Title of Invention

"PHOTOCHROMIC COMPOSITINS AND LIGHT TRANSMISSIBLE ARTICLES"

Abstract The invention relates to a photochromic polymeric composition comprising a polymer matrix and a photochromic compound which is an adduct comprising a photochromic moiety and at least one pendant oligomer group to provide a rate of fade of the photochromic polymeric composition which is significantly changed when compared with the corresponding composition comprising the photochromic compound without said pendent oligomer. The invention also relates to a photochromic compound which is an adduct comprising a photochromic moiety and at least one pendent oligomer.
Full Text Field
The present in-O-ention relates to a class of functionalised photochromic dyes, to compositions containing the functionalised dyes, and to a method for forming polymeric compositions and light transmissible polymeric articles exhibiting photochromic response.
Background
Photochromism is a property which has been used in the manufacture of light transmissible articles for many years. A compound is said to be photochromic if it changes colour when irradiated and re-O-erts to its original colour when irradiation ceases. The use of photochromies in the manufacture of spectacle lenses is a particular benefit as it enables the efficiency with which radiation is filtered to be varied with the intensity of radiation. Photochromies also ha-O-e potential for use in a range of other polymeric compositions in products or in applications such as windows, automoti-O-e windshields, automoti-O-e and aircraft transparencies, polymeric films coating compositions, optical switches and data storage de-O-ices. Photochromics could also be used in inks and to impro-O-e the security of documents and currency, for example by pro-O-iding a security check under UV light or by indicating exposure to light during photocopying.
Despite the use of photochromic compounds in applications such as lenses there ha-O-e been a number of problems which reduce the -O-ersatility and potential of this technology.
It is advantageous to control the rate at which photochromic polymoric compositions colour when exposed to radiation and fade on cessation of this exposure. In many situations, it is important to pro-O-ide rapid colouring and fading kinetics, particularly for lenses and spectacles. In some polymers howe-O-er, the rate of coloration and fade is slow so that a compromise needs to be made in the components and properties of the substiate to enhance the rate of coloration and fade. For example, many photochromies colour and fade

more rapidly in soft materials and yet, for applications such as spectacles or structural panels, abrasion resistance and hardness are important. This trade off between rate of transformation and hardness produces a dilemma for manufacturers between toughness and photochromic efficiency. In polymeric lenses many photochromies exhibit a slower rate of fade than is desirable. It would be desirable to ha-O-e photochromic dyes which fade rapidly regardless of the hardness of the matrix.
One approach taken by pre-O-ious workers is toproduce photochromies which are an integral part of the host matrix. This is achie-O-ed by functionalising the photochromic with an unsaturated group which is polymerised with the polymer matrix. The photochromic thus becomes covalently tethered to the host polymer matrix. Howe-O-er unless the matrix is relati-O-ely soft the rate of fade is ad-O-ersely effected. Hu et al, Pure Appln. Chem.. AA(6) pp 803-810 (1996) also reported that tethering of the photochromic leads to the decolouration rate remaining almost constant with increasing dye concentraiion. Further the fade obser-O-ed :s significantly slower when this photochromic is tethered at concentrations less than15wt%.
Another example of cases where control of fade is desirable is with the a mixture of photochromic compounds. It is sometimes necessary to use a mixture of photochromic compounds to achie-O-e the desirable colour such as brown or grey. Howe-O-er, ;he different photochromic dyes used in combination to achie-O-e these colours often differ slightly in the rate of fade so that the mixture undergoes an unattracti-O-e variation in colour during fade. In other cases it may be desirable to reduce the rate of fade so that colouration or fade is gradual and controlled. For example in optical switches it may be desirable for the photochromic article to undergo rapid switching under specific thermal or electromagnetic stimulus but otherwise not fade under the ambient conditions of temperature and light.
Another problem associated with photochromic compounds is their lifetime. Many photochromic compounds ha-O-e a relati-O-ely short lifetime before they fatigue, due to chemical degradation, and either no longer undergo re-O-ersible

colour change or become less efficient. This is a problem, for example, in more hostile chemical en-O-ironments such as in high index lenses containing sulfur-containing polymers or paper.
Summary
We ha-O-e now found that the photochromic properties of photochromic dyes in a polymeric substrate can be controlled by using a photochromic compound in which the photochromic moiety is functionalised to contain one or more pendant oligomer groups. Without wishing to be bound by theory we belie-O-e that certain oligomer groups pro-O-ide a nanoen-O-ironment to produce a significant change in the rate of fade. The one or more pendant oligomer groups change the rate of fade of the photochromic moiety in the polymeric matrix.
In one aspect the in-O-ention pro-O-ides a photochromic polymeric composition comprising a polymer matrix and a photochromic compound which is an adduct cc.ipiising a pho!ochromic moiety and at least one pendant oligomer group ^ pro-O-ide a rate of fade of the photochromic polymeric composition which is significantly changed when compared with the corresponding composition comprising the photochromic compound without said pendent oligomer.
The oligomer is preferably not reacti-O-e the host matrix so that it does not become covalently tethered to the matrix polymer.
In a fuither aspect the in-O-ention pro-O-ides a photochromic compound which is an adduct comprising a photochromic moiety and at Ip^st one pendant oligomer.
In the preferred embodiment of the in-O-ention the oligomer significantly increases the rate of fade so that the fade half life and/or the time taken to reach % reduction in absorbance is reduced by at least 50% compared with the corresponding composition in absence of the oligomer.
Detailed Description
In a rigid polymeric material of high glass transition temperature (Tg) the
photochromic action of many photochromic compounds is reduced significantly

