition of the present invention, 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. [0157] 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. As used herein, by "cured" 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.

{01581 The polymer compositions of the present Invention can also, with some embodiments, include pigments and fillers. Examples of 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. Examples of fillers include, but are not limited to: silica, such as precipitated silicas; clay; and barium sulfate. When used In the polymer compositions of the present invention, 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).

[0159] 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. Examples of 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).

[0180] The polymer compositions of the present can, with some embodiments, include solvents, selected from water, organic solvents, and combinations thereof,

[01611 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. , tetrahydrofuran and dioxane; 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 ,3~dimeihyi-2-imi.dazo!idinone; and sulfur containing compounds -such as thiog!ycoi, dimethyl sulfoxide and tetra methylene suifone.

[01621 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,

[0163J With some embodiments, the polymer composition includes an additive- selected from heat stabilizers, light stabilizers, and combinations thereof. Examples of 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).

[0184] The present invention also relates to meehanocbromie articles that include the polymer composition of the present invention as described previously herein. With some embodiments, the mechanochromic article is selected from films, sheets, and 3-dimenslonal articles. [010S] 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.

[0186] The mechanochromic articles of the present Invention, with some embodiments, are selected from ophthalmic articles, and the ophthalmic articles are selected from corrective lenses, non-corrective lenses, contact lenses, and magnifying lenses. As used herein the term "ophthalmic" means pertaining to or associated with the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses, including single vision or 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.

[0167] The mechanochromic articles of the present invention, with some embodiments, are selected from display articles, and the display articles are selected from screens, monitors, and security elements. As used herein the term "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.

[0168] The mechanochromic articles of the present invention, with some embodiments, are selected from protective articles, and the protective articles are selected from protective lenses, protective visors, protective headgear, and protective housings. Examples of 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. Examples of 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. Examples of protective headgear 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. Examples of 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).

[0169] 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,

[0170] The mechanochromic article of the present invention, with some embodiments, 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.

[0171] The mechanochromic article of the present invention, with some embodiments, 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.

[0172] With some embodiments, 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. With some embodiments 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. 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. With some embodiments, and for purposes of non-limiting Illustration, 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.

[0173] There is also provided 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. With some embodiments, and for purposes of non-limiting illustration, 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.

[0174] The present Invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations therein will be apparent to those skilled in the art. Unless otherwise specified, all parts and percentages are by weight,

EXAMPLES

The examples of 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

Exam pie 1.

Into a 2oz jar flushed with Nitrogen was added 3-phenyl-3-(4~(2- hydroxyethoxyp enyl))~6,7~dimethoxy-13-ethyi-13-(2-hydrGxyethoxy)-3,13-dihy dro- irrdenO: 2 i ,3 , :3.4]naphtho[1 l 2~b]pyran (0.56g, 1 equiv), inethyiamine (0.28g, 3.1 equiv), and dichlorornethane (10.2g). This mixture was cooled in a dry ice/ethanol bath, and a solution of 2-bromopropionyi bromide (0.58g, 3 equiv) in dichlorornethane (1.5g) was added. The jar was resealed and allowed to warm to room temperature. After stirring for 18 hours, 10mL of water was added. The layers were separated, arid the aqueous layer was extracted three times with dichlorornethane. The combined organic layers were washed with saturated sodium bicarbonate, dried over gS0 4 , and concentrated under vacuum. The residue was filtered through a piug of silica, eiuting with dichlorornethane. After concentration of the eiuent, 0.83g of a brown oil was obtained, which was consistent with 3-phenyl~3-(4-(2-{2- romopropionato)ethoxyphenyi))-6, 7-dimethoxy-13-ethyM 3-(2- bromopropionatoethoxy)-3, 13-dihydro-indeno[2 , ,3':3,4]naphi o{1 ,2-b]pyran by 1 H a d 13 C N R.

Example 2.

