Polymeric matrix compatibilized naphthopyrans

Described are polymeric matrix compatibilized naphthopyran compounds, examples of which are certain 2H-naphtho[1,2-b]pyrans, 3H-naphtho[2,1-b]pyrans and indeno[2,1-f]naphtho[1,2-b]pyrans each having at least one substituent containing terminal and/or pendant groups selected from hydroxyl, carboxyl, sulfo, sulfono, (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl, epoxy or a mixture thereof. Specific substituents are also present on the naphtho, indeno and/or pyrano portions of the compounds. These compounds may be represented by the following graphic formulae: ##STR1## Also described are various substrates that contain or that are coated with such compounds. Optically clear articles such as contact lenses or other plastic transparencies that incorporate the novel naphthopyran compounds or combinations thereof with complementary photochromic compounds, are also described.

 

We claim:

1. A naphthopyran compound represented by the following graphic formulae: ##STR14##

wherein,

(a) R.sub.1 is the group R which is represented by one of the following formulae:

--A; (1)

--D--A; (2)

--D--E--U; (3)

--D--U; (4)

--E--U; (5)

or

--U; (6)

wherein --A is represented by the following formula:

--[(OC.sub.2 H.sub.4).sub.x (OC.sub.3 H.sub.6).sub.y (OC.sub.4 H.sub.8).sub.z ]--J

wherein --J is selected from: --OCH.sub.2 COOH; --OCH(CH.sub.3)COOH; --OC(O)(CH.sub.2).sub.w COOH; --OC.sub.6 H.sub.4 SO.sub.3 H; --OC.sub.5 H.sub.10 SO.sub.3 H; --OC.sub.4 H.sub.8 SO.sub.3 H; --OC.sub.3 H.sub.6 SO.sub.3 H; --OC.sub.2 H.sub.4 SO.sub.3 H; or --OSO.sub.3 H; w is an integer from 1 to 18; x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 1 and 50; --D-- is --C(O)-- or --CH.sub.2 --; --E-- is represented by the following formula:

--[(OC.sub.2 H.sub.4).sub.x (OC.sub.3 H.sub.6).sub.y (OC.sub.4 H.sub.8).sub.z ]--

wherein x, y and z are the same as defined for --A; --U is a residue of an organic polyol having at least one hydroxyl group, or a derivative of said residue wherein one or more of said hydroxyls have been reacted to form the carboxyl, sulfo or sulfono group containing substituents --J, the group selected from (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl or epoxy, or a mixture thereof provided that --U is not the same as --E--OH; or R.sub.1 is hydrogen, C.sub.1 -C.sub.3 alkyl or the group, --C(O)W, W being --OR.sub.7, --N(R.sub.8)R.sub.9, piperidino or morpholino, wherein R.sub.7 is allyl, C.sub.1 -C.sub.6 alkyl, phenyl, mono(C.sub.1 -C.sub.6)alkyl substituted phenyl, mono(C.sub.1 -C.sub.6)alkoxy substituted phenyl, phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkyl substituted phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkoxy substituted phenyl(C.sub.1 -C.sub.3)alkyl, C.sub.1 -C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl or C.sub.1 -C.sub.6 haloalkyl; R.sub.8 and R.sub.9 are each selected from the group consisting of C.sub.1 -C.sub.6 alkyl, C.sub.5 -C.sub.7 cycloalkyl, phenyl, mono-substituted phenyl and di-substituted phenyl, said phenyl substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy, and said halo substituent being chloro or fluoro;

(b) R.sub.1 ' is the group R, C.sub.1 -C.sub.3 alkyl or the group, --C(O)W, W being --OR.sub.7, --N(R.sub.8)R.sub.9, piperidino or morpholino, wherein R.sub.7 is allyl, C.sub.1 -C.sub.6 alkyl, phenyl, mono(C.sub.1 -C.sub.6)alkyl substituted phenyl, mono(C.sub.1 -C.sub.6)alkoxy substituted phenyl, phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkyl substituted phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkoxy substituted phenyl(C.sub.1 -C.sub.3)alkyl, C.sub.1 -C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl or C.sub.1 -C.sub.6 haloalkyl; R.sub.8 and R.sub.9 are each selected from the group consisting of C.sub.1 -C.sub.6 alkyl, C.sub.5 -C.sub.7 cycloalkyl, phenyl, mono-substituted phenyl and di-substituted phenyl, said phenyl substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy, and said halo substituent being chloro or fluoro;

(c) R.sub.2 is selected from the group consisting of the group R, mono-R-substituted phenyl, hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.7 cycloalkyl, phenyl, mono-substituted phenyl, di-substituted phenyl and the groups --OR.sub.10 and --OC(O)R.sub.10, wherein R.sub.10 is C.sub.1 -C.sub.6 alkyl, phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkyl substituted phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkoxy substituted phenyl(C.sub.1 -C.sub.3)alkyl, C.sub.1 -C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl, C.sub.3 -C.sub.7 cycloalkyl or mono(C.sub.1 -C.sub.4)alkyl substituted C.sub.3 -C.sub.7 cycloalkyl, and said phenyl substituent being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy;

(d) each R.sub.3 and R.sub.4 are selected from the group consisting of the group R, hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.7 cycloalkyl, phenyl, mono-substituted phenyl, di-substituted phenyl and the groups --OR.sub.10 and --OC(O)R.sub.10, wherein R.sub.10 is C.sub.1 -C.sub.6 alkyl, phenyl(C.sub.1 -C.sub.3)-alkyl, mono(C.sub.1 -C.sub.6)alkyl substituted phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkoxy substituted phenyl(C.sub.1 -C.sub.3)alkyl, C.sub.1 -C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl, C.sub.3 -C.sub.7 cycloalkyl or mono(C.sub.1 -C.sub.4)alkyl substituted C.sub.3 -C.sub.7 cycloalkyl, and n is selected from the integers 0, 1 and 2 and said phenyl substituent being C.sub.1-C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy;