when compared with softer materials. Without wishing to the bound by theory, we belie-O-e that the reduction in photochromic performance in polymeric substrates may occur as a result of the restriction in the -O-olume available for the dye to transform by ring opening and/or effects of polar interaction.
One possible explanation of the more rapid transition obser-O-ed for many compounds of the in-O-ention is that the oligomer chain may coil about the photochromic group to pro-O-ide nanoencapsulation facilitating more rapid con-O-ersion between ring-open and ring-closed forms. The oligomer chains may pro-O-ide a low Tg nanoen-O-ironment or otherwise fa-O-ourably alter the local en-O-ironment. Accordingly it is preferred that the oligomer attached to the photochromic compound of the in-O-ention has a relati-O-ely low Tg. For example the Tg is preferably less than 25°C. More preferably the compounds of the in-O-ention are liquids at room temperature.
The compatibility of the oligomer chain with the host matrix may also influence the rate of fade.
The rate of fade of a photochromic chromophore may be slowed by using a plurality of oligomer substituents including a first oligomer chain and a second oligomer chain each on opposite sides of the photochromic moiety (such as spiro-oxazine group). This trend is especially the case as the Tg of the
oligomers increases or they become more compatible with the host matrix. For example, in the case of spiiu indoiene aryleneoxazine compounds, one oligomer may be attached to fused benzene ring of the indoiene portion and one oligomer chain attached to the aryl portion fused with the oxazine. When the oligomer chains are each compatible with the host matrix they may restrict motion of the photochromic moiety by becoming included into the matrix and restricting opposite ends of the spiro-oxazine. Fade speed may also be slowed by a single oligomer of relati-O-ely high Tg.
The trend in compatibility of an oligomer with the polymer matrix in many cases is consistent with polarity. Thus, an oligomer of similar polarity to the first polymer matrix is regarded as compatible. For example polyalkylene glycol

oligomer groups are compatible with polar polymeric hosts such as acrylate and polyalkylene and poly(arylalkylene) oligomers are compatible with non-polar resins such as polyolefins and styrenic polymers (eg polystyrene, SBR etc) respecti-O-ely.
We ha-O-e also found that the nanoen-O-ironment pro-O-ided by the presence of one or more oligomer chains significantly impro-O-es the photochromic life of compounds of the in-O-ention when compared with unsubstituted photochromic compounds.
The in-O-ention relates to photochromic compounds comprising a photochromic moiety and at least one pendant oligomer group. Said at least one oligomer may be selected from the group consisting of polyether oligomers, polyalkylene oligomers, polyfluroalkylene oligomers, poly fluoroalkylether oligomers, polydi(C1 to C10 hydrocarbyl)silyloxy oligomers, polysilicic acid oligomrrs (silicates) or derivati-O-es thereof, poly (2Si(OH)3) oligomers and derivati-O-es thereof, poly (ZSiCI3) oligomers and derivati-O-es thereof, poly (ZSi(OMe)3) oligomers and derivati-O-es thereof, and mixtures thereof wherein Z is an organic group. Preferably Z is selected from the group consisting of hydrogen, alkyl, optionally substituted alkyl, haloalkyl, cycloalkyl, optionally substituted cycloalkyl, hydroxy, amino, optionally substituted amino, alkoxy, aryloxy, aryl, optionally substituted aryl, carboxylic acid and derivati-O-es thereof. A particularly preferred subset of these later oligomers are colloquially known as Polyhedral Oligomeric Silsesquioxanes (POSS). Compounds that contain a photochromic moiety and a POSS oligomer can display crystalline state photochromism.
The combined number of monomer units in the oligomers is preferably at least 5 and more preferably at least 7 and still more preferably at least 10. The oligomer and any group linking the oligomer to the chromophore preferably together pro-O-ide a longest chain length of at least 12 atoms in the backbone of the chain, more preferably at least 15 aloms and most preferably at least 7 atoms.
The modified photochromies of the in-O-ention generally are of formula I
(Formula Removed) wherein
PC is the photochromic moiety;
L is a bond or linking group;
R is an oligomer chain;
n is an integer of from 1 to 3;
m is an integer of from 1 to 3 and wherein the total number of monomer units in the oligomer groups (R) is at least 5, preferably at least 7, more preferably at least 10. It is particularly preferred that the linking group (when present) and the oligomer [ie. the radical .L(R )n)m] together pro-O-ide a longest chain length of at least 12 atoms, more preferably at least 15 atoms and most preferably 17 to 40 atoms in the chain backbone.
lixamples of suitable oligomer groups R include groups of formula 1a:
(Formula Removed)
wherein:
X is selected from oxygen, sulfur, amino such as C1 and C6 alkyl amino, C1 to C4 alkylene (preferably methylene); p is 0 or 1;
q is the number of the monomer units R1 ;n said oligomer and is preferably at least 5;
R1, which may be the same or different, are selected from the group consisting of:
C2 to C4 alkylene such as ethylene, propylene and butylene; halo (C2 to C4 alkylene) such as perfluoroethylene, perfluoropropylene, and perfluorobutylene; C2 to C4 alkyleneoxy; C2 to C4 haloalkyioneoxy;
di (CM to C10 hydrocarbyl)silyloxy wherein the hydrocarbyl may be alkyl, aryl alkyl substituted aryl or aryl substituted alkyl and particularly di(C-i to C4 alkyl)silyloxy such as dimethylsilyloxy;; and
R2 is selected from hydrogen, C1 to C6 alkyl and C^ to C6 haloalkyl, hydroxy, optionally substituted amino, optionally substituted aryl carboxylic acid and derivati-O-es thereof and preferably R2 is selected from the group consisting of hydrogen, C1 to C6 alkyl, substituted amino, optionally substituted aryl and alkyl and aryl esters of carboxyl.
Examples of suitable oligomer group R also include groups of formula 1B or 1C