A solution of 1-nitroso-2,3-dihydroxynaphthaiene, (1.08g) in 13.75 mL of 1 ,2- dichloroethane was charged to a round bottomed flask and warmed to reflux. A mixture of 5-hydroxy-1 , 2,3, 3-ietramethyi-3H-indoM -turn iodide (1 .74g} and

triethyiamine {1 , 15g) was added dropwise. The resulting dark solution was refiuxed for 1 hour, then cooled to room temperature and a blue product was collected via filtration. This was immediately placed into a Nitrogen-flushed 2oz jar. To the jar was added triethyiamine (2.88g), and dichloromethane (6.5 mL). This mixture was cooled in a dry ice/ethanol bath, and a solution of 2-bromoisobutyryi bromide (3.94g) in dichloromethane (1 .5 ml) was added. The jar was resealed and allowed to warm to room temperature. After stirring for 2 hours, the residue was dry packed onto a 6 Inch by ¾ Inch silica plug and eluted with 500 mL of a 2:1 solution of

dichloromethane:heptanes, increasing to 5:1 dich!orornethane:heptanes. The filtrate was concentrated, then the residue was purified by column chromatography with an e!ution gradient of 1:1 dich!oromethane:heptanes, up to 4:1

dichioromethane:heptanes on silica, to provide 1 1 3 ( 3 rimethylspiro[indoiine~2 t 3'~ naphtho[2, 1 -bj 1 ,4]oxazine]-5,5 -diyl bis(2-bromo-2-methylpropionate) as a dark brown solid which was photochromic upon exposure to UV irradiation.

Into a 20 mL scintillation vial was charged 3-(4-methoxyphenyl)-3~(4~{2~

hydroxyethoxyphenyl))~6J-dfmethoxy-11 ~carboxy~13, 13-dimethy!-3, 13-dihydro- ,2-bjpyran (0.1323g), dicyclohexy!carbodiimide (DCC, 0.044g), ethylene glycol (0.57g), dimethyiaminopyridine (0.00 3g), and

dichforomeihane (3.2 ml) The resulting solution was stirred at room temperature for 3 hours, at which time TLC analysis (100% ethyi acetate} on silica gel indicated complete consumption of starting material. The reaction was partitioned between dichloromethane and water, and the layers were separated. The organic layer was washed with water, dried over sodium sulfate and concentrated, yielding a green solid. This material wa§ then converted to the initiator according to the general procedure in example 2, using 0.19g of bromoisobutyry! bromide, 0.103g

triethyiamine and 3 mL of dlchioromethane (1.5 mL). Purification via column chromatography (methylene chloride, siiica gel) yielded 0.1 1g of a photochromic compound consistent with 3-(4-metho) phenyi)-3-{4-(2-bromo-2- methy!propionato)ethoxyphenyi))-6,7-dimeihoxy-1 1--(2--bromo~2~

methy!propionatoethoxyoxyi) -13, 13 « dimethy!-3,13-cJihydro- indeno{2 , ,3 ! :3,4]naphtho[1 ! 2-b]pyran by 1 and 13 C NMR.

3-{4~2-hydroxyethoxyphenyi)-3~{4-meihoxyphenyi)-6-methoxy-&g t;7-{3~

hydroxymethyl)piperidin-1 -yl)-13, 13-dimeihyi-3, 13-dshydro- !ndenol2' ; 3 , ;3 i 4]naphtho[1 ,2-b]pyran (0.038g) was placed into a Nitrogen-flushed 2 oz jar. To the jar was added triethy!amine (0.028g), and dichloromeihane (1g). This mixture was cooled in a dry ice/ethanol bath, and 2~bromoisobutyryi bromide (0.05g,) in dichforomethane (1g) was added. The jar was reseaied and allowed to warm to room temperature. After stirring overnight, the reaction was diluted with 4m L of water. The layers were separated, and the aqueous layer was extracted three times with dlchioromethane. The combined organies were dried over gS0 4 , and concentrated under vacuum. The residue purified by column chromatography (silica gel) using an eiution gradient from 100% cyciohexane to 1 :1 cyc!ohexane:dieihyl ether. After concentration of the eiuent, 3.4mg of 3-(4-(2-bromo-2- methylpropionylethoxypheny1)--3-(4-meihoxypheny!)--6~rnethox y--7-(3-(2-bromO"2~ methy[propionyloxymethyi)piperidin-1~yl)-13, 13-dimethyi-3,13-dihydro- indeno[2 ! ,3':3,4]naphtho[1 ,2-b3pyran was obtained as a photochromic solid. Example 5.