(e) R.sub.5 and R.sub.6 together form an oxo group, a spiro-carbocyclic ring containing 3 to 6 carbon atoms or a spiro-heterocyclic group containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, said spiro-carbocyclic and spiro-heterocyclic groups being annellated with 0, 1 or 2 benzene rings; or R.sub.5 and R.sub.6 are each the group R, hydrogen, hydroxy, C.sub.1 -C.sub.6 alkyl, C.sub.3 -C.sub.7 cycloalkyl, allyl, phenyl, mono-substituted phenyl, benzyl, mono-substituted benzyl, chloro, fluoro, the group, --C(O)X, wherein X is hydroxy, C.sub.1 -C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, phenyl, mono-substituted phenyl, amino, mono(C.sub.1 -C.sub.6)alkylamino, or di(C.sub.1 -C.sub.6)alkylamino; or R.sub.5 and R.sub.6 are each the group, --OR.sub.11, wherein R.sub.11 is C.sub.1 -C.sub.6 alkyl, phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkyl substituted phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.6)alkoxy substituted phenyl(C.sub.1 -C.sub.3)alkyl, C.sub.1 -C.sub.6 alkoxy(C.sub.2 -C.sub.4)alkyl, C.sub.3 -C.sub.7 cycloalkyl, mono(C.sub.1 -C.sub.4)alkyl substituted C.sub.3 -C.sub.7 cycloalkyl, C.sub.1 -C.sub.6 chloroalkyl, C.sub.1 -C.sub.6 fluoroalkyl, allyl, the group, --CH(R.sub.12)Y, wherein R.sub.12 is hydrogen or C.sub.1 -C.sub.3 alkyl and Y is CN, CF.sub.3, or COOR.sub.13 and R.sub.13 is hydrogen or C.sub.1 -C.sub.3 alkyl; or R.sub.11 is the group, --C(O)Z, wherein Z is hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl, phenoxy, mono- or di-(C.sub.1 -C.sub.6)alkyl substituted phenoxy, mono- or di-(C.sub.1 -C.sub.6)alkoxy substituted phenoxy, amino, mono(C.sub.1 -C.sub.6)alkylamino, di(C.sub.1 -C.sub.6)alkylamino, phenylamino, mono- or di-(C.sub.1 -C.sub.6)alkyl substituted phenylamino, or mono- or di-(C.sub.1 -C.sub.6)alkoxy substituted phenylamino, each of said phenyl, benzyl and aryl group substituents being C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.6 alkoxy;

(f) B and B' are each selected from the group consisting of:

(i) mono-R-substituted phenyl;

(ii) the unsubstituted, mono-, di- and tri-substituted aryl groups, phenyl and naphthyl;

(iii) 9-julolidinyl and the unsubstituted, mono- and di-substituted heteroaromatic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazolyl and fluorenyl, each of said aryl and heteroaromatic substituents in (f)(ii) and (iii) being selected from the group consisting of hydroxy, aryl, mono(C.sub.1 -C.sub.6)alkoxyaryl, di(C.sub.1 -C.sub.6)alkoxyaryl, mono(C.sub.1 -C.sub.6)alkylaryl, di(C.sub.1 -C.sub.6)alkylaryl, chloroaryl, fluoroaryl, C.sub.3 -C.sub.7 cycloalkylaryl, C.sub.3 -C.sub.7 cycloalkyl, C.sub.3 -C.sub.7 cycloalkyloxy, C.sub.3 -C.sub.7 cycloalkyloxy(C.sub.1 -C.sub.6)alkyl, C.sub.3 -C.sub.7 cycloalkyloxy(C.sub.1 -C.sub.6)alkoxy, aryl(C.sub.1 -C.sub.6)alkyl, aryl(C.sub.1 -C.sub.6)alkoxy, aryloxy, aryloxy(C.sub.1 -C.sub.6)alkyl, aryloxy(C.sub.1 -C.sub.6)alkoxy, mono- and di-(C.sub.1 -C.sub.6)alkylaryl(C.sub.1 -C.sub.6)alkyl, mono- and di-(C.sub.1 -C.sub.6)alkoxyaryl(C.sub.1 -C.sub.6)alkyl, mono- and di-(C.sub.1 -C.sub.6)alkylaryl(C.sub.1 -C.sub.6)alkoxy, mono- and di-(C.sub.1 -C.sub.6)alkoxyaryl(C.sub.1 -C.sub.6)alkoxy, amino, mono(C.sub.1 -C.sub.6)alkylamino, di(C.sub.1 -C.sub.6)alkylamino, diarylamino, N-(C.sub.1 -C.sub.6)alkylpiperazino, N-arylpiperazino, aziridino, indolino, piperidino, arylpiperidino, morpholino, thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 chloroalkyl, C.sub.1 -C.sub.6 fluoroalkyl, C.sub.1 -C.sub.6 alkoxy, mono(C.sub.1 -C.sub.6)alkoxy(C.sub.1 -C.sub.4)alkyl, acryloxy, methacryloxy, bromo, chloro and fluoro, said aryl being phenyl or naphthyl;

(iv) the unsubstituted or mono-substituted groups, pyrazolyl, imidazolyl, pyridyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl or acridinyl, each of said substituents being selected from the group consisting of C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.4 alkoxy, phenyl, fluoro, chloro and bromo;

(v) monosubstituted phenyl, having a substituent at the para position that is a linking group, --(CH.sub.2).sub.t -- or --O--(CH.sub.2).sub.t --, wherein t is the integer 1, 2, 3, 4, 5 or 6, connected to an aryl group, which is a member of another photochromic naphthopyran;

(vi) the groups represented by the following graphic formulae: ##STR15##

wherein L is carbon or oxygen and M is oxygen or substituted nitrogen, provided that when M is substituted nitrogen, L is carbon, said nitrogen substituents being selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 alkyl and C.sub.2 -C.sub.6 acyl; each R.sub.14 is C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkoxy, hydroxy, chloro or fluoro; R.sub.15 and R.sub.16 are each hydrogen or C.sub.1 -C.sub.6 alkyl; and q is the integer 0, 1 or 2;

(vii) C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 chloroalkyl, C.sub.1 -C.sub.6 fluoroalkyl, C.sub.1 -C.sub.6 alkoxy(C.sub.1 -C.sub.4)alkyl, C.sub.3 -C.sub.6 cycloalkyl, mono(C.sub.1 -C.sub.6)alkoxy(C.sub.3 -C.sub.6)cycloalkyl, mono(C.sub.1 -C.sub.6)alkyl(C.sub.3 -C.sub.6)-cycloalkyl, chloro(C.sub.3 -C.sub.6)cycloalkyl, fluoro(C.sub.3 -C.sub.6)cycloalkyl and C.sub.4 -C.sub.12 bicycloalkyl; and

(viii) the group represented by the following graphic formula: ##STR16##

wherein P is hydrogen or C.sub.1 -C.sub.4 alkyl and Q is selected from the unsubstituted, mono-, and di-substituted members of the group consisting of naphthyl, phenyl, furanyl and thienyl, each of said group substituents being C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, fluoro or chloro; or

(g) B and B' taken together form fluoren-9-ylidene, mono-, or di-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C.sub.3 -C.sub.12 spiro-monocyclic hydrocarbon rings, saturated C.sub.7 -C.sub.12 spiro-bicyclic hydrocarbon rings, and saturated C.sub.7 -C.sub.12 spiro-tricyclic hydrocarbon rings, each of said fluoren-9-ylidene substituents being selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, fluoro and chloro, provided that there is at least one R group or mono-R-substituted phenyl on said naphthopyran.

