Photochromic indeno-fused phenanthropyran compounds
阅读说明：本技术 光致变色茚并稠合的菲并吡喃化合物 (Photochromic indeno-fused phenanthropyran compounds ) 是由 A·库马尔 D·R·达比迪恩 袁胜稳 M·托马苏洛 于 2017-05-10 设计创作，主要内容包括：本发明涉及光致变色的由下式(I)表示的茚并稠合的菲并吡喃化合物,<Image he="599" wi="700" file="DDA0002312411520000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>在一些实施方案中,由式(I)表示的光致变色化合物包括至少一个延长基团(例如R<Sup>6</Sup>和/或R<Sup>7</Sup>各自独立地为延长基团),以及本发明的化合物是光致变色-二向色化合物。本发明还涉及光致变色组合物和光致变色制品,如光致变色眼科制品,其包括一种或更多种由式(I)表示的光致变色化合物。(The present invention relates to photochromic indeno-fused phenanthropyran compounds represented by the following formula (I), in some embodiments, the photochromic compound represented by formula (I) comprises at least one extending group (e.g., R) 6 And/or R 7 Each independently an elongation group), and the compounds of the invention are photochromic-dichroic compounds. The present invention also relates to photochromic compositions and photochromic articles, such as photochromic ophthalmic articles, comprising one or more photochromic compounds represented by formula (I).)
1. A photochromic compound represented by the following formula (I),
wherein n is 1 to 3, and m is 1 to 4,
R2selected from hydrogen; halogen; straight or branched C1-C20An alkyl group; straight or branched C1-C20A perhaloalkyl group; -ORa；-SRaWherein each R isaIndependently selected from hydrogen, linear or branched C1-C20Alkyl and straight or branched C1-C20A perhaloalkyl group;
-C(O)ORbwherein R isbIs hydrogen or straight or branched C1-C10An alkyl group; substituted or unsubstituted aryl, each aryl substituent being independently selected from the group consisting of hydroxy, halogen, carbonyl, straight or branched C1-C20Alkoxycarbonyl, cyano, straight-chain or branched C1-C20Haloalkyl, straight-chain or branched C1-C20Alkyl, straight or branched C1-C20Alkoxy and straight or branched C1-C20A perhaloalkyl group; and a group Y1；
R6And R7Each independently selected from hydrogen; halogen; an elongation group L1；-ORcand-SRcWherein each R iscIndependently selected from hydrogen, an elongation group L2Straight or branched C1-C20Alkyl, -C (O) -RdAnd S (O) ReWherein R isdAnd ReEach independently selected from linear or branched C1-C10Alkyl, straight or branched C1-C10Perhaloalkyl, phenyl, straight or branched C1-C10Alkyl-substituted phenyl and straight or branched C1-C10A phenyl group substituted with a perhaloalkyl group,
provided that R is6And R7Is not hydrogen;
R1independently for each of n and R3Independently for each m is independently selected from
Hydrogen;
a cyano group;
a reactive substituent;
an elongation group L3；
Halogen selected from fluorine, chlorine and bromine;
straight or branched C1-C20An alkyl group;
straight or branched C1-C20A perhaloalkyl group;
C3-C10a cycloalkyl group;
radical Y2；
Substituted or unsubstituted phenyl, saidThe phenyl substituents are selected from at least one of the following groups: hydroxy, halogen, carbonyl, straight or branched C1-C20Alkoxycarbonyl, cyano, straight-chain or branched C1-C20Haloalkyl, straight-chain or branched C1-C20Alkyl, straight or branched C1-C20Alkoxy, straight or branched C1-C20Perhaloalkyl, and combinations thereof;
-O-R10’、-S-R10’、-C(O)-R10’、-C(O)-OR10’、-OC(O)-R10’、
-OC(O)O-R10’、-C(O)N(R10’)R10’、-N(R10’)C(O)N(R10’)(R10’) Or is or
-Si(OR10’)w(R10’)tWherein each R is10' independently hydrogen, straight or branched C1-C20Alkyl, phenyl (C)1-C20) Alkyl, mono (C)1-C20) Alkyl-substituted phenyl (C)1-C20) Alkyl, mono (C)1-C20) Alkoxy-substituted phenyl (C)1-C20) Alkyl, (C)1-C20) Alkoxy (C)2-C20) Alkyl radical, C3-C10Cycloalkyl or mono (C)1-C20) Alkyl substituted C3-C10Cycloalkyl, and w and t are each independently 0 to 3, provided that w + t is 3; and
-N(R11’)R12', wherein R11' and R12' independently of one another are hydrogen, straight-chain or branched C1-C20Alkyl, phenyl, naphthyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, benzopyridyl, fluorenyl, straight-chain or branched C1-C20Alkylaryl group, C3-C10Cycloalkyl radical, C4-C20Bicycloalkyl radical, C5-C20Tricycloalkyl or straight or branched C1-C20Alkoxyalkyl wherein the aryl group is phenyl or naphthyl, or R11' and R12' together with the nitrogen atom form a ring;
R4and R5Each independently selected from
(i) Hydrogen, hydroxy, straight or branched C1-C20Alkyl, straight or branched C1-C20Haloalkyl, C3-C10Cycloalkyl, allyl, benzyl or substituted benzyl, the benzyl substituents being selected from halogen, straight or branched C1-C20Alkyl or straight or branched C1-C20An alkoxy group;
(ii) unsubstituted, mono-, di-or tri-substituted group selected from phenyl, naphthyl, phenanthryl, pyrenyl, quinolinyl, isoquinolinyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl or indolyl, said group substituents in each case being independently selected from halogen, linear or branched C1-C20Alkyl or straight or branched C1-C20An alkoxy group; and
(iii) radical Y3(ii) a Or
(iv)R4And R5Together form a spiro substituent selected from the group consisting of: a substituted or unsubstituted spirocarbocyclic ring containing 3 to 10 carbon atoms, a substituted or unsubstituted spiroheterocyclic ring containing 1 or 2 oxygen atoms and 3 to 10 carbon atoms including a spirocarbon atom, said spirocarbocyclic and spiroheterocyclic rings being annelated with 0,1 or 2 benzene rings, said substituents being hydrogen or straight or branched C1-C20An alkyl group; and
b and B 'are each independently selected from unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, alkenyl, and alkynyl groups, or B and B' together form a ring structure,
wherein each of the extending groups L1、L2And L3Independently represented by the following formula (II),
formula (II)
–[S1]c-[Q1–[S2]d]d’-[Q2–[S3]e]e’-[Q3–[S4]f]f’–S5–P
Wherein:
(a)Q1、Q2and Q3Independently at each occurrence is a divalent group selected from the group consisting of: unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted heterocycloalkyl, and substituted heterocycloalkyl;
wherein said aryl, heteroaryl, cycloalkyl and heterocycloalkyl substituents are each independently selected from P, mesogen, halogen, poly (C)1-C18Alkoxy group), C1-C18Alkoxycarbonyl, C1-C18Alkylcarbonyl group, C1-C18Alkoxycarbonyloxy, aryloxycarbonyloxy, perfluoro (C)1-C18) Alkoxy, perfluoro (C)1-C18) Alkoxycarbonyl, perfluoro (C)1-C18) Alkylcarbonyl, perfluoro (C)1-C18) Alkylamino, di- (perfluoro (C)1-C18) Alkyl) amino, perfluoro (C)1-C18) Alkylthio radical, C1-C18Alkylthio radical, C1-C18Acetyl, C3-C10Cycloalkyl radical, C3-C10Cycloalkoxy, straight chain C1-C18Alkyl and branched C1-C18An alkyl group;
wherein said straight chain C1-C18Alkyl and branched C1-C18The alkyl group is monosubstituted with a group selected from: cyano, halogen and C1-C18An alkoxy group; or
Wherein said straight chain C1-C18Alkyl and branched C1-C18The alkyl group is polysubstituted with at least two groups independently selected from the group consisting of: halogen, -M (T)(v-1)and-M (OT)(v-1)Wherein M is selected from the group consisting of aluminum, antimony, tantalum, titanium, zirconium and silicon, and T is selected from the group consisting of organofunctional groups, organofunctional groupsA hydrocarbon group, an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and v is the valence of M;
(b) c, d, e and f are each independently selected from integers from 1 to 20; and each S1、S2、S3、S4And S5Independently at each occurrence, is selected from a spacer unit selected from:
(i) alkylene, substituted alkylene, haloalkylene, substituted haloalkylene, -Si (CH)2)g-and- (Si [ (CH)3)2]O)h-, wherein g is independently selected at each occurrence from an integer of 1 to 20; h is independently at each occurrence an integer selected from 1 to 16; and the substituents of said alkylene and haloalkylene groups are independently selected from C1-C18Alkyl radical, C3-C10Cycloalkyl and aryl groups;
(ii)-N(Z)-、-C(Z)＝C(Z)-、-C(Z)＝N-、-C(Z’)2-C(Z’)2-、-N(Z)-C(Z)2-and a single bond, wherein Z is independently at each occurrence selected from hydrogen, C1-C18Alkyl radical, C3-C10Cycloalkyl and aryl, and Z' is independently at each occurrence selected from C1-C18Alkyl radical, C3-C10Cycloalkyl and aryl groups; and
(iii) -O-, -C (═ O) -, -C ≡ C-, -N ═ N-, -S (═ O) -, - (O ═ S (═ O) O-, -O (O ═) S (═ O) O-, and linear or branched C ═ O) O-1-C24Alkylene residue of said C1-C24The alkylene residue is unsubstituted, mono-substituted by cyano or halogen, or poly-substituted by halogen,
provided that when two spacer units containing a heteroatom are linked together, the spacer units are linked such that the heteroatoms are not directly linked to each other, and S5The bond with P does not contain two heteroatoms attached to each other;
(c) p is independently at each occurrence selected from hydroxy, amino, C2-C18Alkenyl radical, C2-C18Alkynyl, azido, silyl, siloxy, silylhydride, (tetrahydro-2H-Pyran-2-yl) oxy, thio, isocyanato, thioisocyanato, acryloxy, methacryloxy, 2- (acryloxy) ethylcarbamoyl, 2- (methacryloxy) ethylcarbamoyl, aziridinyl, allyloxycarbonyloxy, epoxy, carboxylic acid ester, acrylamido, methacrylamido, aminocarbonyl, C1-C18Alkylaminocarbonyl, aminocarbonyl (C)1-C18) Alkyl radical, C1-C18Alkoxycarbonyloxy, halocarbonyl, hydrogen, aryl, hydroxy (C)1-C18) Alkyl radical, C1-C18Alkyl radical, C1-C18Alkoxy, amino (C)1-C18) Alkyl radical, C1-C18Alkylamino, di- (C)1-C18) Alkylamino radical, C1-C18Alkyl radical (C)1-C18) Alkoxy radical, C1-C18Alkoxy (C)1-C18) Alkoxy, nitro, poly (C)1-C18) Alkyl ethers, (C)1-C18) Alkyl radical (C)1-C18) Alkoxy (C)1-C18) Alkyl, polyethyleneoxy, polypropyleneoxy, ethylene, acryloyl, acryloyloxy (C)1-C18) Alkyl, methacryloyl, methacryloyloxy (C)1-C18) Alkyl, 2-chloropropenoyl, 2-phenylpropenoyl, acryloxyphenyl, 2-chloropropenamido, 2-phenylacrylaminocarbonyl, oxetanyl, glycidyl, cyano, isocyanato (C)1-C18) Alkyl, itaconate, vinyl ether, vinyl ester, styrene derivatives, main and side chain liquid crystalline polymers, siloxane derivatives, ethyleneimine derivatives, maleic acid derivatives, maleimide derivatives, fumaric acid derivatives, unsubstituted cinnamic acid derivatives, cinnamic acid derivatives substituted with at least one of methyl, methoxy, cyano and halogen, and substituted or unsubstituted chiral or achiral monovalent or divalent groups selected from the group consisting of steroid groups, terpene groups, alkaloid groups and mixtures thereof, wherein the substituents are independently selected from the group consisting of C1-C18Alkyl radical, C1-C18Alkoxy, amino, C3-C10Cycloalkyl radical, C1-C18Alkyl radical (C)1-C18) Alkoxy, fluoro (C)1-C18) Alkyl, cyano (C)1-C18) Alkyl, cyano (C)1-C18) Alkoxy groups or mixtures thereof, or P is a structure having 2 to 4 reactive groups, or P is an unsubstituted or substituted ring opening metathesis polymerization precursor, or P is a substituted or unsubstituted photochromic compound; and
(d) d ', e' and f 'are each independently selected from 0,1, 2,3 and 4, provided that the sum of d' + e '+ f' is at least 1; and
wherein each group Y1、Y2And Y3Independently comprises the residue of at least one ring-opened cyclic monomer, wherein each ring-opened cyclic monomer is independently selected from the group consisting of a ring-opened cyclic ester monomer and a ring-opened cyclic carbonate monomer.
