US 7,582,749 B2 · Photochromic compounds

Abstract

Various non-limiting embodiments disclosed herein relate generally to photochromic compounds, which may be thermally reversible or non-thermally reversible, and articles made therefrom. Other non-limiting embodiments relate to photochromic-dichroic compounds, which may be thermally reversible or non-thermally reversible, and articles made therefrom. For example, one non-limiting embodiment provides a thermally reversible, photochromic compound adapted to have at least a first state and a second state, wherein the thermally reversible, photochromic compound has an average absorption ratio greater than 2.3 in at least one state as determined according to CELL METHOD. Another non-limiting embodiment provides a photochromic compound comprising: (a) at least one photochromic group chosen from a pyran, an oxazine, and a fulgide; and (b) at least one lengthening agent L attached to the at least one photochromic group and represented by the formula—[S1]c-[Q1 —[S2]d]d′-[Q2 —[S3]e]e′-[Q3 —[S4]f]f′—S5—P, which is described herein.

A non-thermally reversible photochromic compound represented by one of Formula X and Formula XI:

wherein:
(a) A is chosen from naphthol benzo, phenanthro, fluorantheno, antheno, quinolino, thieno, furo, indolo, indolino, indeno, benzofuro, benzothieno, thiopheno, indeno-fused naphthol, heterocyclic-fused naphthol, and heterocyclic-fused benzo;
(b) Y′ is chosen from:
—(Y1)C═C(Y2)—, —O—, —S—, —S(O)(O)—, and —N(X7)—, wherein Y1 and Y2 together form benzo, naphtho, phenanthro, furo, thieno, benzofuro, benzothieno and indolo, and X7 is chosen from:
(i) a lengthening agent L, hydrogen, C1-C12 alkyl, C1-C12acyl, phenyl(C1-C12)alkyl, mono(C1-C12)alkyl substituted phenyl(C1-C12)alkyl, mono(C1-C12)alkoxy substituted phenyl(C1-C12)alkyl;
C1-C12alkoxy(C1-C12)alkyl;
C3-C7 cycloalkyl;
mono(C1-C12)alkyl substituted C3-C7 cycloalkyl, C1-C12 haloalkyl, allyl, benzoyl, mono-substituted benzoyl, naphthoyl or mono-substituted naphthoyl, wherein each of said benzoyl and naphthoyl substituents are independently chosen from C1-C12 alkyl, and C1-C12 alkoxy;
(ii) —CH(X8)X9, wherein X8 is chosen from a lengthening agent L, hydrogen or C1-C12 alkyl;
and X9 is chosen from a lengthening agent L, —CN, —CF3, or —COOX10, wherein X10 is chosen from a lengthening agent L, hydrogen or C1-C12 alkyl;
(iii) —C(O)X6, wherein X6 is chosen from at least one of:
a lengthening agent L, hydrogen, C1-C12 alkoxy, phenoxy that is unsubstituted, mono- or di-substituted with C1-C12 alkyl or C1-C12alkoxy, an aryl group that is unsubstituted, mono- or di-substituted with C1-C12 alkyl or C1-C12alkoxy, an amino group that is unsubstituted, mono- or di-substituted with C1-C12 alkyl, and a phenylamino group that is unsubstituted, mono- or di-substituted with C1-C12 alkyl or C1-C12 alkoxy;
(iv) tri(C1-C12)alkylsilyl, tri(C1-C12)alkoxysilyl, di(C1-C12)alkyl(C1-C12alkoxy)silyl, or di(C1-C12)alkoxy(C1-C12 alkyl)silyl;
(c) B is chosen from:
(i) hydrogen, C1-C12 alkyl, C2-C12 alkylidene, C2-C12alkylidyne, vinyl, C3-C7 cycloalkyl, C1-C12 haloalkyl, allyl, halogen, and benzyl that is unsubstituted or mono-substituted with at least one of C1-C12alkyl and C1-C12 alkoxy;
(ii) phenyl that is mono-substituted at the para position with at least one substituent chosen from:
C1-C7 alkoxy, linear or branched chain C1-C20 alkylene, linear or branched chain C1-C4 polyoxyalkylene, cyclic C3-C20 alkylene, phenylene, naphthylene, C1-C4 alkyl substituted phenylene, mono- or poly-urethane(C1-C20)alkylene, mono- or poly-ester(C1-C20)alkylene, mono- or poly-carbonate(C1-C20)alkylene, polysilanylene, polysiloxanylene and mixtures thereof, wherein the at least one substituent is connected to an aryl group of a photochromic material;
(iii) —CH(CN)2 and —CH(COOX1)2;
(iv) —CH(X2)(X3);
(v) an unsubstituted, mono-, di-, or tri-substituted aryl group;
9-julolidinyl;
or an unsubstituted, mono- or di-substituted heteroaromatic group chosen from pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl, or fluorenyl;