3~{4--(3" ydroxymethylpiperidsn-1 -y }-'3-p enyl--6-methoxy-7-{3"

hydroxymethyl)piperidin~1 -yl)-11 -bromo-13, 13~dimetbyi-3, 13-dihydro- indenop^S^S.^naphthoh .S-blp ran (0.1g) was placed into a Nitrogen-flushed 25 ml round bottomed flask. To the flask was added dichioromethane (1.5g), then the mixture was cooled in an ice water bath. Triethyiamine (0.0647g) was added, followed by 2-bromoisobutyry! bromide (0.088g,). The flask was allowed to warm to room temperature. After stirring overnight, the solvent was removed and the residue was redissoived in diethyl ether. The safe were removed via filtration, and the eiuent was concentrated. The residue was filiered through a short silica column to provide 3~{4~(3~(2-bromo-2'methy!prop!onyioxymethy!)piperidin-1-yl)) -3-phenyi-6-rnethoxy-7~ (3~(2-bromo-2-rrieth.ylpropionyioxymethyi)pip8ridin-1-yl)-1 1 -bromo-13, 13-dimethyl- 3,13-dihydro-irx1eno[2\3 :3,4]naphiho[1 ,2-b]pyran (0.1 16g, 84%) as a bluish-black photochrome solid.

Part 2, Preparation of polymer dyes by controlled radical polymerization

Example 6.

Into a f!ask Immersed in a room temperature water bath was placed the initiator 3- phenyl-3-(4-(2-(2-bromoproptonato)ethoxyphenyl))-6, 7-dirnethoxy-13-ethy 3-{2- bromoproplonatoethoxy)"3,1 S-dihydro-sndenop'^'^^jnaphtho l ,2-bjpyran of Example 1 (0.1 g, 1 equiv), Cu metal (0.03g, 4 equivs), tris(2~ dimethylarninoethyl)amjne (0.1 g, 4 equivs), and dry DMSO (10.7 mL). The resulting mixture was purged with dry Nitrogen for 20 min. Methyl acryiate {21.3g, 2500 equsvs) was filtered through a plug of alumina, purged with Nitrogen for 20 minutes, then added to the flask. The mixture was allowed to stir overnight at room temperature, after which a significant increase in viscosity was observed. The materia! was dissolved in tetrahydrofuran (THF, 20.7g) and stirred open to the atmosphere for 5 minutes, at which time the viscous solution was filtered. The polymer was purified by precipitation into methanol. The off-white polymer was collected and dried under vacuum. ! he resulting polymeric compound was found to be reversibly photochrome under UV irradiation.

Example 7.

Into -a flask immersed in a room temperature water bath was placed the Initiator 1.S.S-trimeth ispiroiindoiine^^'-Ffa htho^, 1 -b][1 ,4]oxazine]-5,5'-diyl bis(2~bromo-2- methylpropionate) of Example 2 (0.5g, 1 equlv), Cu metal (0.029g, 2 equivs), tris(2- dimethylaminoeihy amine (0,79 g, 2 equivs), and dry butyl acetate (1.3 ml). The resulting mixture was purged with dry Nitrogen for 20 min. Methyl acryfate (0.73, 37 equiv) and hydroxypropyl acrylate (0.96g, 33 equlv) were then added to the flask. The mixture was allowed to stir overnight at room temperature, after which a significant Increase in viscosity was observed. The material was dissolved in THF (20.7g) then filtered through a plug of glass wool. To the filtrate was added approximately 2g of AM8 . ERLITE® IRC-748 (an ion exchange resin available from Dow Chemical) and 4 drops of acetic acid. This was stirred for 1 h, then filtered and concentrated to yield a thick oil. 1 H NMR was consistent with the expected polymerization product containing the residue of the initiator of Example 1. The resulting polymeric material was found to be reversibly photochrome under UV irradiation.