2. The photochromic compound of claim 1 wherein,
R2selected from hydrogen; fluorine; chlorine; bromine; straight or branched C1-C10An alkyl group; straight or branched C1-C10A perhaloalkyl group; -ORa；-SRaWherein each R isaIndependently selected from hydrogen, linear or branched C1-C10Alkyl and straight or branched C1-C10A perhaloalkyl group; -C (O) ORbWherein R isbIs hydrogen or straight or branched C1-C6An alkyl group; substituted or unsubstituted phenyl, each phenyl substituent being independently selected from hydroxy, halogen, carbonyl, straight or branched C1-C10Alkoxycarbonyl, cyano, straight-chain or branched C1-C10Haloalkyl, straight-chain or branched C1-C10Alkyl, straight or branched C1-C10Alkoxy and straight or branched C1-C10A perhaloalkyl group; and a group Y1；
R6And R7Each independently selected from hydrogen; fluorine; chlorine; bromine; an elongation group L1；-ORc(ii) a and-SRcWherein each R iscIndependently selected from hydrogen, an elongation group L2Straight or branched C1-C10Alkyl, -C (O) -RdAnd S (O) ReWherein R isdAnd ReEach independently selected from linear or branched C1-C6Alkyl, straight or branched C1-C6Perhaloalkyl, phenyl, straight or branched C1-C6Alkyl-substituted phenyl and straight or branched C1-C6Perhaloalkyl-substituted phenyl; and
R1independently for each of n and R3Independently for each m is independently selected from
Hydrogen;
a cyano group;
an elongation group L3；
Halogen selected from fluorine, chlorine and bromine;
straight or branched C1-C10An alkyl group;
straight or branched C1-C10A perhaloalkyl group;
C3-C7a cycloalkyl group;
-O-R10’；
-S-R10’；
radical Y2(ii) a And
a substituted or unsubstituted phenyl, said phenyl substituent being selected from at least one of the following groups: hydroxy, halogen, carbonyl, straight or branched C1-C10Alkoxycarbonyl, cyano, straight-chain or branched C1-C10Haloalkyl, straight-chain or branched C1-C10Alkyl, straight or branched C1-C10Alkoxy, straight or branched C1-C10Perhaloalkyl, and combinations thereof;
wherein-O-R10' and-S-R10' Each R of10' independently hydrogen, straight or branched C1-C10Alkyl, benzeneRadical (C)1-C10) Alkyl, mono (C)1-C10) Alkyl-substituted phenyl (C)1-C10) Alkyl, mono (C)1-C10) Alkoxy-substituted phenyl (C)1-C10) Alkyl, (C)1-C10) Alkoxy (C)2-C10) Alkyl radical, C3-C7Cycloalkyl or mono (C)1-C10) Alkyl substituted C3-C7A cycloalkyl group;
R4and R5Each independently selected from hydrogen; straight or branched C1-C10An alkyl group; straight or branched C1-C10A haloalkyl group; c3-C7A cycloalkyl group; and a group Y3(ii) a Or R4And R5Together form a spiro substituent which is a substituted or unsubstituted spirocarbocyclic ring containing from 3 to 10 carbon atoms; and
b and B' are independently selected in each occurrence from:
an aryl group monosubstituted with a reactive substituent; a substituted phenyl group; a substituted aryl group; substituted 9-julolidinyl; a substituted heteroaromatic group selected from pyridyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl, wherein the phenyl, aryl, 9-julolidinyl or heteroaromatic substituent is a reactive substituent R; unsubstituted, mono-, di-or tri-substituted phenyl or aryl; 9-julolidinyl; or an unsubstituted, mono-substituted or di-substituted heteroaromatic group selected from the group consisting of pyridyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl, wherein each of the phenyl, aryl and heteroaromatic substituents is independently:
hydroxy, group-C (═ O) R21Wherein R is21is-OR22，-N(R23)R24Piperazine and piperazinePyridyl or morpholinyl, wherein R22Is allyl, straight-chain or branched C1-C20Alkyl, phenyl, mono (C)1-C20) Alkyl substituted phenyl, mono (C)1-C20) Alkoxy-substituted phenyl, phenyl (C)1-C20) Alkyl, mono (C)1-C20) Alkyl-substituted phenyl (C)1-C20) Alkyl, mono (C)1-C20) Alkoxy-substituted phenyl (C)1-C20) Alkyl radical, C1-C20Alkoxy (C)2-C20) Alkyl or C1-C20Haloalkyl, R23And R24Each independently is C1-C20Alkyl radical, C5-C10Cycloalkyl, phenyl or substituted phenyl, the phenyl substituent being C1-C20Alkyl or C1-C20Alkoxy, and said halo substituent is chloro or fluoro, aryl, mono (C)1-C20) Alkoxyaryl, di (C)1-C20) Alkoxyaryl, mono (C)1-C20) Alkylaryl, di (C)1-C20) Alkylaryl, haloaryl, C3-C10Cycloalkyl aryl, C3-C10Cycloalkyl radical, C3-C10Cycloalkoxy, C3-C10Cycloalkoxy (C)1-C20) Alkyl radical, C3-C10Cycloalkoxy (C)1-C20) Alkoxy, aryl (C)1-C20) Alkyl, aryl (C)1-C20) Alkoxy, aryloxy (C)1-C20) Alkyl, aryloxy (C)1-C20) Alkoxy, mono-or di (C)1-C20) Alkylaryl (C)1-C20) Alkyl, mono-or di- (C)1-C20) Alkoxyaryl (C)1-C20) Alkyl, mono-or di- (C)1-C20) Alkylaryl (C)1-C20) Alkoxy, mono-or di- (C)1-C20) Alkoxyaryl (C)1-C20) Alkoxy, amino, mono-or di- (C)1-C20) Alkylamino, diaryl radicalsAmino, piperazinyl, N- (C)1-C20) Alkylpiperazino, N-arylpiperazinyl, aziridino, indolinyl, piperidinyl, morpholinyl, thiomorpholinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, pyrrolidinyl, C1-C20Alkyl radical, C1-C20Haloalkyl, C1-C20Alkoxy, mono (C)1-C20) Alkoxy (C)1-C20) Alkyl, acryloxy, methacryloxy or halogen;
an unsubstituted or mono-substituted radical selected from the group consisting of pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, each of said substituents being C1-C20Alkyl radical, C1-C20Alkoxy, phenyl or halogen;
a group represented by one of:
wherein K is-CH2-or-O-, and M is-O-or a substituted nitrogen, with the proviso that when M is a substituted nitrogen, K is-CH2-, said substituted nitrogen substituents being hydrogen, C1-C20Alkyl or C1-C20Acyl radical, each R25Independently at each occurrence is selected from C1-C20Alkyl radical, C1-C20Alkoxy, hydroxy and halogen, R26And R27Each independently is hydrogen or C1-C20Alkyl, and u is an integer in the range of 0 to 2; or
A group represented by:
wherein R is28Is hydrogen or C1-C20Alkyl, and R29Is an unsubstituted, mono-or di-substituted radical selected from the group consisting of naphthyl, phenyl, furyl and thienyl, whereinThe substituent is C1-C20Alkyl radical, C1-C20Alkoxy or halogen; or
B and B' together form one of a fluoren-9-ylidene, mono-substituted or di-substituted fluoren-9-ylidene, each fluoren-9-ylidene substituent being independently selected from C1-C20Alkyl radical, C1-C20Alkoxy and halogen;
wherein Y is independently for each group1、Y2And Y3，
Each cyclic ester monomer of each ring-opened cyclic ester monomer is independently represented by the following formula (A),
wherein for formula (a), I and J are each independently an integer in the range of 1 to 8; r13、R14、R15And R16For each carbon unit (C)IAnd (C)JIndependently selected from-H and C1-C16 alkyl; k is 0 or 1; and D is-O-when k is 1; and
each cyclic carbonate monomer of each ring-opened cyclic carbonate monomer is independently represented by the following formula (B),
wherein for formula (B), m and q are each independently an integer in the range of 1 to 3; r17、R18、R19And R20For each carbon unit (C)mAnd (C)qEach independently selected from-H and C1-C16 alkyl; t is 0 or 1; and E is-O-when t is 1.
3. The photochromic compound of claim 2 wherein,
R2selected from hydrogen; fluorine; chlorine; bromine; straight or branched C1-C6An alkyl group; straight or branched C1-C6A perhaloalkyl group; -ORa；-SRaWhich isEach R inaIndependently selected from hydrogen, linear or branched C1-C6Alkyl and straight or branched C1-C6A perhaloalkyl group; -C (O) ORbWherein R isbIs hydrogen or straight or branched C1-C3An alkyl group; substituted or unsubstituted phenyl, each phenyl substituent being independently selected from hydroxy, halogen, straight or branched C1-C6Alkoxycarbonyl, cyano, straight-chain or branched C1-C6Haloalkyl, straight-chain or branched C1-C6Alkyl, straight or branched C1-C6Alkoxy and straight or branched C1-C6A perhaloalkyl group; and a group Y1；
R6And R7Each independently selected from hydrogen; fluorine; chlorine; bromine; an elongation group L1；-ORc(ii) a and-SRcWherein each R iscIndependently selected from hydrogen, an elongation group L2Straight or branched C1-C6Alkyl, -C (O) -RdAnd S (O) ReWherein R isdAnd ReEach independently selected from linear or branched C1-C3Alkyl, straight or branched C1-C3Perhaloalkyl, phenyl, straight or branched C1-C3Alkyl-substituted phenyl and straight or branched C1-C3A phenyl group substituted with a perhaloalkyl group,
R1independently for each of n and R3Independently for each m is independently selected from
Hydrogen;
a cyano group;
an elongation group L3；
Straight or branched C1-C6An alkyl group;
C3-C6a cycloalkyl group;
straight or branched C1-C8A perhaloalkyl group;
fluorine;
chlorine;
the bromine is added to the reaction mixture,
-O-R10’，
-S-R10’；
radical Y2(ii) a And
a substituted or unsubstituted phenyl, said phenyl substituent being selected from at least one of the following groups: hydroxy, halogen, straight or branched C1-C6Alkoxycarbonyl, cyano, straight-chain or branched C1-C6Haloalkyl, straight-chain or branched C1-C6Alkyl, straight or branched C1-C6Alkoxy and straight or branched C1-C6A perhaloalkyl group;
wherein-O-R10' and-S-R10' Each R of10' independently hydrogen, straight or branched C1-C6Alkyl, phenyl (C)1-C6) Alkyl, mono (C)1-C6) Alkyl-substituted phenyl (C)1-C6) Alkyl, mono (C)1-C6) Alkoxy-substituted phenyl (C)1-C6) Alkyl, (C)1-C6) Alkoxy (C)2-C6) Alkyl radical, C3-C6Cycloalkyl or mono (C)1-C6) Alkyl substituted C3-C6A cycloalkyl group;
R4and R5Each independently selected from hydrogen; straight or branched C1-C8An alkyl group; straight or branched C1-C8A haloalkyl group; c3-C6A cycloalkyl group; and a group Y3(ii) a Or R4And R5Together form a spiro substituent which is a substituted or unsubstituted spirocarbocyclic ring containing from 3 to 10 carbon atoms; and
b and B' are in each case independently selected from
An unsubstituted aryl group, a substituted aryl group,
by straight or branched C1-C6An alkoxy-substituted aryl group, wherein the aryl group is substituted with an alkoxy group,
by straight or branched C1-C6A perhaloalkyl-substituted aryl group,
aryl substituted by morpholinyl, and
an aryl group substituted with a piperidinyl group,
wherein Y is independently for each group1、Y2And Y3，
Each cyclic ester monomer of each ring-opened cyclic ester monomer is independently selected from epsilon (epsilon) -caprolactone; ζ (zeta) -heptalactone; delta (delta) -valerolactone; monoalkyl delta valerolactone; monoalkyl, dialkyl or trialkyl-epsilon (epsilon) -caprolactone; beta (beta) -lactone; gamma (gamma) -lactone; a dilactone; and ketodioxanone; and
each cyclic carbonate monomer of each ring-opened cyclic carbonate monomer is independently selected from ethylene carbonate; 3-ethyl-3-hydroxymethyltrimethylene carbonate; propylene carbonate, trimethylene carbonate; trimethylolpropane monocarbonate; 4, 6-dimethyl-1, 3-propylene carbonate; 2, 2-dimethyltrimethylene carbonate; and 1, 2-dioxepan-2-one.
4. The photochromic compound of claim 1 wherein,
R6and R7At least one is selected from the group consisting of the elongation groups L1and-ORcWherein R iscIs an elongation group L2。
5. The photochromic compound of claim 1 wherein,
independently for each of the elongation groups L represented by formula (II)1、L2And L3，
(a)Q1、Q2And Q3Independently at each occurrence, is selected from the group consisting of unsubstituted aryl, substituted aryl, unsubstituted cycloalkyl and substituted cycloalkyl,
(b) each S1、S2、S3、S4And S5Independently at each occurrence, is selected from a spacer unit selected from
(ii)-N(Z)-、-C(Z)＝C(Z)-、-C(Z)＝N-、-C(Z’)2-C(Z’)2-、-N(Z)-C(Z’)2And a single bond, wherein Z is at each occurrenceIndependently at present, is selected from hydrogen, C1-C8Alkyl radical, C3-C6Cycloalkyl and aryl, and Z' is independently at each occurrence selected from C1-C8Alkyl radical, C3-C6Cycloalkyl and aryl, and
(iii) -O-, -C (═ O) -, -C ≡ C-, -N ═ N-, -S (═ O) -, and linear or branched C1-C12Alkylene residue of said C1-C12The alkylene residue being unsubstituted, mono-substituted by cyano or halogen or poly-substituted by halogen, and
(c) p is independently at each occurrence selected from hydrogen, hydroxy, amino, C2-C8Alkenyl radical, C2-C8Alkynyl, acryloyloxy, methacryloyloxy, 2- (acryloyloxy) ethylcarbamoyl, 2- (methacryloyloxy) ethylcarbamoyl, epoxy, carboxylic acid, carboxylic ester, acrylamido, methacrylamido, aminocarbonyl, C1-C8Alkylaminocarbonyl, aminocarbonyl (C)1-C8) Alkyl radical, C1-C8Alkoxycarbonyloxy, halocarbonyl, aryl, hydroxy (C)1-C8) Alkyl radical, C1-C8Alkyl radical, C1-C8Alkoxy, amino (C)1-C8) Alkyl radical, C1-C8Alkylamino, di- (C)1-C8) Alkylamino radical, C1-C8Alkyl radical (C)1-C8) Alkoxy radical, C1-C8Alkoxy (C)1-C8) Alkoxy, nitro, poly (C)1-C8) Alkyl ether, (C)1-C8) Alkyl radical (C)1-C8) Alkoxy (C)1-C8) Alkyl, polyethyleneoxy, polypropyleneoxy, ethylene, acryloyl, acryloyloxy (C)1-C18) Alkyl, methacryloyl, methacryloyloxy (C)1-C8) Alkyl, 2-chloropropenoyl, 2-phenylpropenoyl, acryloxyphenyl, 2-chloropropenamido, 2-phenylacrylaminocarbonyl, oxetanyl, glycidyl, cyano, isocyanato (C)1-C18) Alkyl, itaconate, vinyl ether and vinyl ester.
6. The photochromic compound of claim 5 wherein,
independently for each of the elongation groups L represented by formula (II)1、L2And L3，
(b) Each S1、S2、S3、S4And S5Independently at each occurrence, is selected from a spacer unit selected from
(ii) -n (Z) -, -C (Z) ═ C (Z) -and single bonds, wherein Z is independently selected at each occurrence from hydrogen, C, and C1-C8Alkyl radical, C3-C6Cycloalkyl and aryl, and Z' is independently at each occurrence selected from C1-C8Alkyl radical, C3-C6Cycloalkyl and aryl, and
(iii) -O-, -C (═ O) -, -C ≡ C-, and straight or branched C1-C6Alkylene residue of said C1-C6The alkylene residue being unsubstituted, mono-substituted by cyano or halogen or poly-substituted by halogen, and
(c) p is independently at each occurrence selected from hydrogen, hydroxy, amino, C2-C8Alkenyl radical, C2-C8Alkynyl and aryl.
7. The photochromic compound of claim 4, wherein R6And R7Each independently selected from the group consisting of an elongation group L1and-ORcWherein R iscIs an elongation group L2。
8. The photochromic compound of claim 1, wherein R6Selected from the group consisting of the extending groups L1and-ORcWherein R iscIs an elongation group L2And R7Is halogen.
9. The photochromic compound of claim 4 wherein,
r in the 11 position3Selected from halogen, -CN, straight or branched C1-C8Perhaloalkyl, unsubstituted phenyl, and halogen and straight or branched C1-C8At least one substituted phenyl group in perhaloalkyl.