2. The naphthopyran of claim 1 wherein there is one R group or mono-R-substituted phenyl on said naphthopyran.

3. The naphthopyran of claim 1 represented by graphic formula I or III, wherein:

(a) R.sub.1 ' is the group R which is represented by formula: (a)(1); (a)(2); (a)(5); or (a)(6); or R.sub.1 ' is the group, --C(O)W, W being --OR.sub.7 or --N(R.sub.8)R.sub.9, wherein R.sub.7 is C.sub.1 -C.sub.4 alkyl, phenyl, mono(C.sub.2 -C.sub.4)alkyl substituted phenyl, mono(C.sub.1 -C.sub.4)alkoxy substituted phenyl, phenyl(C.sub.1 -C.sub.2)alkyl, mono(C.sub.1 -C.sub.4)alkyl substituted phenyl(C.sub.1 -C.sub.2)alkyl, mono(C.sub.1 -C.sub.4)alkoxy substituted phenyl(C.sub.1 -C.sub.2)alkyl, mono(C.sub.1 -C.sub.4)alkoxy(C.sub.2 -C.sub.3)alkyl or C.sub.1 -C.sub.4 haloalkyl; R.sub.8 and R.sub.9 are each selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.5 -C.sub.7 cycloalkyl, phenyl, mono-substituted phenyl and di-substituted phenyl, said phenyl substituents being C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy, said halo substituents being chloro or fluoro;

(b) R.sub.2 is selected from the group consisting of the group R, mono-R-substituted phenyl, hydrogen, C.sub.1 -C.sub.3 alkyl, C.sub.3 -C.sub.5 cycloalkyl, phenyl, mono-substituted phenyl, di-substituted phenyl and the group --OR.sub.10, wherein R.sub.10 is C.sub.1 -C.sub.4 alkyl, phenyl(C.sub.1 -C.sub.2)alkyl, mono(C.sub.1 -C.sub.4)alkyl substituted phenyl(C.sub.1 -C.sub.2)alkyl, mono(C.sub.1 -C.sub.4)alkoxy substituted phenyl(C.sub.1 -C.sub.2)alkyl, C.sub.1 -C.sub.4 alkoxy(C.sub.2 -C.sub.4)alkyl, C.sub.5 -C.sub.7 cycloalkyl or mono(C.sub.1 -C.sub.3)alkyl substituted C.sub.5 -C.sub.7 cycloalkyl and said phenyl substituents being C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 alkoxy;

(c) each R.sub.3 is selected from the group consisting of the group R, hydrogen, C.sub.1 -C.sub.3 alkyl, C.sub.3 -C.sub.5 cycloalkyl, phenyl, mono-substituted phenyl, di-substituted phenyl and the group --OR.sub.10, wherein R.sub.10 is C.sub.1 -C.sub.4 alkyl, phenyl(C.sub.1 -C.sub.2)alkyl, mono(C.sub.1 -C.sub.4)alkyl substituted phenyl(C.sub.1 -C.sub.2)alkyl, mono(C.sub.1 -C.sub.4)alkoxy substituted phenyl(C.sub.1 -C.sub.2)alkyl, C.sub.1 -C.sub.4 alkoxy(C.sub.2 -C.sub.4)alkyl, C.sub.5 -C.sub.7 cycloalkyl or mono(C.sub.1 -C.sub.3)alkyl substituted C.sub.5 -C.sub.7 cycloalkyl and said phenyl substituents being C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 alkoxy;

(d) R.sub.5 and R.sub.6 are each selected from the group consisting of the group R, hydrogen, hydroxy, C.sub.1 -C.sub.4 alkyl, C.sub.3 -C.sub.6 cycloalkyl, chloro, fluoro and the group, --OR.sub.11, wherein R.sub.11 is C.sub.1 -C.sub.3 alkyl, phenyl(C.sub.1 -C.sub.2)alkyl, mono(C.sub.1 -C.sub.3)alkyl substituted phenyl(C.sub.1 -C.sub.3)alkyl, mono(C.sub.1 -C.sub.3)alkoxy substituted phenyl(C.sub.1 -C.sub.3)alkyl, C.sub.1 -C.sub.3 alkoxy(C.sub.2 -C.sub.4)alkyl, C.sub.1 -C.sub.3 chloroalkyl, C.sub.1 -C.sub.3 fluoroalkyl, the group, --CH(R.sub.12)Y, wherein R.sub.12 is hydrogen or C.sub.1 -C.sub.2 alkyl and Y is CN or COOR.sub.13, and R.sub.13 is hydrogen or C.sub.1 -C.sub.2 alkyl, or R.sub.11 is the group, --C(O)Z, wherein Z is hydrogen, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, phenyl, naphthyl, mono-substituted aryl groups, phenyl or naphthyl, phenoxy, mono- or di-(C.sub.1 -C.sub.3)alkyl substituted phenoxy, mono- or di-(C.sub.1 -C.sub.3)alkoxy substituted phenoxy, mono(C.sub.1 -C.sub.3)alkylamino, phenylamino, mono- or di-(C.sub.1 -C.sub.3)alkyl substituted phenylamino, or mono- or di-(C.sub.1 -C.sub.3)alkoxy substituted phenylamino, and said aryl substituents being C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 alkoxy;

(e) B and B' are each selected from the group consisting of:

(i) mono R-substituted phenyl;

(ii) phenyl, mono-substituted and di-substituted phenyl;