Example 8.

The initiator 3-(4-methoxypheny!)-3-{4-(2-bromo-2-methyipropionato)ethoxyp henyi))- 6,7-dimethoxy-l 1 -(2-bromo-2-m . ethyipropionatoethoxyoxyi) -13, 13-dimethyl-3, 13~ dihydro~indenoi2 ! ,3';3 i 4]naphtho[1 i 2-b]pyran of 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.

Example 9.

The initiator 3-(4~(2'bromo-2-methylpropfonylethoxyphenyl)-3-(4-methoxyphe nyl)-6- methoxy-7-{3 2-bromo-2-methy!propiony!oxyrnethy!)piperidin-1-yl)-13, 13-dimethyl- 3, 13-dihydro-indeno[2',3':3,43naphtho[1 ,2-b]pyran of Example 4 (13.4 mg) was subjected to the polymerization conditions described in Example 6 except that 0.0035g Cu, 0.013g tris{2-dimethyiaminoethyi)amine, 1.9g of methyl acrylate, and 1.2g of DMSO was used. Gel Permeation Chromatography in THF indicated a peak MW of 163569 (theory 140,000) relative to a linear polystyrene standard. Example 10,

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.

Example 1.

The initiator 3-(4-(3"(2-bromo-2*methy!propiony!oxymethyi)piperidin-1 -y1)}-3-phenyl~8- methoxy-7-(3-{2-bfomo-2-methy!propionyioxymethyl)piperid.in- 1 -yi)-11 -bromo-13, 13- di.methy!-3, 13-dihydr -indenoi2' ! 3':3,4]naphthon ,2-bjpyran of Example 5 (0.0815g) was placed into a flask immersed in a room temperature water. To this was added Cu powder (Q.Q096g), tris(2-dimet yiaminQethyi)amtne {0.027 g), and dry butyl acetate (1.0 mL), The resulting mixture was purged with dry Nitrogen for 10 minutes, Methyl acrylate (0.24) and hydroxypropy! acrylate (0.242g) were then added to the flask. The mixture was allowed to stir overnight at room temperature, after which no significant increase in viscosity was observed. The mixture was then heated to 70°C and stirred for six hours, then cooled and stirred overnight. The resulting material was dissolved in THF {10mL) then filtered through a plug of glass wool. To the filtrate was added approximately 2g of AMBERLITE IRC-748 resin and 4 drops of acetic acid. This was stirred for 1 h, then filtered and concentrated to yield a thick oil. The resulting material was found to be reverslfaly photochromic under UV irradiation.

Example 12.

3-{4-{3-hydroxyrnethyi)piperidtn-1 -yi))-3-phenyi-6~methoxy-7-(3- hydroxymethy! )piperidin-1~yl)-11 -bromo-13, 3-dimetfiy!-3, 13-dihydro- indenoi2',3':3 ! 4inaphtho[1 ,2-b]pyran (0,22g) , toluene (6.58g) and epsHon- caproiactone (0.58g) were added into a 20mL glass vial, The glass vial was placed on a hot plate with magnetic stirring, set to 108°C. After stirring for 30 minutes, a dark solution was formed, and then 0.09g diphenyl phosphate was added to the glass vial. When the concentration of epsilon-caprolactone was be tow 0.1 % as measured by gas chromatography, the reaction solution was cooled to room temperature,, and of triethylamine (G.14g) was added. The mixture was stirred at room temperature tor 30 minutes, then 10mL of dich ' toromethane was added, and the mixture was washed with deionized water three times. The organic layer was dried over sodium sulfate, and a wax material was obtained upon removal of solvent.