10. The photochromic compound of claim 1 wherein R is at position 123Is an elongation group L3。
11. The photochromic compound of claim 4 wherein R at the 11-position3Is halogen.
12. The photochromic compound of claim 1 wherein each extending group L1、L2And L3In each case independently selected from
L (5)4- (4-pentyl-phenylazo) -phenylcarbamoyl
L (7) {4- [5- (4-propyl-benzoyloxy) -pyrimidin-2-yl ] -phenyl } ester
L (8) {4- [2- (4' -methyl-biphenyl-4-carbonyloxy) -1, 2-diphenyl-ethoxycarbonyl ] -phenyl } ester
L (10)4- [4- (4- {4- [3- (6- {4- [4- (4-nonyl-benzoyloxy) -phenoxycarbonyl ] -phenoxy } -hexyloxycarbonyl) -propionyloxy ] -benzoyloxy } -benzoyloxy) -phenyl ] -piperazin-1-yl
L (11) {4- [4- (4- {4- [4- (4-nonyl-benzoyloxy) -benzoyloxy ] -benzoyloxy } -benzoyloxy) -phenyl ] -piperazin-1-yl }
L (12)4- (4' -propyl-biphenyl-4-ylethynyl) -phenyl
L (16)4- (biphenyl-4-carbonyloxy) -piperidin-1-yl
L (18)4- (4-phenylcarbamoyl) -piperidin-1-yl
L (19)4- (4- (4-phenylpiperidin-1-yl) -benzoyloxy) -piperidin-1-yl
L (20) 4-butyl- [1, 1'; 4',1 "] terphenyl-4-yl
L (21)4- (4-pentadecafluoroheptyloxy-phenylcarbamoyl) -benzyloxy
L (24)4- [4- (4-cyclohexyl-phenylcarbamoyl) -benzoyloxy ] -piperidin-1-yl
L (25) N- {4- [ (4-pentyl-benzylidene) -amino ] -phenyl } -acetylamino
L (28)4- (4' -hexyloxy-biphenyl-4-carbonyloxy) -piperidin-1-yl
L (30a) 1-methyl-4- ((4'- (((1-methylpiperidin-4-yl) oxy) carbonyl) - [1,1' -biphenyl ] -4-carbonyl) oxy) piperidin-1-yl
L (30b) bis (1-yl-piperidin-4-yl) [1,1 '-biphenyl ] -4,4' -dicarboxylate
L (31)4- (4- (9- (4-butylphenyl) -2,4,8, 10-tetraoxaspiro [5.5] undecan-3-yl) phenyl) piperazin-1-yl
L (32)4- (6- (4-butylphenyl) carbonyloxy- (4, 8-dioxabicyclo [3.3.0] oct-2-yl)) oxycarbonyl) phenyl
L (33)1- {4- [5- (4-butyl-phenyl) - [1,3] dioxan-2-yl ] -phenyl } -4-methyl-piperazin-1-yl
L (34)4- (7- (4-Propylphenylcarbonyloxy) bicyclo [3.3.0] oct-2-yl) oxycarbonyl) phenyl
L (35)4- [17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthren-3-yloxycarbonyloxy
L(a)
L(c)
L(g)
L(h)
L(i)
L(j)
L(k)
L(l)
L(m)
L(r)
L(t)
L(v)
L(z)
L(ac)
L(ad)
L-DC- (a) (4-trans- (4-pentylcyclohexyl) benzoylamino) phenyl,
L-DC- (d)4- ((trans- (4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-yl) oxy) carbonyl) phenyl,
L-DC- (g)4- (4'- (4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-carbonyl) piperazin-1-yl,
L-DC- (h)4- (4- (4-trans- (4-pentylcyclohexyl) phenyl) benzoylamino) -2- (trifluoromethyl) phenyl,
L-DC- (i) 2-methyl-4-trans- (4- ((4' -trans- (4-pentylcyclohexyl) biphenyl-4-yloxy) carbonyl) cyclohexanecarboxamido) phenyl,
L-DC- (j)4'- (4' -pentylbis (cyclohexane-4-) carbonyloxy) biphenylcarbonyloxy,
L-DC- (k)4- (((3S,8S,9S,10R,13R,14S,17R) -10, 13-dimethyl-17- ((R) -6-methylheptan-2-yl) -2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthren-3-yloxy) carbonyl) piperazin-1-yl, and
L-DC- (L)4- ((S) -2-methylbutoxy) phenyl) -10- (4- (((3R,3aS,6S,6aS) -6- (4' -trans- (4-pentylcyclohexyl) biphenylcarbonyloxy) hexahydrofuro [3,2-b ] furan-3-yloxy) carbonyl) phenyl,
provided that, for-ORcWherein R iscIs an elongation group L2-O and an elongation group L2The bond between does not contain two heteroatoms attached to each other.
13. A photochromic compound represented by the following formula (III),
formula (III)
Ly-(PC)n’
Wherein the content of the first and second substances,
n' is at least 2 and is,
PC is independently for each n' a residue of a photochromic compound according to claim 1, and
Lyis a polyvalent linking group selected from
A first multivalent compound which is a multivalent polymer, and
a second multivalent compound, different from the first multivalent compound, that is non-polymeric and comprises a residue selected from: residues of polyisocyanates, residues of polyols, residues of polycarboxylic acids, residues of polycarbonate functional materials, and combinations thereof.
14. The photochromic compound of claim 13 wherein,
said multivalent polymer of said first multivalent compound is selected from the group consisting of multivalent polyurethanes, multivalent polyesters, multivalent polyethers, multivalent poly (meth) acrylates, multivalent polyvinyl alcohols, multivalent polycarbonates, multivalent polysiloxanes, and multivalent cyclic polysiloxanes, and
with respect to the second polyvalent compound, the first polyvalent compound,
the polyisocyanate is selected from the group consisting of aliphatic polyisocyanates, cycloaliphatic polyisocyanates, heterocyclic polyisocyanates, and aromatic polyisocyanates, each independently having at least two isocyanate groups, dimers thereof, trimers thereof, and mixtures of one or more thereof,
the polyol is selected from the group consisting of aliphatic polyols, cycloaliphatic polyols, heterocyclic polyols, and aromatic polyols, each independently having at least two hydroxyl groups,
the polycarboxylic acid is selected from the group consisting of aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, heterocyclic polycarboxylic acids, and aromatic polycarboxylic acids, each independently having at least two carboxylic acid groups, and
the polycarbonate functional material is selected from the group consisting of aliphatic polycarbonate functional compounds, alicyclic polycarbonate functional compounds, heterocyclic polycarbonate functional compounds, and aromatic polycarbonate functional compounds, each independently having at least two cyclic carbonate groups.
15. A photochromic composition comprising the photochromic compound of claim 1.
Technical Field
The present invention relates to photochromic indeno-fused phenanthropyran compounds, photochromic compositions and photochromic articles, such as ophthalmic articles, comprising such compounds.
Background
Photochromic compounds and materials, when responsive to certain wavelengths of electromagnetic radiation (or "actinic radiation"), typically undergo a transition from one form or state to another, and each form has a characteristic or distinguishable absorption spectrum associated with it. Typically, upon exposure to actinic radiation, many photochromic materials transform from a closed form (which corresponds to the unactivated (or bleached, or substantially colorless) state of the photochromic material) to an open form (which corresponds to the activated (or colored) state of the photochromic material). Such photochromic materials reversibly convert from an activated (or colored) state back to an unactivated (or bleached) state in the absence of exposure to actinic radiation. Compositions and articles such as ophthalmic lenses that contain photochromic materials or have photochromic materials applied thereto (e.g., in the form of a photochromic coating composition) typically exhibit colorless (or transparent) and colored states that correspond to the colorless and colored states of the photochromic materials contained therein and/or applied thereto. Photochromic compounds, when exposed to actinic radiation and properly aligned together, such as when including one or more extending groups covalently bonded thereto, can provide a combination of both photochromic and dichroic properties. Dichroic properties relate to the ability of photochromic-dichroic compounds to linearly polarize incident unpolarized light. Photochromic compounds and materials are typically characterized by different properties such as photochromic properties, including but not limited to decay (fade) rates; optical density change (sometimes referred to as Δ OD); and dichroic properties (as in the case of photochromic-dichroic compounds), which can be quantified in terms of Absorbance (AR) values.
It is desirable to develop new photochromic compounds. It is further desirable that such newly developed photochromic compounds have properties, such as photochromic properties and optionally dichroic properties, that are at least equal to or superior to those of existing photochromic compounds.
Disclosure of Invention
According to the present invention, there is provided a photochromic compound represented by the following formula (I),
with respect to formula (I), R2Selected from hydrogen; halogen; straight or branched C1-C20An alkyl group; straight or branched C1-C20A perhaloalkyl group; -ORa；-SRaWherein each R isaIndependently selected from hydrogen, linear or branched C1-C20Alkyl and straight or branched C1-C20A perhaloalkyl group; -C (O) ORbWherein R isbIs hydrogen or straight or branched C1-C10An alkyl group; substituted or unsubstituted aryl, each aryl substituent being independently selected from the group consisting of hydroxy, halogen, carbonyl, straight or branched C1-C20Alkoxycarbonyl, cyano, straight-chain or branched C1-C20Haloalkyl, straight-chain or branched C1-C20Alkyl, straight or branched C1-C20Alkoxy and straight or branched C1-C20A perhaloalkyl group; and a group Y1(as described further herein).
In addition to the formula (I), R6And R7Each independently selected from hydrogen; halogen; an elongation group L1(as described in additional detail herein); -ORcand-SRcWherein each R iscIndependently selected from hydrogen, an elongation group L2(as described in additional detail herein), straight or branched C1-C20Alkyl, -C (O) -RdAnd S (O) ReWherein R isdAnd ReEach independently selected from linear or branched C1-C10Alkyl, straight or branched C1-C10Perhaloalkyl, phenyl, straight or branched C1-C10Alkyl-substituted phenyl and straight or branched C1-C10Perhaloalkyl substituted phenyl. R for formula (I)6And R7Provided that R is6And R7Is not hydrogen.
With respect to formula (I), n is 1 to 3, and m is 1 to 4. In addition to the formula (I), R1Independently for each of n and R3Independently for each m each independently selected from: (1) hydrogen; (2) a cyano group; (3) a reactive substituent; (4) an elongation group L3(as described in additional detail herein); (5) halogen selected from fluorine, chlorine and bromine; (6) straight or branched C1-C20An alkyl group; (7) straight or branched C1-C20A perhaloalkyl group; (8) c3-C10A cycloalkyl group; (9) radical Y2(as described in additional detail herein); (10) a substituted or unsubstituted phenyl group, the phenyl substituent being selected from at least one of the following groups: hydroxy, halogen, carbonyl, straight or branched C1-C20Alkoxycarbonyl, cyano, straight-chain or branched C1-C20Haloalkyl, straight-chain or branched C1-C20Alkyl, straight or branched C1-C20Alkoxy, straight or branched C1-C20Perhaloalkyl, and combinations thereof; (11) -O-R10’、-S-R10’、-C(O)-R10’、-C(O)-OR10’、-OC(O)-R10’、-OC(O)O-R10’、-C(O)N(R10’)R10’、-N(R10’)C(O)N(R10’)(R10’) OR-Si (OR)10’)w(R10’)tWherein each R is10' independently hydrogen, straight or branched C1-C20Alkyl, phenyl (C)1-C20) Alkyl, mono (C)1-C20) Alkyl-substituted phenyl (C)1-C20) Alkyl, mono (C)1-C20) Alkoxy-substituted phenyl (C)1-C20) Alkyl, (C)1-C20) Alkoxy (C)2-C20) Alkyl radical, C3-C10Cycloalkyl or mono (C)1-C20) Alkyl substituted C3-C10Cycloalkyl, and w and t are each independentlyFrom 0 to 3 on site, provided that w + t is 3; and (12) -N (R)11’)R12', wherein R11' and R12' independently of one another are hydrogen, straight-chain or branched C1-C20Alkyl, phenyl, naphthyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, benzopyridyl, fluorenyl, straight-chain or branched C1-C20Alkylaryl group, C3-C10Cycloalkyl radical, C4-C20Bicycloalkyl radical, C5-C20Tricycloalkyl or straight or branched C1-C20Alkoxyalkyl in which the aryl radical is phenyl or naphthyl, or R11' and R12' together with the nitrogen atom form a ring, e.g. C3-C20Hetero-bicycloalkyl ring or C4-C20A heterotricycloalkyl ring.
With respect to formula (I), R4And R5Each independently selected from: (i) hydrogen, hydroxy, straight or branched C1-C20Alkyl, straight or branched C1-C20Haloalkyl, C3-C10Cycloalkyl, allyl, benzyl or substituted benzyl, the benzyl substituent being selected from halogen, straight or branched C1-C20Alkyl or straight or branched C1-C20An alkoxy group; (ii) an unsubstituted, mono-, di-or tri-substituted group selected from phenyl, naphthyl, phenanthryl, pyrenyl, quinolinyl, isoquinolinyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl or indolyl, the group substituents in each case being independently selected from halogen, straight-chain or branched C1-C20Alkyl or straight or branched C1-C20An alkoxy group; and (iii) a group Y3(ii) a Or (iv) R4And R5Together form a spiro substituent selected from the group consisting of: a substituted or unsubstituted spirocarbocyclic ring containing from 3 to 10 carbon atoms, a substituted or unsubstituted spiroheterocyclic ring containing from 1 or 2 oxygen atoms and from 3 to 10 carbon atoms including a spirocarbon atom, the spirocarbocyclic ring andthe spiroheterocyclic ring being annelated with 0,1 or 2 benzene rings (annelated), the substituents being hydrogen or C, straight-chain or branched1-C20An alkyl group.
Further with respect to formula (I), B and B 'are each independently selected from unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, alkenyl and alkynyl, or B and B' taken together form a ring structure.
With respect to formula (I) and the various groups thereof, each of the extending groups L1、L2And L3Independently represented by the following formula (II):
formula (II)
–[S1]c-[Q1–[S2]d]d’-[Q2–[S3]e]e’-[Q3–[S4]f]f’–S5–P
With respect to the formulae (II), (a) Q1、Q2And Q3Independently at each occurrence is a divalent group selected from the group consisting of: unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted cycloalkyl, substituted cycloalkyl, unsubstituted heterocycloalkyl, and substituted heterocycloalkyl. Q1、Q2And Q3Each of the aryl, heteroaryl, cycloalkyl and heterocycloalkyl substituents of (a) is independently selected from P (as described in further detail herein), liquid crystal mesogens, halogens, poly (C)1-C18Alkoxy group), C1-C18Alkoxycarbonyl, C1-C18Alkylcarbonyl group, C1-C18Alkoxycarbonyloxy, aryloxycarbonyloxy, perfluoro (C)1-C18) Alkoxy, perfluoro (C)1-C18) Alkoxycarbonyl, perfluoro (C)1-C18) Alkylcarbonyl, perfluoro (C)1-C18) Alkylamino, di- (perfluoro (C)1-C18) Alkyl) amino, perfluoro (C)1-C18) Alkylthio radical, C1-C18Alkylthio radical, C1-C18Acetyl, C3-C10Cycloalkyl radical, C3-C10Cyclic alkoxy radicalBasic, straight chain C1-C18Alkyl and branched C1-C18An alkyl group. (Q)1、Q2And Q3Aryl, heteroaryl, cycloalkyl and heterocycloalkyl substituents of (a) a straight chain C1-C18Alkyl and branched C1-C18Each alkyl group is independently selected from cyano, halogen and C1-C18The radical of alkoxy is monosubstituted. Or, (Q)1、Q2And Q3Aryl, heteroaryl, cycloalkyl and heterocycloalkyl substituents of (a) a straight chain C1-C18Alkyl and branched C1-C18Each alkyl group is independently polysubstituted with at least two groups independently selected from: halogen, -M (T)(v-1)and-M (OT)(v-1)Wherein M is selected from the group consisting of aluminum, antimony, tantalum, titanium, zirconium, and silicon, T is selected from the group consisting of organofunctional groups, organofunctional hydrocarbon groups, aliphatic hydrocarbon groups, and aromatic hydrocarbon groups, and v is the valence state of M.
Further with respect to formula (II), (b) subscripts c, d, e, and f are each independently selected from integers of 1 to 20; and each S1、S2、S3、S4And S5Independently at each occurrence, is selected from a spacer unit selected from: (i) alkylene, substituted alkylene, haloalkylene, substituted haloalkylene, -Si (CH)2)g-and- (Si [ (CH)3)2]O)h-, wherein g is independently selected at each occurrence from an integer of 1 to 20; h is independently at each occurrence an integer selected from 1 to 16; and the substituents of alkylene and haloalkylene are independently selected from C1-C18Alkyl radical, C3-C10Cycloalkyl and aryl groups; (ii) -N (Z) -, -C (Z) ═ C (Z) -, -C (Z) ═ N-, -C (Z')2-C(Z’)2-、-N(Z)-C(Z)2-and a single bond, wherein Z is independently at each occurrence selected from hydrogen, C1-C18Alkyl radical, C3-C10Cycloalkyl and aryl, and Z' is independently at each occurrence selected from C1-C18Alkyl radical, C3-C10Cycloalkyl and aryl groups; and (iii) -O-, -C (═ O) -, -C ≡ C-, -N ═ N-, -S (═ O) -, - (O ═ S (═ O) O-, -O (O ═) S (═ O) O-, and linear or branched C ═ O) O —1-C24An alkylene residue of1-C24An alkylene residue is unsubstituted, mono-substituted by cyano or halogen or poly-substituted by halogen. With respect to S1、S2、S3、S4And S5Provided that when two heteroatom-containing spacer units are linked together, the spacer units are linked such that the heteroatoms are not directly linked to each other, and S5The bond with P does not contain two heteroatoms attached to each other.