(iii) the unsubstituted, mono- and di-substituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl, benzothien-2-yl, dibenzofuran-2-yl, and dibenzothien-2-yl, each of said phenyl and heteroaromatic substituents in (e)(ii) and (iii) being selected from the group consisting of hydroxy, aryl, arlyoxy, aryl(C.sub.1 -C.sub.3)alkyl, amino, mono(C.sub.1 -C.sub.3)alkylamino, di(C.sub.1 -C.sub.3)alkylamino, N--(C.sub.1 -C.sub.3)alkylpiperazino, indolino, piperidino, morpholino, pyrryl, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 chloroalkyl, C.sub.1 -C.sub.3 fluoroalkyl, C.sub.1 -C.sub.3 alkoxy, mono(C.sub.1 -C.sub.3)alkoxy(C.sub.1 -C.sub.3)alkyl, chloro and fluoro;

(iv) the groups represented by the following graphic formulae; ##STR17##

wherein L is carbon and M is oxygen, R.sub.14 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 alkoxy; R.sub.15 and R.sub.16 are each hydrogen or C.sub.1 -C.sub.4 alkyl; and q is 0 or 1;

(v) C.sub.1 -C.sub.4 alkyl; and

(vi) the group represented by the following graphic formula: ##STR18##

wherein P is hydrogen or methyl and Q is phenyl or mono-substituted phenyl, said phenyl substituents being C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy or fluoro; or

(f) B and B' taken together form fluoren-9-ylidene, mono-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C.sub.3 -C.sub.8 spiro-monocyclic hydrocarbon rings, saturated C.sub.7 -C.sub.10 spiro-bicyclic hydrocarbon rings, and saturated C.sub.7 -C.sub.10 spiro-tricyclic hydrocarbon rings, said fluoren-9-ylidene substituent being selected from the group consisting of C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, fluoro and chloro.

4. The naphthopyran of claim 1 represented by graphic formula III, wherein:

(a) each R.sub.3 is the group R which is represented by formula (a)(5) or (a)(6); or each R.sub.3 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.3 alkyl, phenyl, mono-substituted phenyl, di-substituted phenyl and the group, OR.sub.10, wherein R.sub.10 is C.sub.1 -C.sub.3 alkyl and said phenyl substituents being methyl or methoxy;

(b) R.sub.5 and R.sub.6 are each the group R, hydrogen, hydroxy, C.sub.1 -C.sub.4 alkyl, or the group, --OR.sub.11, wherein R.sub.11 is C.sub.1 -C.sub.3 alkyl;

(c) B and B' are each selected from the group consisting of:

(i) mono-R-substituted phenyl;

(ii) phenyl, mono- and di-substituted phenyl;

(iii) the unsubstituted, mono- and di-substituted heteroaromatic groups furanyl, benzofuran-2-yl, thienyl and benzothien-2-yl, each of said phenyl and heteroaromatic substituents in (c)(ii) and (iii) being selected from the group consisting of hydroxy, C.sub.1 -C.sub.3 alkyl, C.sub.1 -C.sub.3 alkoxy, phenyl, indolino, fluoro and chloro; and

(iv) the group represented by the following graphic formula: ##STR19##

wherein L is carbon and M is oxygen, R.sub.14 is C.sub.1 -C.sub.3 alkyl or C.sub.1 -C.sub.3 alkoxy; R.sub.15 and R.sub.16 are each hydrogen or C.sub.1 -C.sub.3 alkyl; and q is 0 or 1; or

(f) B and B' taken together form fluoren-9-ylidene, adamantylidene, bornylidene, norbornylidene, or bicyclo[3.3.1]nonan-9-ylidene.

5. A naphthopyran compound selected from the group consisting of:

(a) 3,3-di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2,3-dihydroxy)propoxy-indeno [2,1-f]naphtho[1,2-b]pyran;

(b) 3,3-di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2-(2-2-bis[(2-hydroxyethoxy) methyl]-3-hydroxypropyloxy)ethoxy)-indeno[2,1-f]naphtho[1,2-b]pyran;

(c) 3,3-di(4-methoxyphenyl)-6,11-dimethoxy-13-methyl-13-(2,3-dihydroxy)propoxy -indeno[2,1-f]naphtho[1,2-b]pyran;

(d) 3-phenyl-3-(4-morpholinophenyl)-13-methyl-13-(2,3-dihydroxy)propoxy-indeno [2,1-f]naphtho[1,2-b]pyran;

(e) 2,2-diphenyl-5-((2,3-dihydroxy)propoxy)carbonyl-8-methyl-[2H]-naphtho[1,2- b]pyran;

(f) 3,3-di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2-(3-carboxypropanoyloxy)eth oxy)-indeno[2,1-f]naphtho[1,2-b]pyran;

(g) 3,3-di(4-methoxyphenyl)-6,11-dimethoxy-13-methyl-13-(2,3-dimethacryloxy)pr opoxyindeno[2,1-f]naphtho[1,2-b]pyran;

(h) 3,3-di(4-methoxyphenyl)-6,11,13-trimethyl-13-(2,3-di(2-sulfonoethyloxy))pr opoxy-indeno[2,1-f]naphtho[1,2-b]pyran;

(i) 3-phenyl-3-(4-morpholinophenyl)-6,11-dimethoxy-13-methyl-13-(2,3-di(4-sulf onophenoxy))propoxy-indeno[2,1-f]naphtho[1,2-b]pyran; and

(j) 3,3-di(4-methoxyphenyl)-6,11-dimethoxy-13-methyl-13-(2,3-di(epoxymethoxy)) propoxy-indeno[2,1-f]naphtho[1,2-b]pyran.

6. A photochromic article comprising a polymeric organic host material selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bismethacrylate), poly(ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane, poly(vinylpyrrolidone), poly((meth)acrylamide), poly(dimethyl acrylamide), poly(hydroxyethyl methacrylate), poly((meth)acrylic acid), and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate)monomers, diethylene glycol dimethacrylate monomers, ethoxylated phenol bismethacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers, and a photochromic amount of the naphthopyran compound of claim 5.

7. A photochromic article comprising a polymeric organic host material and a photochromic amount of the naphthopyran compound of claim 1.

8. The photochromic article of claim 7 wherein the polymeric organic host material is selected from the group consisting of polyacrylates, polymethacrylates, poly(C.sub.1 -C.sub.12) alkyl methacrylates, polyoxy(alkylene methacrylates), poly (alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), poly(vinylpyrrolidone), poly((meth)acrylamide), poly(dimethyl acrylamide), poly(hydroxyethyl methacrylate), poly((meth)acrylic acid), thermoplastic polycarbonates, polyesters, polyurethanes, polythiourethanes, poly(ethylene terephthalate), polystyrene, poly(alpha methylstyrene), copoly(styrene-methylmethacrylate), copoly(styrene-acrylonitrile), polyvinylbutyral and polymers of members of the group consisting of polyol(allyl carbonate)monomers, mono-functional acrylate monomers, mono-functional methacrylate monomers, polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, alkoxylated polyhydric alcohol monomers and diallylidene pentaerythritol monomers.