wherein each substituent is independently chosen for each occurrence from:
(A) a lengthening agent L;
(B) —C(O)X6;
(C) aryl, haloaryl, C3-C7 cycloalkylaryl, and an aryl group that is mono- or di-substituted with C1-C12 alkyl or C1-C12 alkoxy;
(D) C1-C12 alkyl, C3-C7 cycloalkyl, C3-C7 cycloalkyloxy(C1-C12)alkyl, aryl(C1-C12)alkyl, aryloxy(C1-C12)alkyl, mono- or di-(C1-C12)alkylaryl(C1-C12)alkyl, mono- or di-(C1-C12)alkoxyaryl(C1-C12)alkyl, haloalkyl, and mono(C1-C12)alkoxy(C1-C12)alkyl;
(E) C1-C12 alkoxy, C3-C7 cycloalkoxy, cycloalkyloxy(C1-C12)alkoxy, aryl(C1-C12)alkoxy, aryloxy(C1-C12)alkoxy, mono- or di-(C1-C12)alkylaryl(C1-C12)alkoxy, and mono- or di-(C1-C12)alkoxyaryl(C1-C12)alkoxy;
(F) amido, amino, mono- or di-alkylamino, diarylamino, piperazino, N—(C1-C12)alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl, hydroxy, acryloxy, methacryloxy, and halogen;
(G) —OX7 or —N(X7)2;
(H) —SX11, wherein X11 is chosen from a lengthening agent L, C1-C12alkyl, an aryl group that is unsubstituted, or mono- or di-substituted with C1-C12alkyl, C1-C12alkoxy, or halogen;
(I) a nitrogen containing ring represented by Formula i:
wherein
(1) n is an integer chosen from 0, 1, 2, and 3, provided that if n is 0, U′ is U, and each U is independently chosen for each occurrence from —CH2—, —CH(X12)—, —C(X12)2—, —CH(X13)—, —C(X13)2—, and —C(X12)(X13)—, wherein X12 is chosen from a lengthening agent L represented by Formula I above and C1-C12 alkyl, and X13 is chosen from a lengthening agent L represented by Formula I above, phenyl and naphthyl, and
(2) U′ is chosen from U, —O—, —S—, —S(O)—, —NH—, —N(X12)— or —N(X13)—, and m is an integer chosen from 1, 2, and 3, and
(J) a group represented by Formula ii or iii:
wherein X14, X15, and X16 are independently chosen for each occurrence from a lengthening agent L, C1-C12 alkyl, phenyl or naphthyl, or X14 and X15 together form a ring of 5 to 8 carbon atoms;
p is an integer chosen from 0, 1, or 2, and X17 is independently chosen for each occurrence from a lengthening agent L, C1-C12 alkyl, C1-C12 alkoxy, or halogen;
(vi) an unsubstituted or mono-substituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolidinyl, phenothiazinyl, phenoxazinyl, phenazinyl, or acridinyl, wherein each substituent is independently chosen from a lengthening agent L, C1-C12 alkyl, C1-C12 alkoxy, phenyl, hydroxy, amino or halogen;
(vii) a group represented by Formula iv or v:
(A) V′ is independently chosen in each formula from —O—, —CH—, C1-C6 alkylene, and C3-C7 cycloalkylene,
(B) V is independently chosen in each formula from —O— or —N(X21)—, wherein X21 is from a lengthening agent L represented by Formula I above, hydrogen, C1-C12 alkyl, and C2-C12 acyl, provided that if V is —N(X21)—, V′ is —CH2—,
(C) X18 and X19 are each independently chosen from a lengthening agent L, hydrogen and C1-C12 alkyl, and
(D) k is chosen from 0, 1, and 2, and each X20 is independently chosen for each occurrence from a lengthening agent L, C1-C12 alkyl, C1-C12 alkoxy, hydroxy and halogen;
and
(viii) a group represented by Formula vi:
wherein
(A) X22 is chosen from a lengthening agent L, hydrogen and C1-C12 alkyl, and
(B) X23 is chosen from a lengthening agent L and an unsubstituted, mono-, or di-substituted group chosen from naphthyl, phenyl, furanyl and thienyl, wherein each substituent is independently chosen for each occurrence from C1-C12 alkyl, C1-C12 alkoxy, and halogen;
and
(d) i is an integer chosen from 0 to 4, and each R2 is independently chosen for each occurrence from:
(i) a group represented by B;
(ii) —C(O)X24;
(iii) —OX7 and —N(X7)2;
(iv) —SX11;
(v) the nitrogen containing ring represented by Formula i;
(vi) the group represented by Formula ii or iii;
(vii) immediately adjacent R2 groups together form at a group represented by Formula vii, viii, or ix:
wherein
(A) W and W′ are independently chosen for each occurrence from —O—, —N(X7)—, —C(X14)—, —C(X17)—,
(B) X14, X15 and X17, and
(C) q is an integer chosen from 0, 1, 2, 3, and 4;