In addition, with respect to formula (II), (C) P is independently selected at each occurrence from hydroxy, amino, C2-C18Alkenyl radical, C2-C18Alkynyl, azido, silyl, siloxy, silylhydride, (tetrahydro-2H-pyran-2-yl) oxy, thio, isocyanato, thioisocyanato, acryloxy, methacryloxy, 2- (acryloxy) ethylcarbamoyl, 2- (methacryloxy) ethylcarbamoyl, aziridinyl, allyloxycarbonyloxy, epoxy, carboxylic acid ester, acrylamido, methacrylamido, aminocarbonyl, C1-C18Alkylaminocarbonyl, aminocarbonyl (C)1-C18) Alkyl radical, C1-C18Alkoxycarbonyloxy, halocarbonyl, hydrogen, aryl, hydroxy (C)1-C18) Alkyl radical, C1-C18Alkyl radical, C1-C18Alkoxy, amino (C)1-C18) Alkyl radical, C1-C18Alkylamino, di- (C)1-C18) Alkylamino radical, C1-C18Alkyl radical (C)1-C18) Alkoxy radical, C1-C18Alkoxy (C)1-C18) Alkoxy, nitro, poly (C)1-C18) Alkyl ethers, (C)1-C18) Alkyl radical (C)1-C18) Alkoxy (C)1-C18) Alkyl, polyethyleneoxy, polypropyleneoxy, ethylene, acryloyl, acryloyloxy (C)1-C18) Alkyl, methacryloyl, methacryloyloxy (C)1-C18) Alkyl, 2-chloropropenoyl, 2-phenylpropenoyl, acryloxyphenyl, 2-chloropropenamido, 2-phenylacrylaminocarbonyl, oxetanyl, glycidyl, cyano, isocyanato (C)1-C18) Alkyl, itaconate, vinyl ether, vinyl ester, styrene derivatives, main and side chain liquid crystalline polymers, siloxane derivatives, ethyleneimine derivatives, maleic acid derivatives, maleimide derivatives, fumaric acid derivatives, unsubstituted cinnamic acid derivatives, cinnamic acid derivatives substituted with at least one of methyl, methoxy, cyano and halogen, and substituted or unsubstituted chiral or achiral monovalent or divalent groups selected from steroid groups, terpene groups, alkaloid groups and mixtures thereof, wherein the substituents are independently selected from C1-C18Alkyl radical, C1-C18Alkoxy, amino, C3-C10Cycloalkyl radical, C1-C18Alkyl radical (C)1-C18) Alkoxy, fluoro (C)1-C18) Alkyl, cyano (C)1-C18) Alkyl, cyano (C)1-C18) Alkoxy groups or mixtures thereof, or P is a structure having 2 to 4 reactive groups, or P is an unsubstituted or substituted ring opening metathesis polymerization precursor, or P is a substituted or unsubstituted photochromic compound.
Still further with respect to formula (II), subscripts d ', e', and f 'are each independently selected from 0,1, 2,3, and 4, provided that the sum of d' + e '+ f' is at least 1.
With respect to formula (I) and the various groups thereof, each group Y1、Y2And Y3Independently comprises the residue of at least one ring-opened cyclic monomer, wherein each ring-opened cyclic monomer is independently selected from the group consisting of a ring-opened cyclic ester monomer and a ring-opened cyclic carbonate monomer.
The features that characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. These and other features of the present invention, its operating advantages and specific objects attained by its uses will be more fully understood from the following detailed description in which non-limiting embodiments of the invention are illustrated and described.
Drawings
Fig. 1(a) is an illustrative representative first part (part 1) of a general scheme (scheme 1) for preparing compounds according to some embodiments of the invention, as represented by formula (I), otherwise described herein;
FIG. 1(b) is an illustrative representative second part (part 2) of the general scheme (scheme 1) of FIG. 1 (a); and
fig. 1(c) is an illustrative representative third section (section 3) of the general scheme (scheme 1) of fig. 1(a) and 1 (b).
In fig. 1(a) to 1(c), similar characters refer to the same compounds and/or reactants as appropriate, unless otherwise specified.
Detailed Description
As used herein, the articles "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent otherwise.
Unless otherwise indicated, all ranges or ratios disclosed herein are to be understood to encompass any and all subranges or sub-ratios subsumed therein. For example, an indicated range or ratio of "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10 (and including 1 and 10); that is, all subranges or sub-ratios 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.
As used herein, unless otherwise indicated, a representation of a linking group, such as a divalent linking group, from left to right includes other suitable orientations, such as, but not limited to, right to left orientations. For non-limiting illustrative purposes, divalent linking groups
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about".
As used herein, the molecular weight values, such as weight average molecular weight (Mw) and number average molecular weight (Mn), of a polymer are measured by gel permeation chromatography using appropriate standards, such as polystyrene standards.
As used herein, polydispersity index (PDI) values represent the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) of a polymer (i.e., Mw/Mn).
As used herein, the term "polymer" means homopolymers (e.g., prepared from a single monomer species), copolymers (e.g., prepared from at least two monomer species), and graft polymers.
As used herein, the term "(meth) acrylate" and similar terms, such as an ester of "(meth) acrylic acid," means a methacrylate and/or an acrylate. As used herein, the term "(meth) acrylic" means methacrylic and/or acrylic.
The photochromic compounds of the present invention are also referred to herein in some embodiments as photochromic-dichroic compounds (e.g., when they include one or more extending groups, such as L1、L2And/or L3Time).
The photochromic compounds of the present invention, as described herein, include, but are not limited to, photochromic compounds represented by formula (I), and in each case may optionally additionally include one or more by-products (copreducts) resulting from the synthesis of such compounds.
As used herein, the term "photochromic" and similar terms, such as "photochromic compound" are meant to have an absorption spectrum for at least visible radiation that changes in response to the absorption of at least actinic radiation. Further, as used herein, the term "photochromic material" means any substance that is adapted to exhibit photochromic properties (e.g., is adapted to have an absorption spectrum for at least visible radiation that changes in response to absorption of at least actinic radiation), and that includes at least one photochromic compound.
As used herein, the term "actinic radiation" means electromagnetic radiation capable of causing a response in a material, such as, but not limited to, converting a photochromic material from one form or state to another, as will be discussed in further detail herein.
As used herein, the term "photochromic materials" includes thermally reversible photochromic materials and compounds as well as non-thermally reversible photochromic materials and compounds. As used herein, the term "thermally reversible photochromic compound/material" means a compound/material that is capable of transforming from a first state, e.g., a "clear state," to a second state, e.g., a "colored state," in response to actinic radiation, and reverting back to the first state in response to thermal energy. As used herein, the term "non-thermally reversible photochromic compound/material" means a compound/material that is capable of transforming from a first state, e.g., "clear state," to a second state, e.g., "colored state," in response to actinic radiation, and reverts back to the first state in response to actinic radiation of one or more wavelengths that are substantially the same as one or more absorptions of the colored state (e.g., discontinuing exposure to such actinic radiation).
As used herein to modify the term "state," the terms "first" and "second" are not intended to imply any particular order or sequence, but instead imply two different conditions or properties. For non-limiting illustration purposes, the first state and the second state of the photochromic compound may differ in at least one optical property, such as, but not limited to, visible and/or UV radiation absorption. Thus, according to various non-limiting embodiments disclosed herein, the photochromic compounds of the present invention can have different absorption spectra in each of the first and second states. For example, although not limited thereto, the photochromic compounds of the present invention may be transparent in the first state and colored in the second state. Alternatively, the photochromic compounds of the present invention can have a first color in the first state and a second color in the second state.
As used herein, the term "optical" is intended to pertain to or be related to light and/or vision. The optical article or element or device may be selected from ophthalmic articles, elements and devices, display articles, elements and devices, windows, mirrors, and active and passive liquid crystal cell articles, elements and devices, for example, according to various non-limiting embodiments disclosed herein.
As used herein, the term "ophthalmic" is meant to relate to or relate to the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses, including monofocal or multifocal lenses, which may be segmented or non-segmented multifocal lenses (such as, but not limited to, bifocal lenses, trifocal lenses, and progressive lenses), as well as other elements for correcting, protecting, or enhancing (decorative or otherwise) vision, including, but not limited to, contact lenses, intraocular lenses, magnifying lenses, and protective lenses or goggles.
As used herein, the term "display" means a visible or machine-readable representation of information in the form of words, numbers, symbols, designs, or drawings. Non-limiting examples of display elements include screens, monitors, and security elements, such as security markers.
As used herein, the term "window" means an aperture adapted to allow transmission of radiation therethrough. Non-limiting examples of windows include automotive and aircraft transparencies, windshields, filters, shutters and optical switches.
As used herein, the term "mirror" refers to a surface that specularly reflects a substantial portion of incident light.
As used herein, the term "liquid crystal cell" refers to a structure containing a liquid crystal material capable of ordering. A non-limiting example of a liquid crystal cell element is a liquid crystal display.
As used herein, spatial or directional terms, such as "left", "right", "inner", "outer", "upper", "lower", and the like, relate to the invention as it is shown in the drawings. It is to be understood, however, that the invention may assume various alternative orientations and, accordingly, such terms are not to be considered as limiting.
As used herein, the terms "formed on …," "deposited on …," "provided on …," "applied on …," "present on …," or "disposed on …" mean formed, deposited, provided, applied, present on, or disposed on, but not necessarily in direct (or contiguous) contact with an underlying element or underlying element surface. A layer "disposed on" a substrate, for example, does not preclude the presence of one or more other layers, coatings or films of the same or different composition, which are positioned or formed between the layer and the substrate.
As used herein, references to ring positions, such as, but not limited to, the x position (e.g., position 11 or 12) means a particular position in the ring structure, e.g., fused ring structure, of a compound, e.g., a photochromic indeno-fused phenanthropyran compound of the present invention, and is represented herein, according to some embodiments, by a number within the ring structure of a representative formula.
All documents mentioned herein, such as but not limited to issued patents and patent applications, are to be considered "incorporated by reference" in their entirety unless otherwise indicated.
As used herein, a recitation of a "linear or branched" group, such as a linear or branched alkyl group, is understood herein to include: methylene or methyl; straight-chain (linear/straight) radicals, e.g. straight-chain C2-C20An alkyl group; and suitably branched groups such as branch C3-C20An alkyl group.
As used herein, references to alkyl, alkenyl, and alkynyl groups comprising greater than two carbon atoms include straight or branched chain forms (or arrangements) thereof.
As used herein, recitation of an "optionally substituted" group means that the group includes, but is not limited to, alkyl, cycloalkyl, heterocycloalkyl, arylAnd/or heteroaryl, wherein at least one hydrogen thereof has been optionally replaced or substituted by a group other than hydrogen, such as, but not limited to: halo groups (e.g., F, Cl, I, and Br); a hydroxyl group; an ether group; a thiol group; a thioether group; a carboxylic acid group; a carboxylate group; a phosphate group; a phosphate group; a sulfonic acid group; a sulfonate group; a nitro group; a cyano group; an alkyl group; an alkenyl group; an alkynyl group; cycloalkyl (including fused ring cycloalkyl and polycycloalkyl); a heterocycloalkyl group; aryl (including aryl substituted with hydroxy, such as phenol, and including aryl of multiple fused rings); heteroaryl (including polycyclic heteroaryl); aralkyl group; amine groups such as-N (R)11’)(R12') wherein R is11' and R12' each is independently selected from hydrogen, straight or branched C in some embodiments1-C20Alkyl radical, C3-C12Cycloalkyl radical, C3-C12Heterocycloalkyl, aryl and heteroaryl; and reactive substituents, including those classes and examples otherwise described herein.
As used herein, recitation of "halogen-substituted" and related terms (such as, but not limited to, haloalkyl, haloalkenyl, haloalkynyl, haloaryl and haloheteroaryl) mean groups wherein at least one and up to and including all available hydrogen groups thereof are substituted with a halo group. The term "halo-substituted" includes "perhalosubstituted". As used herein, the term "perhalosubstituted" group and related terms (such as, but not limited to, perhaloalkyl, perhaloalkenyl, perhaloalkynyl, perhaloaryl and perhaloheteroaryl) refer to groups in which all of its available hydrogen groups are substituted by halo groups. For example, perhalomethyl is-CX3(ii) a Perhalophenyl is-C6X5Wherein X represents one or more halo groups such as, but not limited to, F.
According to some embodiments, as used herein, the term "alkyl" means a straight or branched chain alkyl group, such as, but not limited to, straight or branched chain C1-C25Alkyl, or straight or branched C1-C10Alkyl, or straight or branched C2-C10An alkyl group. Examples of alkyl groups from which the various alkyl groups of the present invention may be selected may include, but are not limited to, those previously recited herein. The alkyl groups of the various compounds of the present invention may in some embodiments include one or more unsaturated linkers selected from the group consisting of-CH ═ CH-groups and/or one or more-C ≡ C-groups, provided that the alkyl group does not have two or more conjugated unsaturated linkers. In some embodiments, the alkyl group is free of unsaturated linking groups, such as-CH ═ CH-groups and-C ≡ C-groups.
According to some embodiments, as used herein, the term "cycloalkyl" means a suitably cyclic group, such as, but not limited to C3-C12Cycloalkyl (including but not limited to cyclic C)5-C7Alkyl) groups. Examples of cycloalkyl groups include, but are not limited to, those previously recited herein. According to some embodiments, as used herein, the term "cycloalkyl" also includes: bridged cyclic polycyclic alkyl groups (or bridged cyclic polycyclic alkyl groups), such as, but not limited to, bicyclo [2.2.1 ]]Heptyl (or norbornyl) and bicyclo [2.2.2]Octyl; and fused ring polycyclic alkyl groups (or fused ring polycyclic alkyl groups) such as, but not limited to, octahydro-1H-indenyl and decahydronaphthyl.
According to some embodiments, as used herein, the term "heterocycloalkyl" means a suitably cyclic group, such as, but not limited to, C3-C12Heterocycloalkyl or C5-C7Heterocycloalkyl group and which has at least one heteroatom in a cyclic ring, such as, but not limited to O, S, N, P and combinations thereof. Examples of heterocycloalkyl groups include, but are not limited to, those previously recited herein. According to some embodiments, as used herein, the term "heterocycloalkyl" also includes: bridged cyclic polycyclic heterocycloalkyl, such as, but not limited to, 7-oxabicyclo [2.2.1]A heptalkyl group; and fused ring polycyclic heterocycloalkyl, such as, but not limited to, octahydrocyclopenta [ b]Pyranyl, and octahydro-1H-isochromanyl.
According to some embodiments, as used herein, the term "heteroaryl" includes, but is not limited to, C5-C18Heteroaromatic compoundsRadicals, such as but not limited to C5-C10Heteroaryl (including fused ring polycyclic heteroaryl) and means aryl having at least one heteroatom in an aromatic ring, or in the case of fused ring polycyclic heteroaryl, at least one heteroatom in at least one aromatic ring. Examples of heteroaryl groups include, but are not limited to, those previously recited herein.