9. The photochromic article of claim 8 wherein the polymeric organic material is a homopolymer or copolymer of monomer(s) selected from the group consisting of acrylates, methacrylates, methyl methacrylate, ethylene glycol bis methacrylate, ethoxylated bisphenol A dimethacrylate, vinyl acetate, vinylbutyral, urethane, thiourethane, diethylene glycol bis(allyl carbonate), diethylene glycol dimethacrylate, diisopropenyl benzene, and ethoxylated trimethylol propane triacrylate.

10. The photochromic article of claim 8 wherein the photochromic compound is present in an amount of from 0.05 to 2.0 milligram per square centimeter of polymeric organic host material surface to which the photochromic substance(s) is incorporated or applied.

11. The photochromic article of claim 7 wherein said polymeric organic host material is an optical element.

12. The photochromic article of claim 11 wherein said optical element is a lens.

13. A photochromic article comprising, in combination, a solid substrate and a photochromic amount of each of (a) at least one naphthopyran compound of claim 1, and (b) at least one other organic photochromic compound having at least one activated absorption maxima within the range of between 400 and 700 nanometers.

14. A photochromic article comprising a polymerizate of an optical organic resin monomer and a photochromic amount of the naphthopyran compound of claim 1.

15. The photochromic article of claim 14 wherein the refractive index of the polymerizate is from about 1.35 to about 1.75.

16. The photochromic article of claim 14 wherein the polymerizate is an optical element.

17. The photochromic article of claim 16 wherein said optical element is an ophthalmic spectacle lens or a contact lens.

18. A photochromic article comprising, in combination, a solid substrate and on at least one surface thereof a cured coating of a coating composition having a photochromic amount of the naphthopyran compound of claim 1.

19. The photochromic article of claim 18 wherein said coating composition is selected from the group consisting of a polymeric coating composition, paint and ink.

20. The photochromic article of claim 19 wherein the substrate is selected from the group consisting of glass, masonry, textiles, ceramics, metals, wood, paper and polymeric organic material.

DESCRIPTION OF THE INVENTION

The present invention relates to certain novel naphthopyran compounds. More particularly, this invention relates to photochromic naphthopyrans having substituents that make the compounds more compatible for use in different matrices, e.g., hydrophilic or hydrophobic polymeric matrices. This invention also relates to compositions and articles containing such novel photochromic compounds. When exposed to electromagnetic radiation containing ultraviolet rays, such as the ultraviolet radiation in sunlight or the light of a mercury lamp, many photochromic compounds exhibit a reversible change in color. When the ultraviolet radiation is discontinued, such a photochromic compound will return to its original color or colorless state.

Various classes of photochromic compounds have been synthesized and suggested for use in applications in which a sunlight-induced reversible color change or darkening is desired. U.S. Pat. No. 3,567,605 (Becker) describes a series of pyran derivatives, including certain benzopyrans and naphthopyrans. U.S. Pat. No. 5,458,814 describes photochromic 2,2-di-substituted-5,6-substituted-2H-naphtho[1,2-b]pyran compounds primarily for use in lenses and other plastic transparencies. These compounds have an acceptable fade rate in addition to a high activated intensity and a high coloration rate. U.S. Pat. No. 5,585,042 discloses 3,3-di-substituted-8-substituted-3H-naphtho[2,1-b]pyran compounds for similar uses. These compounds exhibit an improved solar response, a higher activating wavelength than unsubstituted naphthopyrans, and an acceptable bleach or fade rate. U.S. Pat. No. 5,645,767 describes photochromic indeno[2,1-f]naphtho[1,2-b]pyrans having a high activated intensity, an acceptable fade rate and high coloration rate.

International Patent Application WO 97/05213 describes a photochromic monomer having a photochromic dye moiety bonded to an organic spacer group which terminates with a polymerizable group. It is reported that when the photochromic monomer is incorporated into a cross-linking polymerizable casting composition, the photochromic material has a reduced sensitivity to temperature.

Although 3H-naphtho[2,1-b]pyrans, 2H-naphtho[1,2-b]pyrans and indeno[2,1-f]naphtho[1,2-b]pyrans of good intensity and reasonable fade are currently available, in certain circumstances it is desirable to modify the comparability of the photochromic compound with the substrate or host material. By making the photochromic compound more compatible with the polymeric matrix, it is less likely that the combination will demonstrate cloudiness or haze and phase separation which may become evident as the formation of crystals within the matrix or a bloom on the surface resulting from the migration of the photochromic after curing, and it is more likely that the photochromic compound will be more soluble and uniformly distributed throughout the matrix. Other properties of the photochromic compounds that may or may not be effected by the substituents of the present invention include fade and/or activation rate, saturated optical density, molar absorptivity or molar extinction coefficient, activated color and leachability from the polymeric matrix. Modifications to such properties may be done to match the same properties of complementary photochromic compounds or to enable the use of such compounds in hydrophilic or hydrophobic coatings, thin films or in rigid to flexible plastic matrices, e.g., contact lenses.

In accordance with the present invention, there have been discovered novel photochromic compounds; namely, certain 2H-naphtho[1,2-b]pyrans, 3H-naphtho[2,1-b]pyrans and indeno[2,1-f]naphtho[1,2-b]pyrans, that have at least one substituent containing terminal and/or pendant groups selected from hydroxyl, carboxyl, sulfo, sulfono, (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl (--OC(O)NHC.sub.2 H.sub.4 OC(O)C(CH.sub.3).dbd.CH.sub.2), epoxy or a mixture thereof. The substituent having the aforementioned groups is a residue of an alkoxylated diol or an organic polyol. Appropriate selection of the substituent, e.g., chain length, the number and type of the terminal and/or pendant groups, enables modification of the aforementioned properties. For example, an increase in the number of or altering the type of substituents on the naphthopyran having terminal groups selected from hydroxyl, carboxyl, sulfo, sulfono or a mixture thereof causes an improvement in the substituted compounds compatibility with polar or hydrophilic matrices and vice versa. Use of the polymerizable groups, epoxy, (meth)acryloxy, i.e., acryloxy or methacryloxy, or 2-(methacryloxy)ethylcarbamyl with or without the aforementioned groups on the substituent enables reacting and binding the photochromic compound into the polymeric matrix to prevent extraction or leaching of the photochromics for example, when the matrix is in contact with liquids. Depending on the location of the previously mentioned substituent(s), certain other substituents may also be present on the naphtho, pyrano and indeno portions of the aforedescribed compounds.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the present invention, it has been discovered that certain properties, e.g., solubility and/or compatability in hydrophilic coatings, films and plastics, leachability, fade rate, activation rate, saturated optical density, fatigue rate, and molar absorption of selected photochromic 2H-naphtho[1,2-b]pyrans, 3H-naphtho[2,1-b]pyrans and indeno[2,1-f]naphtho[1,2-b]pyrans may be modified by including on such compounds at least one substituent containing terminal and/or pendant groups selected from hydroxyl, carboxyl, sulfo, sulfono, (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl, epoxy or a mixture thereof. The substituent may be located on the naphtho, indeno and/or on the pyrano portion of the naphthopyran.