and
(viii) a lengthening agent L;
provided that the non-thermally reversible photochromic compound comprises at least one lengthening agent L and each lengthening agent L is independently chosen for each occurrence from a compound represented by Formula I:
—[S1]c-[Q1-[S2]d]d′-[Q2-[S3]e]e′-[Q3-[S4]f]f′—S5—P I
wherein:
(a) each Q1, Q2, and Q3 is independently chosen for each occurrence from:
a divalent group chosen from:
an unsubstituted or a substituted aromatic group, an unsubstituted or a substituted alicyclic group, an unsubstituted or a substituted heterocyclic group, and mixtures thereof, wherein substituents are chosen from:
a group represented by P, thiol, amide, liquid crystal mesogens, halogen, C1-C18alkoxy, poly(C1-C18alkoxy), amino, amino(C1-C18)alkylene, C1-C18alkylamino, di-(C1-C18)alkylamino, C1-C18 alkyl, C2-C18 alkene, C2-C18 alkyne, C1-C18alkyl(C1-C18)alkoxy, C1-C18alkoxycarbonyl, C1-C18 alkylcarbonyl, C1-C18 alkyl carbonate, aryl carbonate, C1-C18 acetyl, C3-C10 cycloalkyl, C3-C10cycloalkoxy, isocyanato, amido, cyano, nitro, a straight-chain or branched C1-C18 alkyl group that is mono-substituted with cyano, halo, or C1-C18 alkoxy, or poly-substituted with halo, and a group represented by one of the following formulae:
-M(T)(t-1) and -M(OT)(t-1), wherein M is chosen from aluminum, antimony, tantalum, titanium, zirconium and silicon, T is chosen from organofunctional radicals, organofunctional hydrocarbon radicals, aliphatic hydrocarbon radicals and aromatic hydrocarbon radicals, and t is the valence of M;
(b) c, d, e, and f are each independently chosen from an integer ranging from 0 to 20, inclusive;
and each S1, S2, S3, S4, and S5 is independently chosen for each occurrence from a spacer unit chosen from:
(i) —(CH2)g—, —(CF2)h—, —Si(CH2)g—, —(Si[(CH3)2]O)h—, wherein g is independently chosen for each occurrence from 1 to 20;
h is a whole number from 1 to 16 inclusive;
(ii) —N(Z)-, —C(Z)═C(Z)-, —C(Z)═N—, —C(Z′)—C(Z′)-, wherein Z is independently chosen for each occurrence from hydrogen, C1-C6 alkyl, cycloalkyl and aryl, and Z′ is independently chosen for each occurrence from C1-C6 alkyl, cycloalkyl and aryl;
and
(iii) —O—, —C(O)—, —C═C—, —N═N—, —S—, —S(O)—, —S(O)(O)—, straight-chain or branched C1-C24 alkylene residue, said C1-C24 alkylene residue being unsubstituted, mono-substituted by cyano or halo, or poly-substituted by halo;
provided that when two spacer units comprising heteroatoms are linked together the spacer units are linked so that heteroatoms are not directly linked to each other and when S1 and S5 are linked to PC and P, respectively, they are linked so that two heteroatoms are not directly linked to each other;
(c) P is chosen from:
aziridinyl, hydrogen, hydroxy, aryl, alkyl, alkoxy, amino, alkylamino, alkylalkoxy, alkoxyalkoxy, nitro, polyalkyl ether, (C1-C6)alkyl(C1-C6)alkoxy(C1-C6)alkyl, polyethyleneoxy, polypropyleneoxy, ethylene, acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, acryloylphenylene, acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide, epoxy, isocyanate, thiol, thioisocyanate, itaconic acid ester, vinyl ether, vinyl ester, a styrene derivative, siloxane, main-chain and side-chain liquid crystal polymers, ethyleneimine derivatives, maleic acid derivatives, fumaric acid derivatives, unsubstituted cinnamic acid derivatives, cinnamic acid derivatives that are substituted with at least one of methyl, methoxy, cyano and halogen, and substituted and unsubstituted chiral and non-chiral monovalent or divalent groups chosen from steroid radicals, terpenoid radicals, alkaloid radicals and mixtures thereof, wherein the substituents are independently chosen from alkyl, alkoxy, amino, cycloalkyl, alkylalkoxy, fluoroalkyl, cyanoalkyl, cyanoalkoxy and mixtures thereof;
and
(d) d′, e′ and f′ are each independently chosen from 0, 1, 2, 3, and 4, provided that a sum of d′+e′+f′ is at least 1.

81 more elements

Photochromic compounds

Life of this patent

Photochromic compounds

Life of this patent

Abstract

Claims4