As used herein, the term "fused ring polycyclic arylalkyl" and similar terms such as fused ring polycyclic alkylaryl, fused ring polycyclic arylalkyl, and fused ring polycyclic alkylaryl mean fused ring polycyclic groups that include at least one aryl ring and at least one cycloalkyl ring fused together to form a fused ring structure. For non-limiting illustration purposes, examples of fused ring polycyclic arylalkyl groups include, but are not limited to, indenyl, 9H-fluorenyl, cyclopentaphenylmethine (cyclopenapthenyl), and indacenyl (indacenyl).
As used herein and in accordance with some embodiments, the term "aralkyl" includes but is not limited to C6-C24Aralkyl, such as but not limited to C6-C10Aralkyl, and means aryl substituted with alkyl. Examples of aralkyl groups include, but are not limited to, those previously recited herein.
Photochromic indeno-fused phenanthropyran compounds according to the present invention, such as, but not limited to, those represented by formula (I), and the various groups thereof, are described in further detail herein below.
With respect to formula (I) and in some embodiments of the invention, R2Selected from hydrogen; fluorine; chlorine; bromine; straight or branched C1-C10An alkyl group; straight or branched C1-C10A perhaloalkyl group; -ORa；-SRaWherein each R isaIndependently selected from hydrogen, linear or branched C1-C10Alkyl and straight or branched C1-C10A perhaloalkyl group; -C (O) ORbWherein R isbIs hydrogen or straight or branched C1-C6An alkyl group; substituted or unsubstituted phenyl, each phenyl substituent being independently selected from the group consisting of hydroxy, halogen, carbonyl, straight chainOr branched C1-C10Alkoxycarbonyl, cyano, straight-chain or branched C1-C10Haloalkyl, straight-chain or branched C1-C10Alkyl, straight or branched C1-C10Alkoxy and straight or branched C1-C10A perhaloalkyl group; and a group Y1。
In some further embodiments of the invention, and with respect to formula (I), R2Selected from hydrogen; fluorine; chlorine; bromine; straight or branched C1-C6An alkyl group; straight or branched C1-C6A perhaloalkyl group; -ORa；-SRaWherein each R isaIndependently selected from hydrogen, linear or branched C1-C6Alkyl and straight or branched C1-C6A perhaloalkyl group; -C (O) ORbWherein R isbIs hydrogen or straight or branched C1-C3An alkyl group; substituted or unsubstituted phenyl, each phenyl substituent being independently selected from hydroxy, halogen, straight or branched C1-C6Alkoxycarbonyl, cyano, straight-chain or branched C1-C6Haloalkyl, straight-chain or branched C1-C6Alkyl, straight or branched C1-C6Alkoxy and straight or branched C1-C6A perhaloalkyl group; and a group Y1。
With respect to formula (I), and in some embodiments of the invention, R6And R7Each independently selected from hydrogen; fluorine; chlorine; bromine; an elongation group L1；-ORc(ii) a and-SRcWherein each R iscIndependently selected from hydrogen, an elongation group L2Straight or branched C1-C10Alkyl, -C (O) -RdAnd S (O) ReWherein R isdAnd ReEach independently selected from linear or branched C1-C6Alkyl, straight or branched C1-C6Perhaloalkyl, phenyl, straight or branched C1-C6Alkyl-substituted phenyl and straight or branched C1-C6Perhaloalkyl-substituted phenyl。
With further reference to formula (I), and in some further embodiments of the invention, R6And R7Each independently selected from hydrogen; fluorine; chlorine; bromine; an elongation group L1；-ORc(ii) a and-SRcWherein each R iscIndependently selected from hydrogen, an elongation group L2Straight or branched C1-C6Alkyl, -C (O) -RdAnd S (O) ReWherein R isdAnd ReEach independently selected from linear or branched C1-C3Alkyl, straight or branched C1-C3Perhaloalkyl, phenyl, straight or branched C1-C3Alkyl-substituted phenyl and straight or branched C1-C3Perhaloalkyl substituted phenyl.
According to some embodiments of the invention and with respect to figure (I), R1Independently for each of n and R3Independently for each m is each independently selected from (1) hydrogen; (2) a cyano group; (3) an elongation group L3(ii) a (4) Halogen selected from fluorine, chlorine and bromine; (5) straight or branched C1-C10An alkyl group; (6) straight or branched C1-C10A perhaloalkyl group; (7) c3-C7A cycloalkyl group; (8) -O-R10’；(9)-S-R10'; (10) radical Y2(ii) a And (11) substituted or unsubstituted phenyl, wherein the phenyl substituents are selected from at least one of: hydroxy, halogen, carbonyl, straight or branched C1-C10Alkoxycarbonyl, cyano, straight-chain or branched C1-C10Haloalkyl, straight-chain or branched C1-C10Alkyl, straight or branched C1-C10Alkoxy, straight or branched C1-C10Perhaloalkyl, and combinations thereof. In some embodiments, (R)1And/or R3) Of (a) is-O-R10' and-S-R10' Each R of10' independently hydrogen, straight or branched C1-C10Alkyl, phenyl (C)1-C10) Alkyl, mono (C)1-C10) Alkyl-substituted phenyl (C)1-C10) Alkyl, mono (C)1-C10) Alkoxy-substituted phenyl (C)1-C10) Alkyl, (C)1-C10) Alkoxy (C)2-C10) Alkyl radical, C3-C7Cycloalkyl or mono (C)1-C10) Alkyl substituted C3-C7A cycloalkyl group.
According to some further embodiments of the invention and additionally with respect to figure (I), R1Independently for each of n and R3Independently for each m each independently selected from: (1) hydrogen; (2) a cyano group; (3) an elongation group L3(ii) a (4) Straight or branched C1-C6An alkyl group; (5) c3-C6A cycloalkyl group; (6) straight or branched C1-C8A perhaloalkyl group; (7) fluorine, chlorine and bromine; (8) -O-R10’；(9)-S-R10'; (10) radical Y2(ii) a And (11) a substituted or unsubstituted phenyl group, the phenyl substituent being selected from at least one of: hydroxy, halogen, straight or branched C1-C6Alkoxycarbonyl, cyano, straight-chain or branched C1-C6Haloalkyl, straight-chain or branched C1-C6Alkyl, straight or branched C1-C6Alkoxy and straight or branched C1-C6A perhaloalkyl group. In some embodiments, (R)1And/or R3) Of (a) is-O-R10' and-S-R10' Each R of10' independently hydrogen, straight or branched C1-C6Alkyl, phenyl (C)1-C6) Alkyl, mono (C)1-C6) Alkyl-substituted phenyl (C)1-C6) Alkyl, mono (C)1-C6) Alkoxy-substituted phenyl (C)1-C6) Alkyl, (C)1-C6) Alkoxy (C)2-C6) Alkyl radical, C3-C6Cycloalkyl or mono (C)1-C6) Alkyl substituted C3-C6A cycloalkyl group.
In some embodiments, R1Independently for each of n and R3Independently for each m is independently selected in each caseFree from nitrogen containing rings represented by the following graphic formula XIIA,
XIIA
with respect to formula XIIA: each-Y-is independently at each occurrence selected from-CH2-,-CH(R13’)-,-C(R13’)2-, -CH (aryl) -, -C (aryl)2-and-C (R)13') (aryl) -; and Z is-Y-, -O-, -S-, -S (O) -, -SO2-,-NH-,-N(R13') -, or-N (aryl) -, wherein each R is13' independently is C1-C20Alkyl, each aryl group is independently phenyl or naphthyl, m is an integer of 1,2 or 3, and p is an integer of 0,1, 2 or 3, and with the proviso that when p is 0, Z is-Y-.
In some embodiments, R1Independently for each of n and R3Independently for each m is independently selected in each occurrence from the group represented by one of the following graphic formulae XIIB or XIIC,
independently for each of formulas XIIB and XIIC, R15、R16And R17Each independently is hydrogen, C1-C6Alkyl, phenyl or naphthyl, or the radical R15And R16Together form a ring of 5 to 8 carbon atoms, and each RdIndependently at each occurrence is selected from C1-C20Alkyl radical, C1-C20Alkoxy, fluoro or chloro, and Q is an integer of 0,1, 2 or 3.
According to some further embodiments and further with respect to formula (I), two adjacent R are3The groups together form a group represented by the following formula XIID or XIIE:
with respect to formulas XIID and XIIE, T and T' are each independently oxygen or a group-NR11' -, wherein R11’、R15And R16As listed above.
With respect to formula (I), and in some embodiments of the invention, R4And R5Each independently selected from: hydrogen; straight or branched C1-C10An alkyl group; straight or branched C1-C10A haloalkyl group; c3-C7A cycloalkyl group; and a group Y3(ii) a Or R4And R5Together form a spiro substituent which is a substituted or unsubstituted spirocarbocyclic ring containing from 3 to 10 carbon atoms.
With further reference to formula (I), and in some further embodiments of the invention, R4And R5Each independently selected from: hydrogen; straight or branched C1-C8An alkyl group; straight or branched C1-C8A haloalkyl group; c3-C6A cycloalkyl group; and a group Y3(ii) a Or R4And R5Together form a spiro substituent which is a substituted or unsubstituted spirocarbocyclic ring containing from 3 to 10 carbon atoms.
With respect to formula (I), and in some embodiments of the invention, B and B' are independently selected at each occurrence from: an aryl group monosubstituted with a reactive substituent; a substituted phenyl group; a substituted aryl group; substituted 9-julolidinyl; a substituted heteroaromatic group selected from pyridyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl, wherein the phenyl, aryl, 9-julolidinyl or heteroaromatic substituent is a reactive substituent R; unsubstituted, mono-, di-or tri-substituted phenyl or aryl; 9-julolidinyl; or an unsubstituted, mono-substituted or di-substituted heteroaromatic group selected from the group consisting of pyridyl, furyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuryl, dibenzothienyl, carbazolyl, benzopyridyl, indolinyl and fluorenyl.
In some embodiments, each of the phenyl, aryl and heteroaromatic substituents (of B and B') is independently (a) hydroxy, a group-C (═ O) R21Wherein R is21is-OR22、-N(R23)R24Piperidinyl or morpholinyl, wherein R22Is allyl, straight-chain or branched C1-C20Alkyl, phenyl, mono (C)1-C20) Alkyl substituted phenyl, mono (C)1-C20) Alkoxy-substituted phenyl, phenyl (C)1-C20) Alkyl, mono (C)1-C20) Alkyl-substituted phenyl (C)1-C20) Alkyl, mono (C)1-C20) Alkoxy-substituted phenyl (C)1-C20) Alkyl radical, C1-C20Alkoxy (C)2-C20) Alkyl or C1-C20Haloalkyl, R23And R24Each independently is C1-C20Alkyl radical, C5-C10Cycloalkyl, phenyl or substituted phenyl, the phenyl substituent being C1-C20Alkyl or C1-C20Alkoxy, and the halo substituent is chloro or fluoro, aryl, mono (C)1-C20) Alkoxyaryl, di (C)1-C20) Alkoxyaryl, mono (C)1-C20) Alkylaryl, di (C)1-C20) Alkylaryl, haloaryl, C3-C10Cycloalkyl aryl, C3-C10Cycloalkyl radical, C3-C10Cycloalkoxy, C3-C10Cycloalkoxy (C)1-C20) Alkyl radical, C3-C10Cycloalkoxy (C)1-C20) Alkoxy, aryl (C)1-C20) Alkyl, aryl (C)1-C20) Alkoxy, aryloxy (C)1-C20) Alkyl, aryloxy (C)1-C20) Alkoxy, mono-or di (C)1-C20) Alkylaryl (C)1-C20) Alkyl, mono-or di- (C)1-C20) Alkoxy aryl radicals(C1-C20) Alkyl, mono-or di- (C)1-C20) Alkylaryl (C)1-C20) Alkoxy, mono-or di- (C)1-C20) Alkoxyaryl (C)1-C20) Alkoxy, amino, mono-or di- (C)1-C20) Alkylamino, diarylamino, piperazinyl, N- (C)1-C20) Alkylpiperazino, N-arylpiperazinyl, aziridino, indolinyl, piperidinyl, morpholinyl, thiomorpholinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, pyrrolidinyl, C1-C20Alkyl radical, C1-C20Haloalkyl, C1-C20Alkoxy, mono (C)1-C20) Alkoxy (C)1-C20) Alkyl, acryloxy, methacryloxy or halogen.
In some further embodiments, each of the phenyl, aryl, and heteroaromatic substituents (of B and B') is independently: (b) an unsubstituted or mono-substituted radical selected from the group consisting of pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, each of which is C1-C20Alkyl radical, C1-C20Alkoxy, phenyl or halogen.
In some further embodiments, each of the phenyl, aryl, and heteroaromatic substituents (of B and B') is independently: (c) a group represented by one of the following formulae (D) and (E):
with respect to formulas (D) and (E), each K is independently-CH2-or-O-, and each M is independently-O-or a substituted nitrogen, with the proviso that when M is a substituted nitrogen, K is-CH2-, the substituted nitrogen substituents being hydrogen, C1-C20Alkyl or C1-C20Acyl radical, each R25Independently at each occurrence is selected from C1-C20Alkyl radical, C1-C20Alkoxy, hydroxy and halogen, R26And R27Each independently is hydrogen or C1-C20Alkyl, and u is an integer in the range of 0 to 2.
In some further embodiments, each of the phenyl, aryl, and heteroaromatic substituents (of B and B') is independently (d) a group represented by the following formula (F):
with respect to formula (F), R28Is hydrogen or C1-C20Alkyl, and R29Is an unsubstituted, mono-or di-substituted radical selected from the group consisting of naphthyl, phenyl, furyl and thienyl, wherein the substituent is C1-C20Alkyl radical, C1-C20Alkoxy or halogen.
In some alternative embodiments, B and B' of formula (I) together form one of a fluoren-9-ylidene, mono-substituted or di-substituted fluoren-9-ylidene, each fluoren-9-ylidene substituent being independently selected from C1-C20Alkyl radical, C1-C20Alkoxy and halogen.
According to some embodiments of the invention, B and B' of formula (I) are independently selected at each occurrence from: an unsubstituted aryl group; by straight or branched C1-C6Alkoxy-substituted aryl; by straight or branched C1-C6Perhaloalkyl-substituted aryl; aryl substituted with morpholinyl; and aryl substituted with piperidinyl.
In some further embodiments of the invention, B and B' of formula (I) are independently selected at each occurrence from: unsubstituted phenyl; by straight or branched C1-C6Alkoxy-substituted aryl; by straight or branched C1-C6Perhaloalkyl-substituted aryl; aryl substituted with morpholinyl; and aryl substituted with piperidinyl.
With respect to the photochromic compounds of the present invention, such as the photochromic compounds represented by formula (I), and according to some embodiments, Y is independently for each group1、Y2And Y3Each cyclic ester monomer of each ring-opened cyclic ester monomer is independently represented by the following formula (a):
with respect to formula (a), I and J are each independently an integer in the range of 1 to 8; r13、R14、R15And R16For each carbon unit (C)IAnd (C)JIndependently selected from-H and C1-C16 alkyl; k is 0 or 1; and D is-O-when k is 1.