Other than where otherwise indicated, all numbers expressing values, such as, wavelengths, quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about" which means near to in number, quantity, degree, etc.

The disclosures of the related applications, patents and articles cited herein describing materials and/or procedures for making materials such as extended triols, polyester polyols, polycarbonate polyols, carbohydrates, macrocyclic acetals containing lipophilic substituents, propargyl alcohols, photochromic compounds, polymeric host materials, contact lenses and coating application methods are incorporated herein, in toto, by reference.

The naphthopyrans of the present invention also may have certain other substituents. Specifically, the 2H-naphthopyrans may have substituents at the 5 and 6 positions and may have additional substituents at the 7, 8, 9 and 10 positions; the 3H-naphthopyrans may have substituents at the 8 and 9 positions and may have additional substituents at the 5 and 6 positions; and the indeno-fused naphthopyrans may have certain substituents at the 5, 6, 7, 8, 9, 10, 11, 12 or 13 positions. The aforedescribed naphthopyrans may be represented by graphic formulae I, II and III in which the internal numbers 1 through 13 identify the ring atoms of the naphthopyrans and letters a through n represent the sides of the naphthopyran rings. In the definition of the substituents shown in the following graphic formulae I, II and III, like symbols have the same meaning unless stated otherwise. ##STR2##

In graphic formulae I, II and III, R.sub.1, R.sub.1 ', R.sub.2, each R.sub.3, R.sub.4, R.sub.5 and R.sub.6 may be the group R. The R group may be represented by the following formulae IVA to IVF:

--A (IVA);

--D--A (IVB);

--D--E--U (IVC);

--D--U (IVD);

--E--U (IVE);

or

--U (IVF);

wherein --A is represented by the following formula:

--[(OC.sub.2 H.sub.4).sub.x (OC.sub.3 H.sub.6).sub.y (OC.sub.4 H.sub.8).sub.z ]--J

wherein --J is selected from: --OCH.sub.2 COOH; --OCH(CH.sub.3)COOH; --OC(O)(CH.sub.2).sub.w COOH; --OC.sub.6 H.sub.4 SO.sub.3 H; --OC.sub.5 H.sub.10 SO.sub.3 H; --OC.sub.4 H.sub.8 SO.sub.3 H; --OC.sub.3 H.sub.6 SO.sub.3 H; --OC.sub.2 H.sub.4 SO.sub.3 H; or --OSO.sub.3 H; and w is an integer from 1 to 18, preferably from 2 to 12; wherein x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 1 and 50; --D-- is --C(O)-- or --CH.sub.2 --; --E-- is represented by the following formula:

--[(OC.sub.2 H.sub.4).sub.x (OC.sub.3 H.sub.6).sub.y (OC.sub.4 H.sub.8).sub.z ]--

wherein x, y and z are the same as defined for --A; --U is a residue of an organic polyol having at least 1 hydroxyl group or a derivative of the residue wherein one or more of the hydroxyl groups have been reacted to form the carboxyl, sulfo or sulfono group containing substituent --J, a polymerizable group selected from (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl, or epoxy or a mixture thereof provided that --U is not the same as --E--OH.

The group, --U, is a residue of an organic polyol which is defined herein to include hydroxylated carbohydrates discussed hereinafter. The residue is formed by the reaction of one of the hydroxyl groups on the polyol with a precursor of group --D--, such as a carboxylic acid or a methylene halide, a precursor of group --E--, such as polyalkylene glycol or a hydroxyl group as substituent R.sub.1, R.sub.1 ', R.sub.2, each R.sub.3, R.sub.4, R.sub.5 or R.sub.6 on the naphthopyran of graphic formulae I, II or III. The organic polyol may be represented by G(OH).sub.a and the residue --U may be represented by the formula --O--G(OH).sub.a-1, wherein G is the backbone or main chain of the polyhydroxylated compound and a is at least 2, provided that --U is not the same as --E--OH.

All, none or at least one of the hydroxyls of group, --U, may be reacted to form a group represented by --J, a polymerizable group selected from (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl, epoxy or a mixture thereof. The hydroxyl groups of --U may be reacted to form the carboxyl group containing substituent --J by the method of Reactions B and D to produce a carboxylated organic polyol residue. The organic polyol residue --U having the sulfo or sulfono terminating groups of --J on it may be produced by acidic condensation of the hydroxyl groups of --U with HOC.sub.6 H.sub.4 SO.sub.3 H; HOC.sub.5 H.sub.10 SO.sub.3 H; HOC.sub.4 H.sub.8 SO.sub.3 H; HOC.sub.3 H.sub.6 SO.sub.3 H; HOC.sub.2 H.sub.4 SO.sub.3 H; or H.sub.2 SO.sub.4, respectively. The polymerizable groups, (meth)acryloxy, 2-(methacryloxy)ethylcarbamyl or epoxy, may be added to the polyol residue --U by condensation of the polyol with (meth)acryloyl chloride, isocyanatoethyl methacrylate or epichlorohydrin, respectively.

Examples of organic polyols that may be used as --U in the R group substituent of the polymer matrix compatibilized naphthopyrans of the present invention include polyols having at least 2 hydroxy groups such as (a) low molecular weight polyols, i.e., polyols having an average molecular weight less than 500, e.g., aliphatic triols, such as C.sub.2 -C.sub.10 aliphatic triols, polyhydric alcohols and alkoxylated low molecular weight polyols; (b) polyester polyols; (c) polyether polyols; (d) amide-containing polyols; (e) epoxy polyols; (f) polyhydric polyvinyl alcohols; (g) urethane polyols; (h) polyacrylic polyols; (i) polycarbonate polyols; and (j) mixtures of such polyols.