Part 3. Preparation and testing of mechanochromic films and coatings.

Example 13.

According to the amounts in Table 1 , 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.

Table 1.

Parts by

M teri weight

Polymer from Example 7 0,8

,4-diazabicyclo[2.2.2]octane (DABCO) 0.06

anhydrous tetrahydrofuran (THF) 9.68

DESMODUR® W 1 25,75

PolyTHF 250 2 62.44

2 poly tetrahydrofuran of molecular weight approximately 250

Example 14-17,

The following examples demonstrate the preparation of coating compositions and coatings that were tested for mechanochromic activity.

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.

Table 2.

Example Example Example Examp e

Material 1 15 16 17

Paris by Parts by Parts by Parts by

Charge 1 weight eight y weight weight

Polymer dye from Example 12 0.00 6,74 0.00 0.00

Hydroxyi-functionai indeno compound 1 6.15 0.00 0.00 0.00

Polymer dye from Example 1 1 0.00 0.00 6.15 0.00

Polymer dye from Example 7 0.00 0.00 0.00 7.54

T1 UVIN®144 2 0.0.0 2.25 0.00 2,51

N- ethyl-2-pyrroiidone (NMP) 23.66 10.02 23.66 8.89

IRGANOX® 245 3 0.00 2.25 0.00 2.51

Charge 2

!PDi PL 340 34.57 42.49 34.57 42 37 '

Charge 3

Acrylic polyol 6 14.37 17.66 14,37 17.61

PH200D 6 12.57 15.45 12.57 15.41

Charqe 4

BYK® 333 (10% in NMP) 7 0.32 0.40 0.32 0.32

Κ-ΚΆΤ® 348 8 0.47 0.52 0.47 0.52

SILQUEST® A-187 epoxy si!ane 9 2.05 2.59 2.05 2.58

S^echanicaSiy active NO YES HQ YES

: 3-(4-2-hydroxyethoxyphenyf)-3-(4-hydfoxyphenyf)-6-methoxy-7- (3- ydroxyoxymethyf)piperidin-1 -yl}-13, 13~ciirnethyi~3, , 13-dihyd ro--l ndeno[2' , 3 : : :3,4]naphtho[ 2- b]pyran

2 A Hindered Amine Light Stabilizer available from 8ASF

J An antioxidant available from BASF Corporation

4 A diisocyanate available from Bayer Corporation

3 An acrylic polyol comprised of 20.7% friphenylphosphite, 41 .3% tertiary-dodecyl rnercapian,

8% acrylic acid, 13% n-buty! me hacryfate and 17% hydroxypropyl methacryiate, at 60%

solids in glycol acetate solvent, with a molecular weight of 5500.

6 A polycarbonate dioi available from Ube Corporation

' Polyether-modified po!ydimethytsi!oxane available from BYK Chemie

6 Bismuth-based catalyst available from King Industries, Inc.

9 Epoxy silane available from Mornentive Performance Chemicals

Polycarbonate CR39 substrate with an area of 4 square inches (obtained from

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

baked at 125°C for 1 hour. [0175] Mechanical activity was determined by rubbing the coated surface with a sharp or blunt object and observing a visible color change. Mechanical activation for Examples 17, 19, and 20 was observed upon cutting the surface with the tip of a paperclip. Mechanical activity with example 18 was observed upon rubbing the surface with a blunt object, then activating with UV light. Example 18 demonstrates that it is possible to have combined mechanochromic-photochromsc activation,

[0176} The present invention has been described with reference to specific details of particular embodiments thereof. It is not intended that such details be regarded as limitations upon the scope of the invention except insofar as and to the extent that they are Included in the accompanying claims.