With respect to the photochromic compounds of the present invention, such as the photochromic compounds represented by formula (I), and according to some embodiments, Y is independently for each group1、Y2And Y3Each cyclic ester monomer of each ring-opened cyclic ester monomer is independently selected from epsilon (epsilon) -caprolactone; ζ (zeta) -heptalactone; delta (delta) -valerolactone; monoalkyl delta valerolactone; monoalkyl-, dialkyl-or trialkyl-epsilon (epsilon) -caprolactone; beta (beta) -lactone; gamma (gamma) -lactone; a dilactone; and ketone dioxanone. Examples of mono-, di-or tri-alkyl-epsilon (epsilon) -caprolactones include, but are not limited to: monomethyl-, monoethyl-, monohexyl-, dimethyl-, di-n-propyl-, mono-/di-/tri-t (tert) -butyl, di-n-hexyl-, trimethyl-and triethyl-, epsilon (epsilon) -caprolactone; 5-nonyl-oxepan-2-one; 4,4, 6-or 4,6, 6-trimethyl-oxepan-2-one; and 5-hydroxymethyl-oxepan-2-one. Examples of beta (beta) -lactones include, but are not limited to: beta (beta) -propiolactone; and beta (beta) -butyrolactone. Examples of γ (gamma) -lactones include, but are not limited to: gamma (gamma) -butyrolactone; and valerolactone.
With respect to the photochromic compounds of the present invention, such as the photochromic compounds represented by formula (I), and according to some embodiments, Y is independently for each group1、Y2And Y3Each cyclic carbonate monomer of each ring-opened cyclic carbonate monomer is independently represented by the following formula (B),
with respect to formula (B), m and q are each independently an integer in the range of 1 to 3; r17、R18、R19And R20For each carbon unit (C)mAnd (C)qEach independently selected from-H and C1-C16 alkyl; t is 0 or 1; and E is-O-when t is 1.
With respect to the photochromic compounds of the present invention, such as the photochromic compounds represented by formula (I), and according to some embodiments, Y is independently for each group1、Y2And Y3Each cyclic carbonate monomer of each ring-opened cyclic carbonate monomer is independently selected from ethylene carbonate; 3-ethyl-3-hydroxymethyltrimethylene carbonate; propylene carbonate, trimethylene carbonate; trimethylolpropane monocarbonate; 4, 6-dimethyl-1, 3-propylene carbonate; 2, 2-dimethyltrimethylene carbonate; and 1, 2-dioxepan-2-one.
In some embodiments, each group Y1、Y2And Y3Independently and optionally including at least one reactive substituent, which may be selected from those classes and examples of reactive substituents otherwise described herein, such as, but not limited to: active hydrogen groups (e.g., hydroxyl groups); and ethylenically unsaturated and free-radically polymerizable groups (such as vinyl groups and (meth) acryloyl groups). Each reactive substituent may independently be a lateral reactive substituent or a terminal reactive substituent.
In some further embodiments of the invention, for each of the elongation groups L represented by formula (II)1、L2And L3，(a)Q1、Q2And Q3Independently at each occurrence is selected from the group consisting of unsubstituted aryl, substituted aryl, unsubstituted cycloalkyl and substituted cycloalkyl.
According to some further embodiments, and independently for each group L represented by formula (II)1、L2And L3(b) each S1、S2、S3、S4And S5Independently at each occurrence, is selected from a spacer unit selected from (ii) or (iii) as described below. Each S of the formula (II)1、S2、S3、S4And S5In some embodiments, independently at each occurrence, is selected from a spacer unit selected from (ii) -N (Z) -, -C (Z) -, -C (Z) -N-, -C (Z')2-C(Z’)2-、-N(Z)-C(Z’)2-and a single bond, wherein Z is independently at each occurrence selected from hydrogen, C1-C8Alkyl radical, C3-C6Cycloalkyl and aryl, and Z' is independently at each occurrence selected from C1-C8Alkyl radical, C3-C6Cycloalkyl groups and aryl groups. Each S of the formula (II)1、S2、S3、S4And S5In some further embodiments, each occurrence is independently selected from spacer units selected from the group consisting of (iii) -O-, -C (═ O) -, -C ≡ C-, -N ═ N-, -S (═ O) -, and linear or branched C1-C12An alkylene residue of1-C12An alkylene residue is unsubstituted, mono-substituted by cyano or halogen or poly-substituted by halogen.
According to some further embodiments, L is independently for each group represented by formula (II)1、L2And L3(C) P, at each occurrence, is independently selected from hydrogen, hydroxy, amino, C2-C8Alkenyl radical, C2-C8Alkynyl, acryloyloxy, methacryloyloxy, 2- (acryloyloxy) ethylcarbamoyl, 2- (methacryloyloxy) ethylcarbamoyl, epoxy, carboxylic acid, carboxylic ester, acrylamido, methacrylamido, aminocarbonyl, C1-C8Alkylaminocarbonyl, aminocarbonyl (C)1-C8) Alkyl radical, C1-C8Alkoxycarbonyloxy, halocarbonyl, aryl, hydroxy (C)1-C8) Alkyl radical, C1-C8Alkyl radical, C1-C8Alkoxy, amino (C)1-C8) Alkyl radical, C1-C8Alkylamino, di- (C)1-C8) Alkylamino radical, C1-C8Alkyl radical (C)1-C8) Alkoxy radical, C1-C8Alkoxy (C)1-C8) Alkoxy, nitro, poly (C)1-C8) Alkyl ether, (C)1-C8) Alkyl radical (C)1-C8) Alkoxy (C)1-C8) Alkyl, polyethyleneoxy, polypropyleneoxy, ethylene, acryloyl, acryloyloxy (C)1-C18) Alkyl, methacryloyl, methacryloyloxy (C)1-C8) Alkyl, 2-chloropropenoyl, 2-phenylpropenoyl, acryloxyphenyl, 2-chloropropenamido, 2-phenylacrylaminocarbonyl, oxetanyl, glycidyl, cyano, isocyanato (C)1-C18) Alkyl, itaconate, vinyl ether and vinyl ester.
According to some still other embodiments, L is independently for each group represented by formula (II)1、L2And L3(b) each S1、S2、S3、S4And S5Independently at each occurrence, is selected from a spacer unit selected from: (ii) -n (Z) -, -C (Z) ═ C (Z) -and single bonds, wherein Z is independently selected at each occurrence from hydrogen, C, and C1-C8Alkyl radical, C3-C6Cycloalkyl and aryl, and Z' is independently at each occurrence selected from C1-C8Alkyl radical, C3-C6Cycloalkyl and aryl groups; and (iii) -O-, -C (═ O) -, -C ≡ C-and straight or branched C1-C6An alkylene residue of1-C6An alkylene residue is unsubstituted, mono-substituted by cyano or halogen or poly-substituted by halogen.
According to some other further embodiments, L is independently for each group represented by formula (II)1、L2And L3(C) P, at each occurrence, is independently selected from hydrogen, hydroxy, amino, C2-C8Alkenyl radical, C2-C8Alkynyl and aryl.
With respect to some embodiments according to the inventionThe photochromic compounds of embodiment (I), and with respect to formula (I), R6And R7At least one is selected from the group consisting of the elongation groups L1OR-ORcWherein R iscIs an elongation group L2。
With respect to formula (I), in photochromic compounds according to some embodiments of the present invention, R6And R7Each independently selected from the group consisting of an elongation group L1and-ORcWherein R iscIs an elongation group L2。
With further regard to formula (I), in the photochromic compounds according to some embodiments of the present invention: r6Selected from the group consisting of the extending groups L1and-ORcWherein R iscIs an elongation group L2(ii) a And R7Is halogen (e.g. fluorine, chlorine or bromine).
In photochromic compounds according to some embodiments of the invention, and with respect to formula (I), R at the 11-position3Selected from halogen (such as fluorine, chlorine or bromine), -CN, straight or branched C1-C8Perhaloalkyl, unsubstituted phenyl and halogen and/or straight or branched C1-C8Perhaloalkyl substituted phenyl.
In photochromic compounds according to some embodiments of the invention, and with respect to formula (I), R at the 12-position3Is an elongation group L3。
In some further embodiments of the photochromic compounds according to the invention, and with respect to formula (I), R at the 11-position3Is halogen (e.g. fluorine, chlorine or bromine).
Each of the extending groups L of the photochromic compounds of the present invention, as represented by formula (I)1、L2And L3In each case, in some embodiments, independently selected from:
l (1)4- [4- (4-butyl-cyclohexyl) -phenyl ] -cyclohexyloxy
L (2)4 "-butyl- [1, 1'; 4',1 "] Tricyclohexan-4-yloxy
L (3)4- [4- (4-butyl-phenyl) -cyclohexyloxycarbonyl ] -phenoxy
L (4)4' - (4-butyl-benzoyloxy) -biphenyl-4-carbonyloxy
L (5)4- (4-pentyl-phenylazo) -phenylcarbamoyl
L (6)4- (4-dimethylamino-phenylazo) -phenylcarbamoyl
L (7) {4- [5- (4-propyl-benzoyloxy) -pyrimidin-2-yl ] -phenyl } ester
L (8) {4- [2- (4' -methyl-biphenyl-4-carbonyloxy) -1, 2-diphenyl-ethoxycarbonyl ] -phenyl } ester
L (9) [4- (1, 2-Diphenyl-2- {3- [4- (4-propyl-benzoyloxy) -phenyl ] -acryloyloxy } -ethoxycarbonyl) -phenyl ] ester
L (10)4- [4- (4- {4- [3- (6- {4- [4- (4-nonyl-benzoyloxy) -phenoxycarbonyl ] -phenoxy } -hexyloxycarbonyl) -propionyloxy ] -benzoyloxy } -benzoyloxy) -phenyl ] -piperazin-1-yl
L (11) {4- [4- (4- {4- [4- (4-nonyl-benzoyloxy) -benzoyloxy ] -benzoyloxy } -benzoyloxy) -phenyl ] -piperazin-1-yl }
L (12)4- (4' -propyl-biphenyl-4-ylethynyl) -phenyl
L (13)4- (4-fluoro-phenoxycarbonyloxy) -piperidin-1-yl
L (14)2- [17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthren-3-yloxy ] -indan-5-yl
L (15)4- [17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthren-3-yloxycarbonyloxy ] -piperidin-1-yl
L (16)4- (biphenyl-4-carbonyloxy) -piperidin-1-yl
L (17)4- (naphthalene-2-carbonyloxy) -piperidin-1-yl
L (18)4- (4-phenylcarbamoyl) -piperidin-1-yl
L (19)4- (4- (4-phenylpiperidin-1-yl) -benzoyloxy) -piperidin-1-yl
L (20) 4-butyl- [1, 1'; 4',1 "] terphenyl-4-yl
L (21)4- (4-pentadecafluoroheptyloxy-phenylcarbamoyl) -benzyloxy
L (22)4- (4- {4- [17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthren-3-yloxycarbonyloxy ] -benzoyloxy } -phenoxycarbonyl) -phenoxymethyl
L (23)4- [4- (4-cyclohexyl-phenylcarbamoyl) -benzyloxy ] -piperidin-1-yl
L (24)4- [4- (4-cyclohexyl-phenylcarbamoyl) -benzoyloxy ] -piperidin-1-yl
L (25) N- {4- [ (4-pentyl-benzylidene) -amino ] -phenyl } -acetylamino
L (26)4- (3-piperidin-4-yl-propyl) -piperidin-1-yl
L (27)4- (4-hexyloxy-benzoyloxy) -piperidin-1-yl ]
L (28)4- (4' -hexyloxy-biphenyl-4-carbonyloxy) -piperidin-1-yl
L (29)4- (4-butyl-phenylcarbamoyl) -piperidin-1-yl
L (30a) 1-methyl-4- ((4'- (((1-methylpiperidin-4-yl) oxy) carbonyl) - [1,1' -biphenyl ] -4-carbonyl) oxy) piperidin-1-yl
L (30b) bis (1-yl-piperidin-4-yl) [1,1 '-biphenyl ] -4,4' -dicarboxylate
L (31)4- (4- (9- (4-butylphenyl) -2,4,8, 10-tetraoxaspiro [5.5] undecan-3-yl) phenyl) piperazin-1-yl
L (32)4- (6- (4-butylphenyl) carbonyloxy- (4, 8-dioxabicyclo [3.3.0] oct-2-yl)) oxycarbonyl) phenyl
L (33)1- {4- [5- (4-butyl-phenyl) - [1,3] dioxan-2-yl ] -phenyl } -4-methyl-piperazin-1-yl
L (34)4- (7- (4-Propylphenylcarbonyloxy) bicyclo [3.3.0] oct-2-yl) oxycarbonyl) phenyl
L (35)4- [17- (1, 5-dimethyl-hexyl) -10, 13-dimethyl-2, 3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthren-3-yloxycarbonyloxy
L-DC- (a) (4-trans- (4-pentylcyclohexyl) benzoylamino) phenyl,
L-DC- (b) (4- (4-trans- (4-pentylcyclohexyl) phenoxy) carbonyl) phenyl,
L-DC- (c) 4- (4- (4-trans- (4-pentylcyclohexyl) phenyl) benzoylamino) phenyl,
L-DC- (d)4- ((trans- (4 '-pentyl- [1,1' -bis (cyclohexane) ] -4-yl) oxy) carbonyl) phenyl,
L-DC- (e) 4- (4'- (4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-ylcarboxamido) phenyl,
L-DC- (f) 4- ((4'- (4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-carbonyl) oxy) benzoylamino,
L-DC- (g)4- (4'- (4-pentylcyclohexyl) - [1,1' -biphenyl ] -4-carbonyl) piperazin-1-yl,
L-DC- (h)4- (4- (4-trans- (4-pentylcyclohexyl) phenyl) benzoylamino) -2- (trifluoromethyl) phenyl,
L-DC- (i) 2-methyl-4-trans- (4- ((4' -trans- (4-pentylcyclohexyl) biphenyl-4-yloxy) carbonyl) cyclohexanecarboxamido) phenyl,
L-DC- (j)4'- (4' -pentylbis (cyclohexane-4-) carbonyloxy) biphenylcarbonyloxy,
L-DC- (k)4- (((3S,8S,9S,10R,13R,14S,17R) -10, 13-dimethyl-17- ((R) -6-methylheptan-2-yl) -2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydro-1H-cyclopenta [ a ] phenanthren-3-yloxy) carbonyl) piperazin-1-yl, and
L-DC- (L)4- ((S) -2-methylbutoxy) phenyl) -10- (4- (((3R,3aS,6S,6aS) -6- (4' -trans- (4-pentylcyclohexyl) biphenylcarbonyloxy) hexahydrofuro [3,2-b ] furan-3-yloxy) carbonyl) phenyl.
According to some embodiments of the invention, at-ORcIn which R iscIs an elongation group L2-O andan elongation group L2The bond between does not contain two heteroatoms attached to each other.
According to some embodiments, the photochromic compounds of the present invention, such as the photochromic compounds represented by formula (I), are, after their formation, modified for R1、R3、R6And R7May undergo one or more further chemical reactions, thereby converting it into an elongation group L1、L2Or L3Or a group L which is extended1、L2Or L3Substitution, as and in each case as hereinbefore described with reference to formula (II). Examples of additional chemical reactions that one or more photochromic compounds represented by formula (I) may undergo include, but are not limited to, palladium catalyzed cross-coupling, transesterification, esterification, amidation, and condensation.
In some embodiments, the present invention also provides a photochromic compound represented by the following formula (III),
formula (III)
Ly-(PC)n’
With regard to formula (III), n' is at least 2, such as 2 to 100, or 2 to 50, or 2 to 25, or 2 to 20, or 2 to 15, or 2 to 10, or 2 to 8, or 2 to 5, or 2 to 4, or 2 or 3, in each case including the values recited.
Further with respect to formula (III), independently for each n', the PC group or moiety is a residue of a photochromic compound according to the present invention, such as a residue of a photochromic compound represented by formula (I), and as described hereinbefore.