Examples of low molecular weight polyols that can be used in the preparation of the photochromic compounds of the present invention include: tetramethylolmethane, i.e., pentaerythritol, dipentaerythritol, tripentaerythritol; trimethylolethane; trimethylolpropane; ditrimethylolpropane; 1,2,3-propanetriol, i.e., glycerol; 1,2-butanediol; di-(trimethylolpropane)dimethylol propionic acid; 2-(hydroxymethyl)-2-methyl-1,3-propanediol; 2-(hydroxymethyl)-2-ethyl-1,3-propanediol; and extended polyols. Extended polyols are reaction products having terminal hydroxyl groups of the polyol and a suitable reactant, e.g., an alkylene oxide, or a lactone. Examples of such extended polyols include .epsilon.-caprolactone extended trimethylol methane and ethoxylated or propoxylated trimethylolpropane or pentaerythitol having a number average molecular weight less than 500. Extended polyols having a number average molecular weight of 500 or more are described hereinafter as polyester polyols and polyalkoxylated polyols. Further examples of extended triols are disclosed in U.S. Pat. No. 4,398,008.

Polyester polyols are generally known and can have a number average molecular weight in the range of from 500 to 10,000. They are prepared by conventional techniques utilizing low molecular weight triols and polyhydric alcohols known in the art, including but not limited to the previously described low molecular weight polyols with polycarboxylic acids. Examples of suitable polycarboxylic acids include: phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, adipic acid, succinic acid, glutaric acid, fumaric acid, and mixtures thereof. Anhydrides of the above acids, where they exist, can also be employed and are encompassed by the term "polycarboxylic acid". In addition, certain materials that react in a manner similar to acids to form polyester polyols are also useful. Such materials include lactones, e.g., caprolactone, propiolactone and butyrolactone, and hydroxy acids such as hydroxycaproic acid and dimethylol propionic acid. If a triol or polyhydric alcohol is used, a monocarboxylic acid, such as acetic acid and/or benzoic acid, may be used in the preparation of the polyester polyols, and for some purposes, such a polyester polyol may be desirable. Moreover, polyester polyols are understood herein to include polyester polyols modified with fatty acids or glyceride oils of fatty acids and/or alkylene oxides, e.g., ethylene oxide, propylene oxide, etc., to produce polyoxyethylene fatty acid esters such as polyoxyethylene (20) sorbitan monolaurate and related polysorbates. Further examples of polyester polyols having ether and ester groups are described in U.S. Pat. No. 4,677,181.

Polyether polyols are generally known and can have a number average molecular weight in the range of from 500 to 10,000. Examples of polyether polyols include various polyoxyalkylene polyols and polyalkoxylated polyols each having at least 2 hydroxyl groups and a number average molecular weight greater than 500. The polyether polyols can be prepared, according to well-known methods, by condensing alkylene oxide, or a mixture of alkylene oxides using acid or base catalyzed addition, with a polyhydric initiator or a mixture of polyhydric initiators such as low molecular weight polyols, sorbitol and the like. Illustrative alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, amylene oxide, aralkylene oxides, e.g., styrene oxide, and the halogenated alkylene oxides such as trichlorobutylene oxide and so forth. The more preferred alkylene oxides include propylene oxide and ethylene oxide or a mixture thereof using random or step-wise oxyalkylation.

Amide-containing polyols are generally known and typically are prepared from the reaction of diacids or lactones and low molecular weight polyols described herein with diamines or aminoalcohols as described hereinafter. For example, amide-containing polyols may be prepared by the reaction of neopentyl glycol, adipic acid and hexamethylenediamine. The amide-containing polyols may also be prepared through aminolysis by the reaction, for example, of carboxylates, carboxylic acids, or lactones with amino alcohols. Examples of suitable diamines and amino alcohols include hexamethylenediamines, ethylenediamines, phenylenediamine, monoethanolamine, diethanolamine, isophorone diamine and the like.

Epoxy polyols are generally known and can be prepared, for example, by the reaction of glycidyl ethers of polyphenols such as the diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane, with polyphenols such as 2,2-bis(4-hydroxyphenyl)propane. Epoxy polyols of varying molecular weights and average hydroxyl functionality can be prepared depending upon the ratio of starting materials used.

Polyhydric polyvinyl alcohols are generally known and can be prepared, for example, by the polymerization of vinyl acetate in the presence of suitable initiators followed by hydrolysis of at least a portion of the acetate moieties. In the hydrolysis process, hydroxyl groups are formed which are attached directly to the polymer backbone. In addition to homopolymers, copolymers of vinyl acetate and monomers such as vinyl chloride can be prepared and hydrolyzed in similar fashion to form polyhydric polyvinyl alcohol-polyvinyl chloride copolymers.

Urethane polyols are generally known and can be prepared, for example, by reaction of a polyisocyanate with excess organic polyol to form a hydroxyl functional product having at least 2 hydroxyl groups. Examples of polyisocyanates useful in the preparation of urethane polyols include those selected from the group consisting of aliphatic, aromatic, cycloaliphatic and heterocyclic polyisocyanates, and mixtures of such polyisocyanates.

Specific examples of polyisocyanates useful in the preparation of urethane polyols include, but are not limited to, toluene-2,4-diisocyanate; toluene-2,6-diisocyanate; diphenyl methane-4,4'-diisocyanate; diphenyl methane-2,4'-diisocyanate; para-phenylene diisocyanate; biphenyl diisocyanate; 3,3'-dimethyl-4,4'-diphenylene diisocyanate; tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; 2,2,4-trimethyl hexane-1,6-diisocyanate; lysine methyl ester diisocyanate; bis(isocyanato ethyl)fumarate; isophorone diisocyanate; ethylene diisocyanate; dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methyl cyclohexyl diisocyanate; hexahydrotoluene-2,4-diisocyanate; hexahydrotoluene-2,6-diisocyanate; hexahydrophenylene-1,3-diisocyanate; hexahydrophenylene-1,4-diisocyanate; perhydrodiphenylmethane-2,4'-diisocyanate; perhydrodiphenylmethane-4,4'-diisocyanate and mixtures thereof.

Examples of organic polyols useful in the preparation of urethane polyols include the other polyols described herein, e.g., low molecular weight polyols, polyester polyols, polyether polyols, amide-containing polyols, epoxy polyols, polyhydric polyvinyl alcohols, polyacrylic polyols, polycarbonate polyols and mixtures thereof.

The polyacrylic polyols are generally known and can be prepared by free-radical addition polymerization techniques of monomers described hereinafter. Preferably the polyacrylic polyols have a weight average molecular weight of from 500 to 20,000 and a hydroxyl number of from 20 to 225.

Polyacrylic polyols include, but are not limited to, the known hydroxyl-functional addition polymers and copolymers of acrylic and methacrylic acids; their ester derivatives including, but not limited to, their hydroxyl-functional ester derivatives. Examples of hydroxy-functional ethylenically unsaturated monomers to be used in the preparation of the hydroxy-functional addition polymers include hydroxyethyl(meth)acrylate, i.e., hydroxyethyl acrylate and hydroxyethyl methacrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxymethylethyl acrylate, hydroxymethylpropyl acrylate and mixtures thereof.

More preferably, the polyacrylic polyol is a copolymer of hydroxy-functional ethylenically unsaturated (meth)acrylic monomers and other ethylenically unsaturated monomers selected from the group consisting of vinyl aromatic monomers, e.g., styrene, .alpha.-methyl styrene, t-butyl styrene and vinyl toluene; vinyl aliphatic monomers such as ethylene, propylene and 1,3-butadiene; (meth)acrylamide; (meth)acrylonitrile; vinyl and vinylidene halides, e.g., vinyl chloride and vinylidene chloride; vinyl esters, e.g., vinyl acetate; alkyl esters of acrylic and methacrylic acids, i.e. alkyl esters of (meth)acrylic acids, having from 1 to 17 carbon atoms in the alkyl group, including methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isobornyl(meth)acrylate and lauryl(meth)acrylate; epoxy-functional ethylenically unsaturated monomers such as glycidyl(meth)acrylate; carboxy-functional ethylenically unsaturated monomers such as acrylic and methacrylic acids and mixtures of such ethylenically unsaturated monomers.

The hydroxy-functional ethylenically unsaturated (meth)acrylic monomer(s) may comprise up to 95 weight percent of the polyacrylic polyol copolymer. Preferably it composes up to 70 weight percent, and more preferably, the hydroxy-functional ethylenically unsaturated (meth)acrylic monomer(s) comprises up to 45 weight percent of the total copolymer.

The polyacrylic polyols described herein can be prepared by free radical initiated addition polymerization of the monomer(s), and by organic solution polymerization techniques. The monomers are typically dissolved in an organic solvent or mixture of solvents including ketones such as methyl ethyl ketones, esters such as butyl acetate, the acetate of propylene glycol, and hexyl acetate, alcohols such as ethanol and butanol, ethers such as propylene glycol monopropyl ether and ethyl-3-ethoxypropionate, and aromatic solvents such as xylene and SOLVESSO 100, a mixture of high boiling hydrocarbon solvents available from Exxon Chemical Co. The solvent is first heated to reflux, usually 70 to 160.degree. C., and the monomer or a mixture of monomers and free radical initiator is slowly added to the refluxing solvent, over a period of about 1 to 7 hours. Adding the monomers too quickly may cause poor conversion or a high and rapid exothermic reaction, which is a safety hazard. Suitable free radical initiators include t-amyl peroxyacetate, di-t-amyl peroxyacetate and 2,2'-azobis(2-methylbutanenitrile). The free radical initiator is typically present in the reaction mixture at from 1 to 10 percent, based on total weight of the monomers. The polymer prepared by the procedures described herein is non-gelled and preferably has a weight average molecular weight of from 500 to 20,000 grams per mole.

Polycarbonate polyols that can be used to prepare the photochromic compounds of the present invention may be obtained by reacting polyhydric alcohols with a carbonyl component selected from phosgene, a chloroformate, a dialyl carbonate, a diaryl carbonate, an alkylene carbonate or a mixture thereof. Such polycarbonate polyol production methods are described in U.S. Pat. Nos. 3,689,609, 3,689,462, 4,131,731; 4,160,853; 4,533,729, 4,891,421 and 5,266,551.

Polycarbonate polyols having 2 or more hydroxyl groups may also be prepared by the ester interchange reaction of a polycarbonate diol with a triol and/or a tetraol, as described in U.S. Pat. No. 5,143,997. Introduction of carboxyl groups into the polycarbonate polyols may be accomplished by the reaction of a polycarbonate polyol with an acid anhydride or a dicarboxylic acid, as described in U.S. Pat. No. 5,527,879.

Examples of polyhydroxylated carbohydrates that can be used in the R group substituent of the photochromic compounds of the present invention include: low molecular weight carbohydrates of the formula C.sub.n (H.sub.2 O).sub.n wherein n is from 3 to 5, e.g., aldotriose, aldoketose, erythrose, ribose, etc.; monosaccharides, e.g., simple sugars such as glucose and fructose; oligosaccharides, i.e., carbohydrates containing from two to ten monosaccharides linked together, e.g., sucrose and cyclodextrins; polysaccharides, i.e., carbohydrates containing more than ten monosaccharides linked together by glycosidic bonds, e.g., starch, cellulose, glycogen, pectin, agar, carrageenan and natural gums such as arabic and tragacanth.

The polyhydroxylated carbohydrates described herein also include glycosides which are mono- and oligosaccharides linked to nonsugar organic compounds. An example of which is the product of the reaction of D-glucose with ethanol to form ethyl .alpha.- & .beta.-D-glucopyranosides. Another class of polyhydroxylated carbohydrates are the glycoconjugates composed of glycoproteins, proteoglycans, peptidoglycans and glycolipids. Still another class of carbohydrates includes various reaction products such as the sugar alcohols, e.g., xylitol and glucitol, produced by the reduction of mono- and oligosaccharides. A further group of reaction products include low molecular weight carbohydrates, mono- and oligosaccharides in which one or more of the hydroxyl groups has been oxidized to a carboxylic acid functional group, or replaced by an amino group, thiol group or a halogen atom. Further information about carbohydrates that may be suitable for use in the R-group is found in the Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, 1992, Volume 4, pages 911-948.

Preferably, the --U group is selected from low molecular weight polyols and extended polyols. Examples of such polyols include (a) glycerol, pentaerythritol and trimethylolpropane, (b) ethoxylated glycerol, ethoxylated pentaerythritol and ethoxylated trimethyolpropane; and (c) polyols (a) and (b) having at least 1 hydroxyl