In addition to the formulae (III), LyIs a multivalent linking group selected from: (i) a first multivalent compound that is a multivalent polymer; and (ii) a second multivalent compound, different from the first multivalent compound, which is non-polymeric and comprises a residue selected from: residues of polyisocyanates, residues of polyols, residues of polycarboxylic acids, residues of polycarbonate functional materials, and combinations thereof. As used herein, with respect to L from which formula (III) may be selectedyThe term "non-polymeric" of a second multivalent compound of (1)By "synthetic" it is meant that it does not contain repeating monomer units (or repeating monomer residues).
According to some embodiments, and in addition with respect to formula (III), L may be selected therefromyThe polyvalent polymer of the first polyvalent compound of (a) is selected from the group consisting of polyvalent polyurethanes, polyvalent polyesters, polyvalent polyethers, polyvalent poly (meth) acrylates, polyvalent polyvinyl alcohols, polyvalent polycarbonates, polyvalent polysiloxanes and polyvalent cyclic polysiloxanes. From which L can be selectedyThe multivalent polymer of (a) can be prepared according to methods known in the art from materials known in the art, including, but not limited to, monomers known in the art. In some embodiments, (a) the polymer is prepared therefrom (and L thereof)yIs a residue) has covalently bonded thereto one or more photochromic compounds according to the invention; and/or (b) the resulting polymer (L thereof)yIs a residue) is then modified to include the photochromic compound according to the present invention bonded thereto. L isyThe multivalent polymer from which it may be selected may in some embodiments have any suitable backbone structure, such as, but not limited to, an alternating backbone structure (architecture), a block backbone structure, a random backbone structure, and combinations thereof. L isyThe multivalent polymer from which it may be selected may in some further embodiments have any suitable large (macro) polymer structure, such as, but not limited to, linear polymer structures, branched polymer structures, comb polymer structures, star polymer structures, dendritic polymer structures, and combinations thereof.
The class of polyisocyanates which may be the residue of the second polyvalent compound (L of formula (III))yMay be selected from among) including, but not limited to, aliphatic polyisocyanates, aromatic polyisocyanates, cycloaliphatic polyisocyanates, and heterocyclic polyisocyanates, in each case having at least 2 isocyanate groups, dimers of such polyisocyanates, trimers of such polyisocyanates, and mixtures of such polyisocyanates. Examples of polyisocyanates which may be residues of a second polyvalent compound (L of formula (III))yMay be selected from among) include, but are not limited to, toluene-2, 4-diisocyanate; toluene-2, 6-diisocyanate; diphenyl groupMethane-4, 4' -diisocyanate; diphenylmethane-2, 4' -diisocyanate; p-phenylene diisocyanate; a biphenyl diisocyanate; 3,3 '-dimethyl-4, 4' -diphenylene diisocyanate; tetramethylene-1, 4-diisocyanate; hexamethylene-1, 6-diisocyanate; 2,2, 4-trimethylhexane-1, 6-diisocyanate; lysine methyl ester diisocyanate; bis (isocyanatoethyl) fumarate; isophorone diisocyanate; ethylene diisocyanate; dodecane-1, 12-diisocyanate; cyclobutane-1, 3-diisocyanate; cyclohexane-1, 3-diisocyanate; cyclohexane-1, 4-diisocyanate; methylcyclohexyl 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, dimers thereof, trimers thereof, and mixtures thereof.
The class of polyols which may be the residue of the second multivalent compound (L of formula (III))yMay be selected from among) include, but are not limited to, aliphatic polyols, aromatic polyols, cycloaliphatic polyols, and heterocyclic polyols, in each case having at least 2 hydroxyl groups. May be a residue of a second polyvalent compound (L of formula (III))yExamples of polyols from which) may be selected include, but are not limited to, trimethylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane, trihydroxyethylisocyanurate, pentaerythritol, dipentaerythritol, propylene glycol, trimethylene glycol, butylene glycol, heptanediol, hexylene glycol, octanediol, 4'- (propane-2, 2-diyl) bicyclohexanol, 4' -methylenebicyclohexanol, neopentyl glycol, 2, 3-trimethylpentane-1, 3-diol, 1, 4-dimethylolcyclohexane, 2, 4-trimethylpentane diol, 4'- (propane-2, 2-diyl) diphenol, and 4,4' -methylenediphenol.
Class of polycarboxylic acids (L of formula (III)) which may be the residue of the second multivalent compoundyMay be selected from among) include, but are not limited to, aliphatic polycarboxylic acids, aromatic polycarboxylic acids, alicyclic polycarboxylic acids and heterocyclic polycarboxylic acids, having in each case at least 2 carboxylic acid groups and/or carboxylic ester groups. May be a residue of a second polyvalent compound (L of formula (III))yExamples of polycarboxylic acids from which this may be selected) include, but are not limited to, benzene-1, 2, 4-tricarboxylic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endo-bicyclo (endobicyclo) -2,2,1, 5-heptyne-2, 3-dicarboxylic acid, tetrachlorophthalic acid, cyclohexanedicarboxylic acid, succinic acid, isophthalic acid, terephthalic acid, azelaic acid, maleic acid, trimesic acid, 3, 6-dichlorophthalic acid, adipic acid, sebacic acid, and similar polyfunctional carboxylic acids.
A polycarbonate functional material/compound (L of formula (III)) that may be a residue of the second multivalent compoundyMay be selected from among) include, but are not limited to, aliphatic polycarbonate functional compounds, aromatic polycarbonate functional compounds, alicyclic polycarbonate functional compounds, and heterocyclic polycarbonate functional compounds, in each case having at least 2 cyclic carbonate groups. The polycarbonate functional compounds may be prepared according to methods well known in the art. According to some embodiments, the polycarbonate functional compound is prepared by heating an oxirane-functional precursor material in the presence of carbon dioxide and a suitable catalyst, such as tetraalkylammonium iodide and/or tetraalkylammonium bromide, such as tetrabutylammonium iodide and/or tetrabutylammonium bromide. According to some further embodiments, the oxirane-functional precursor material is prepared by reacting one mole of polyol with at least two moles of epichlorohydrin to convert at least two hydroxyl groups of the polyol to oxirane functional groups. The polyol may be selected in some embodiments from those previously described with respect to LyThose classes and examples of polyols described.
According to some embodiments, and as previously described: r1Independently for each of n and R3Independently selected from reactive substituents in each occurrence or each independently substituted with at least one reactive substituent; and B' are each independently an aryl group monosubstituted with a reactive substituent. If the photochromic compounds of the present invention include multiple reactive substituents, each reactive substituent may be independently selected. In some embodiments, each reactive substituent is independently terminal reactiveA substituent or a laterally reactive substituent.
Classes of reactive substituents from which each reactive substituent may be independently selected include, but are not limited to: an active hydrogen group; a group reactive with an active hydrogen group; and ethylenically unsaturated and free-radically polymerizable groups. Examples of active hydrogen groups from which each reactive substituent may be independently selected include, but are not limited to: a hydroxyl group; a thiol group; a carboxylic acid group; a sulfonic acid group; a primary amine group; and secondary amine groups, including cyclic amine groups. Examples of groups that are reactive with active hydrogen groups from which each reactive substituent may be independently selected include, but are not limited to: an isocyanate group; an isothiocyanate group; an oxirane (or epoxide) group; an ethylene sulfide (or thioepoxide) group; an aziridine group; a carboxylate group; a cyclic carboxylate group; a cyclic carboxylic acid anhydride group; a sulfonate group; and a cyclic carbonate group. Ethylenically unsaturated and free radically polymerizable groups from which each reactive substituent may be independently selected include, but are not limited to: vinyl groups, including vinyl ether groups; halogenated vinyl groups such as 1-chloroethenyl; allyl groups, including allyl ether groups; an acryloyl group; and a methacryl group. Acryloyl and methacryloyl groups may be collectively referred to herein as (meth) acryloyl groups.
According to some embodiments of the present invention, and for non-limiting illustrative purposes, additional examples of ethylenically unsaturated and free-radically polymerizable groups from which each reactive substituent may be independently selected include, but are not limited to: an acryloyl group; a methacryloyl group; crotonyl (crotyl); 2- (methacryloyloxy) ethylcarbamoyl; 2- (methacryloyloxy) ethoxycarbonyl; vinylphenyl, such as 4-vinylphenyl; a vinyl group; and 1-halovinyl groups such as 1-chloroethenyl. As used herein, the terms acryloyl, methacryloyl, crotonyl, 2- (methacryloyloxy) ethylcarbamoyl, 2- (methacryloyloxy) ethoxycarbonyl, vinylphenyl, vinyl, and 1-halovinyl refer to the following representative structures:
additional descriptions of reactive substituents that may be used in conjunction with the photochromic compounds of the present invention are provided at column 28, line 34 through column 33, line 49 of U.S. patent No. 9,028,728
In some embodiments, the photochromic compounds of the present invention (as described with respect to formula (I)) can be used each alone or in combination with one or more other photochromic compounds. For example, the photochromic compounds of the present invention can be used in combination with one or more other photochromic compounds having an activated absorption maximum in the range of 300 to 1000 nanometers. Further, the photochromic compounds according to the present invention can be used in combination with one or more complementary conventional polymerizable or compatible photochromic compounds, such as those disclosed in U.S. Pat. nos. 6,113,814 (at
The photochromic compounds of the present invention can be used in combination with mixtures of other photochromic compounds. For example, although not limited herein, mixtures of photochromic compounds can be used to obtain certain activated colors, such as a near neutral gray or near neutral brown. See, for example, U.S. patent No. 5,645,767, column 12, line 66 to column 13, line 19, which describe parameters that define neutral gray and brown, and the disclosure of which is specifically incorporated herein by reference.
Examples of classes of other photochromic compounds that may be used in combination with the photochromic compounds of the present invention include, but are not limited to, indeno-fused naphthopyrans, naphtho [1,2-b ] pyrans, naphtho [2,1-b ] pyrans, spirofluoreno [1,2-b ] pyrans, phenanthropyrans, quinopyrans, fluoranthenopyrans, spiropyrans, benzoxazines, phenoxazines, spiro (indoline) pyridobenzoxazines, spiro (indoline) fluoranthenoxazines, spiro (indoline) quinoxazines, fulgides, fulgimides, diarylethenes, diarylalkylethylenes, diarylalkenylethenes, thermally reversible photochromic compounds, and non-thermally reversible photochromic compounds, and mixtures thereof.
Non-limiting examples of photochromic pyrans that can be used in combination with the photochromic compounds of the present invention include, but are not limited to, benzopyrans, naphthopyrans, e.g., naphtho [1,2-b ] pyrans, naphtho [2,1-b ] pyrans, indeno-fused naphthopyrans, such as those disclosed in U.S. Pat. No. 5,645,767, and heterocyclic-fused naphthopyrans, such as those disclosed in U.S. Pat. Nos. 5,723,072, 5,698,141, 6,153,126, and 6,022,497, which are incorporated herein by reference; spiro-9-fluoreno [1,2-b ] pyrans; phenanthropyrans; quinolinopyrans (quinopyrans); fluoranthene and pyrans; spiropyrans, for example spiro (benzindolinyl) naphthopyrans, spiro (indolinyl) benzopyrans, spiro (indolinyl) naphthopyrans, spiro (indolinyl) quinopyrans and spiro (indolinyl) pyrans. Additional examples of naphthopyrans and complementary organic photochromic compounds are described in U.S. patent 5,658,501, which is specifically incorporated herein by reference. Spiro (indoline) pyrans are also described in the text, Techniques in Chemistry, volume III, "photochromysm", chapter 3, Glenn h.brown, editors, John Wiley and Sons, inc.
Non-limiting examples of photochromic oxazines that may be used in combination with the photochromic compounds of the present invention include, but are not limited to, benzoxazines, phenoxazines and spirooxazines, such as spiro (indoline) phenoxazines, spiro (indoline) pyridobenzoxazines, spiro (benzindoline) phenoxazines, spiro (benzindoline) benzoxazines, spiro (indoline) fluoranthenoxazines and spiro (indoline) quinolinooxazines. Non-limiting examples of photochromic fulgides that may be used in combination with the photochromic compounds of the present invention include, but are not limited to: fulgimides and 3-furyl and 3-thienyl fulgides and fulgimides, which are disclosed in U.S. Pat. No. 4,931,220 (which is specifically incorporated herein by reference) and mixtures of any of the foregoing photochromic materials/compounds.
The photochromic compounds according to the present invention can be prepared according to methods well known in the art. For non-limiting illustrative purposes and with reference to fig. 1(a) to 1(c) of the accompanying drawings,
Referring to fig. 1(a), in a first step, aryl ketone (101) is subjected to a Stobbe condensation, well known in the art, which involves the reaction of aryl ketone (101) with dimethyl succinate (not shown) in the presence of potassium tert-butoxide, resulting in the formation of intermediate (102). Intermediate (102) may then undergo ring closure in the presence of acetic anhydride, followed by methanolysis (e.g., by reaction with methanol in 12N HCl), which results in the formation of intermediate (103).
Referring to FIG. 1(b), intermediate (103) can be reacted with a Grignard reagent (e.g., R)4MgBr and R5MgBr) under Grignard reaction conditions well known in the art, results in the formation of intermediate (104). Intermediate (104) may then be subjected to ring closure under conditions well known in the art (e.g., under acidic conditions in a suitable solvent such as toluene), which results in the formation of intermediate (105). Intermediate (105) may then be reacted with R1The substituted 2, 5-dihydrofuran is reacted in the presence of Lithium Diisopropylamide (LDA) under suitable conditions well known in the art, such as in an ice-water bath, which results in the formation of intermediate (106).
Referring to fig. 1(c), intermediate (106) may next be subjected to reflux conditions in 1, 2-dichloroethane in the presence of dodecylbenzenesulfonic acid (DBSA), which results in the formation of intermediate (107). Intermediate (107) may then be reacted with propargyl alcohol (108) under conditions well known in the art, which results in the formation of intermediate (109) having a 2H-pyran fused ring substituted with B/B'. In some embodiments, intermediate (109) is representative of a photochromic compound according to the present invention.
According to some embodiments, intermediate (109) may be additionally modified to include an extension group at
According to the present invention, there is also provided a photochromic composition comprising at least one photochromic compound according to the present invention, such as a photochromic compound represented by formula (I), as previously described herein.
According to some embodiments of the invention, the photochromic composition comprises: (i) an organic material, wherein the organic material is at least one of a polymeric material, an oligomeric material, and/or a monomeric material; and (ii) a photochromic compound according to the present invention incorporated into at least a portion of the organic material. The photochromic compound can be incorporated into a portion of the organic material by methods including, but not limited to, at least one of the following: the photochromic compound is blended and/or bonded with the organic material or organic material precursor. As used herein with respect to incorporating photochromic compounds into organic materials, the terms "blend" and "blended" mean that the photochromic compounds/materials are intermixed or mixed with at least a portion of the organic materials, but not bonded to the organic materials. Furthermore, as used herein with respect to incorporating photochromic compounds into organic materials, the term "bonded" or "bonded" means that the photochromic compound/material is attached to a portion of the organic material or precursor thereof, for example, by one or more covalent bonds. For example, although not limited thereto, the photochromic material may be linked to the organic material through a reactive substituent.
According to some embodiments of the present invention, when the organic material is a polymeric material, the photochromic compound may be incorporated into at least a portion of the polymeric material or at least a portion of the monomeric or oligomeric material from which the polymeric material is formed. For example, one or more photochromic compounds according to the present invention (which have reactive substituents) may be bonded to an organic material, such as a monomer, oligomer or polymer, which has a group with which a reactive moiety may react, or which may react as a comonomer in a polymerisation reaction (e.g. during copolymerisation) to form the organic material.
As described above, in some embodiments, photochromic compositions according to the present invention can include organic materials selected from polymeric, oligomeric, and/or monomeric materials. Examples of polymeric materials that can be used with the photochromic compositions of the present invention include, but are not limited to, the following polymers: a bis (allyl carbonate) monomer; diethylene glycol dimethacrylate monomer; diisopropenyl benzene monomer; ethoxylated bisphenol a dimethacrylate monomer; ethylene glycol dimethacrylate monomer(ii) a A poly (ethylene glycol) dimethacrylate monomer; an ethoxylated phenol dimethacrylate monomer; alkoxylated polyol acrylate monomers, such as ethoxylated trimethylolpropane triacrylate monomers; a urethane acrylate monomer; a vinyl benzene monomer; and styrene. Additional examples of suitable polymeric materials include, but are not limited to, polymers of multifunctional, e.g., mono-, di-, or multifunctional, acrylate and/or methacrylate monomers; poly (methacrylic acid C)1-C12Alkyl esters), such as poly (methyl methacrylate); poly (oxyalkylene) dimethacrylate; poly (alkoxylated phenol methacrylate); cellulose acetate; cellulose triacetate; cellulose acetate propionate; cellulose acetate butyrate; poly (vinyl acetate); poly (vinyl alcohol); poly (vinyl chloride); poly (vinylidene chloride); a polyurethane; polythiourethane; a thermoplastic polycarbonate; a polyester; poly (ethylene terephthalate); polystyrene; poly (alpha-methylstyrene); copolymers of styrene and methyl methacrylate; copolymers of styrene and acrylonitrile; polyvinyl butyral; and diallyl pentaerythritol, in particular with the following monomers: polyol (allyl carbonate) monomers, such as diethylene glycol bis (allyl carbonate), and acrylate monomers, such as ethyl acrylate, butyl acrylate. Also contemplated are copolymers of the foregoing monomers, combinations and blends of the foregoing polymers, and copolymers with other polymers (e.g., to form interpenetrating network products).
In some embodiments, the transparency of the photochromic composition is desired, in which case the organic material can be a transparent polymeric material. The polymeric material may be in some embodiments an optically clear polymeric material prepared from a thermoplastic polycarbonate resin, such as a resin derived from bisphenol a and phosgene, under the trade name bisphenol a and phosgene
According to some embodiments, the organic material may be a polymeric material selected from poly (carbonate), copolymers of ethylene and vinyl acetate; copolymers of ethylene and vinyl alcohol; copolymers of ethylene, vinyl acetate and vinyl alcohol (e.g., those formed by partial saponification of copolymers of ethylene and vinyl acetate); cellulose acetate butyrate; poly (urethane); poly (acrylates); poly (methacrylates); an epoxide; an aminoplast functional polymer; poly (anhydrides); poly (urea urethanes); an N-alkoxymethyl (meth) acrylamide-functional polymer; poly (siloxane); poly (silanes); and compositions and mixtures thereof.
In some further embodiments, the photochromic compositions of the present invention additionally comprise at least one of: complementary photochromic materials (including one or more of the other photochromic materials and compounds previously described herein), photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers, heat stabilizers, mold release agents, rheology control agents, leveling agents, free radical scavengers, and/or adhesion promoters.
According to some embodiments, the photochromic composition according to the present invention is a photochromic coating composition. Photochromic coating compositions according to some embodiments of the present invention comprise: the photochromic material according to the present invention, as described previously herein with respect to formula (I); a resin composition, which is optionally curable; and optionally a solvent. The photochromic coating composition may be in the form of liquid coatings and powder coatings well known in the art. The photochromic coating composition of the present invention may be a thermoplastic or thermosetting coating composition. In one embodiment, the photochromic coating composition is a curable or thermoset coating composition.
The curable resin composition of the curable photochromic coating composition according to some embodiments of the present invention includes: a first reactant (or component) having a functional group, such as an epoxy functional polymer reactant; and a second reactant (or component) that is a crosslinking agent having a functional group that is reactive with, and can form a covalent bond with, the functional group of the first reactant. The first and second reactants of the curable resin composition of the curable photochromic coating composition can each independently include one or more functional species and each is present in an amount sufficient to provide a cured photochromic coating having a combination of desirable physical properties such as smoothness, optical clarity, solvent resistance and hardness.
Examples of curable resin compositions that may be used with the curable photochromic coating composition of the present invention include, but are not limited to: curable resin compositions comprising epoxy-functional polymers (e.g., (meth) acrylic polymers containing glycidyl (meth) acrylate residues and epoxy-reactive crosslinkers (e.g., containing active hydrogens such as hydroxyl, thiol, and amine), and curable resin compositions comprising hydroxyl-functional polymers and blocked (or blocked) isocyanate-functional crosslinkers.
In some embodiments, the curable resin composition of the photochromic coating composition of the present invention is a curable polyurethane resin composition. The curable polyurethane resin composition useful for the photochromic coating composition of the present invention typically comprises: active hydrogen functional polymers, such as hydroxyl functional polymers; and a blocked (or blocked) isocyanate functional crosslinker. Hydroxy-functional polymers that may be used in such compositions include, but are not limited to, hydroxy-functional vinyl polymers, hydroxy-functional polyesters, hydroxy-functional polyurethanes, and mixtures thereof, as are well known in the art.
Vinyl polymers having hydroxyl functionality can be prepared by free radical polymerization methods known to those of ordinary skill in the art. In one embodiment of the invention, the hydroxy-functional vinyl polymer is prepared from a majority of (meth) acrylate monomers, and is referred to herein as a "hydroxy-functional (meth) acrylic polymer".
Hydroxy-functional polyesters useful in curable photochromic coating compositions comprising a blocked isocyanate-functional crosslinker can be prepared by methods well known in the art. Typically, the diol and the dicarboxylic acid or diester of the dicarboxylic acid are reacted in such proportions that the molar equivalents of hydroxyl groups are greater than the carboxylic acid groups (or esters of carboxylic acid groups), and water or alcohol is simultaneously removed from the reaction medium.
The hydroxyl functional polyurethane may be prepared by methods well known in the art, for example as previously described herein. Typically, one or more difunctional isocyanates are reacted with one or more materials having two active hydrogen groups (e.g., a diol or dithiol) such that the ratio of active hydrogen groups to isocyanate groups is greater than 1, as known to those skilled in the art.
By "blocked (or blocked) isocyanate crosslinker" is meant a crosslinker having two or more blocked isocyanate groups that can be deblocked (or deblocked) under curing conditions, e.g., at elevated temperatures, to form free isocyanate groups and free blocked groups. The free isocyanate groups formed by deblocking of the crosslinker are preferably capable of reacting with active hydrogen groups of the active hydrogen-functional polymer (e.g., with hydroxyl groups of the hydroxyl-functional polymer) and forming substantially permanent covalent bonds.
It is desirable that the blocking group of the blocked isocyanate crosslinker not negatively affect the curable photochromic coating composition when unblocked from the isocyanate (i.e., when it becomes a free blocking group). For example, it is desirable that the free end capping groups neither become trapped as bubbles in the cured film, nor excessively plasticize the cured film. The end capping groups useful in the present invention preferably have the property of being non-volatile or capable of substantially escaping from the coating being formed prior to vitrification thereof. Typically, the free end-capping groups substantially escape from the forming (e.g., curing) coating prior to its vitrification.
The class of blocking groups of the blocked isocyanate crosslinker may be selected from: hydroxy-functional compounds, e.g. straight-chain or branched C2-C8Alcohols, butyl cellosolve, phenol and p-hydroxymethylbenzoate; 1H-azoles, such as 1H-1,2, 4-triazole and 1H-2, 5-dimethylpyrazole; lactams such as epsilon-caprolactam and 2-pyrrolidone; ketoximes, such as 2-acetoxime and 2-butanone oxime. Other suitableThe end capping groups of (a) include morpholine, 3-aminopropylmorpholine and N-hydroxyphthalimide.
The isocyanate or isocyanate mixture of the blocked isocyanate crosslinker has two or more isocyanate groups (e.g., 3 or 4 isocyanate groups). Examples of suitable isocyanates that may be used to prepare the blocked isocyanate crosslinker include monomeric diisocyanates such as alpha, alpha '-xylylene diisocyanate, alpha' -tetramethylxylylene diisocyanate and 1-isocyanato-3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane (isophorone diisocyanate or IPDI), and dimers and trimers of monomeric diisocyanates containing isocyanurate, uretdione (uretidio), biuret or allophanate linkages such as trimers of IPDI.
The blocked isocyanate crosslinker may also be selected from oligomeric blocked isocyanate functional adducts. As used herein, "oligomeric capped polyisocyanate functional adduct" means a material that is substantially free of polymer chain extension. The oligomeric blocked polyisocyanate functional adduct can be prepared by methods known in the art from, for example, a compound containing 3 or more active hydrogen groups such as Trimethylolpropane (TMP) and an isocyanate monomer such as 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), each in a molar ratio of 1: 3. In the case of TMP and IPDI, oligomeric adducts having an average isocyanate functionality of 3 (e.g., "TMP-3 IPDI") can be prepared by using underfeed and/or dilute solution synthesis techniques well known in the art. Then 3 free isocyanate groups per TMP-3IPDI adduct are blocked with a blocking group such as linear or branched C2-C8Alcohol capping.
To catalyze the reaction between the isocyanate groups of the blocked polyisocyanate crosslinker and the hydroxyl groups of the hydroxyl functional polymer, one or more catalysts are typically present in the curable photochromic coating composition in an amount of, for example, 0.1 to 5 weight percent, based on the total resin solids of the composition. Useful classes of catalysts include, but are not limited to, metal compounds, particularly organotin compounds, such as tin (II) octoate and dibutyltin (IV) dilaurate, and tertiary amines, such as diazabicyclo [2.2.2] octane.
The curable photochromic coating composition according to the present invention (which comprises a hydroxy-functional polymer and a blocked isocyanate-functional crosslinker) typically has the hydroxy-functional polymer present therein in an amount of from 55 to 95 percent by weight, based on the total resin solids weight of the composition, for example from 75 to 90 percent by weight, based on the total resin solids weight of the composition. The blocked isocyanate functional crosslinker is typically present in the curable resin composition in an amount corresponding to the balance of these stated ranges, i.e., 5 to 45, specifically 10 to 25 weight percent.
With respect to the curable polyurethane resin composition of the curable photochromic coating composition of the present invention, the equivalent ratio of isocyanate equivalents in the blocked isocyanate crosslinker to hydroxyl equivalents in the hydroxyl functional polymer is typically in the range of 1:3 to 3:1, for example 1:2 to 2: 1. While equivalent ratios outside this range may be used, they are generally less desirable due to performance deficiencies of the cured photochromic films obtained therefrom. The curable photochromic coating composition according to the present invention, which comprises a hydroxy-functional polymer and a blocked isocyanate-functional crosslinker, is typically cured at a temperature of from 120 ℃ to 190 ℃ over a period of from 10 to 60 minutes.
The photochromic coating composition according to the present invention may optionally further comprise a solvent in some embodiments. Examples of suitable solvents include, but are not limited to, acetates, alcohols, ketones, glycols, ethers, aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. Examples of acetates include, but are not limited to, ethyl acetate, butyl acetate, and glycol acetate. Examples of ketones include, but are not limited to, methyl ethyl ketone and methyl-N-amyl ketone. Examples of aromatic hydrocarbons include, but are not limited to, toluene, naphthalene, and xylene. In one embodiment, one or more solvents are added to each of the first reactant and the second reactant. Suitable solvent mixtures may include, for example, one or more acetates, propanols and derivatives thereof, one or more ketones, one or more alcohols and/or one or more aromatic hydrocarbons. If present, the solvent is typically present in an amount of 5 to 60 weight percent, or 5 to 40 weight percent, or 10 to 25 weight percent, based on the total weight of the photochromic coating composition (including the weight of the solvent).
The curable photochromic coating composition according to the present invention may, in some embodiments, optionally contain additives such as waxes for flow and wetting, flow control agents, e.g., poly (2-ethylhexyl) acrylate, auxiliary resins for modifying and optimizing coating properties, antioxidants, and Ultraviolet (UV) light absorbers. Examples of useful antioxidants and UV light absorbers include those commercially available from Ciba-Geigy under the trade names IRGANOX and TINUVIN. These optional additives, when used, are typically present in an amount of up to 20 percent by weight (e.g., 0.5 to 10 percent by weight), based on the total weight of resin solids of the curable resin composition.
Photochromic compositions, photochromic articles and photochromic coating compositions according to the present invention may, in some embodiments, additionally comprise additives well known in the art that aid or assist in the processing and/or performance of the composition or article. Non-limiting examples of such additives include photoinitiators, thermal initiators, polymerization inhibitors, solvents, light stabilizers (such as, but not limited to, ultraviolet light absorbers and light stabilizers, such as Hindered Amine Light Stabilizers (HALS)), heat stabilizers, mold release agents, rheology control agents, leveling agents (such as, but not limited to, surfactants), free radical scavengers, adhesion promoters (such as hexanediol diacrylate and coupling agents), and combinations and mixtures thereof.
The photochromic compounds of the present invention can be used in amounts (or ratios) such that the composition, organic material, or substrate (e.g., photochromic articles and photochromic coatings) into which the photochromic compound is incorporated or otherwise attached exhibits the desired optical properties. In some embodiments, the amount and type of photochromic material can be selected such that the composition, organic material, or substrate is clear or colorless when the photochromic compound is in a closed form (e.g., in a bleached or unactivated state), and can exhibit a desired formed color when the photochromic compound (e.g., the photochromic indeno-fused phenanthropyrans of the present invention) is in an open form (e.g., when activated by actinic radiation). The precise amount of photochromic material used in the various photochromic compositions and articles described herein is not critical, provided that a sufficient amount is used to produce the desired effect. The specific amount of photochromic material used may depend on a number of factors such as, but not limited to, the absorption characteristics of the photochromic compound, the desired color and color intensity upon activation, and the method used to incorporate or attach the photochromic material to the substrate. Photochromic compositions according to some embodiments of the invention may include a photochromic material according to the invention that includes a compound represented by formula (I) in an amount of from 0.01 to 40 weight percent, or from 0.05 to 15, or from 0.1 to 5 weight percent, based on the weight of the photochromic composition. For additional non-limiting illustration purposes, the amount of photochromic compounds/materials comprising the compound represented by formula (I) incorporated into the organic material can range from 0.01 to 40 weight percent, or from 0.05 to 15 weight percent, or from 0.1 to 5 weight percent, based on the weight of the organic material.
The present invention also relates to photochromic articles comprising one or more photochromic compounds according to the present invention, such as the photochromic compounds represented by formula (I). Photochromic articles are prepared in some embodiments by methods well known in the art, such as by the imbibition (entrapment) method, cast-in-place (cast-in-place) method, coating method, in-mold coating method, over-mold (over-mold) method, and lamination method.
In some embodiments, the photochromic article is selected from ophthalmic articles, display articles, windows, mirrors, and active liquid crystal cell articles and passive liquid crystal cell articles.
According to some further embodiments, the photochromic article of the present invention is selected from ophthalmic articles, and the ophthalmic articles are selected from corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses, and visors.
In some further embodiments, the photochromic articles of the present invention are display articles, and the display articles are selected from screens, monitors, and security elements.
The present invention is more particularly described in the following examples that are intended as illustrative only since numerous modifications and variations therein will be apparent to those skilled in the art.
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