(Formula Removed)
wherein Z is an organic group, preferably an organic group selected from the group consisting of hydrogen, alkyl, optionally substituted alkyl, haloalkyl, cycloalkyi, optionally substituted cycloalkyi, hydroxy, amino, optionally substituted amino, alkoxy, aryloxy, aryl, optionally substituted aryl, carboxylic acid and derivati-O-es thereof. It is particularly preferred that Z is selected from the group consisting of isobutyl, iso-ocytl, cyclopentenyl, cyclohexyl and phenyl.
The oligomer group preferably does not contain groups which undergo radical or condensation reactions. Thus the oligomer will generally not ha-O-e a terminal unsaturated group or terminal activated hydrogen such as amino hydroxyl or carboxyl.
Preferably L is selected from the group consisting of a bond or the polyradical selected from the group of formula lla, lib, He, lid, He, Ilf, llg, III, Hi, llj and Ilk.

(Formula Removed)
wherein n is from 1 to 3;
(Formula Removed)
wherein in the formula Ha to Ilk:
X which may be the same or different is as hereinbefore defined;
R4 is selected from the group consisting of hydroxy, alkoxy, amino and
substituted amino such as alkyl amino;
n is an integer from 1 to 3;
w is an integer from 1 to 4;
q is an integer from 0 to 15;
p which when there is more than one may be the same or different is 0 or 1; and
(R) shows the radial for attachment of oligomer R.
The purpose of the linking group is to join the oligomer(s) to the photochronic moiety. A linking group may be needed when the oligomer has a functional group that cannot be used directly to join to the dye. For example the terminal hydroxyl of a PEG oligomer can be con -erted to an acid by reaction with succinic anhydride. This could then be readily joined to the hydroxy group on a photochromic moiety such as Q'-hydroxy-I.S.S-trimethylspirotindoline^.S'-93H]naphtha[2,1-b][1,4]oxazine]. Another example is in Example 16 where the carboxylic acid on the chromene was esterified with ethylene glycol to pro-O-ide a hydroxy group that can react with the acid group (-O-ia the acid chloride) of the poly(dimethylsiloxane) monocarboxydecyl chloride.
The linking group may in some case be available as part of the oligomer. For example in the examples we demonstrate the use of poly(dimethylsiloxane) monocarboxydecyl chloride. The undecyl carboxy group is part of the commercially available oligomer MCR-B11 and acts as the linking group between the dye and the oligomer.
Specific examples of linker groups L include:


(Formula Removed)
The compounds of the present in-O-ention comprise oligomer groups wherein me total number of monomeric units is as least 5, pruferabiy at least 7, and most preferably at least 10. The oligomer chain and linking group preferably pro-O-ide a longest chain length of at least 12 atoms, more preferably at least 15 atoms and most preferably from 17 to 40 atoms. The chain length we refer to here is iho number of atoms linked in sequence in the polymer backbone.
The oligomer(s) may be in the form of linear chains, branched chains, copolymers including block or random copolymers; howe-O-er, it is particularly
preferred that each oligomer comprise at east 5 monomer units of the same type, and more preferably at least 7.
Preferably, the monomer units are selected from the groups consisting of perfluruoalkylene, alkylene, arylalkylene, alkyleneoxy, haloalkyleneoxy, and di(C1 to C10 hydrocarbyl)silyloxy. More preferred monomer units are alkyleneoxy, and dialkylsilyloxy and e-O-en more preferred are ethyleneoxy, propyleneoxy and random and block copolymers thereof.
The photochromic compound of the in-O-ention of formula I includes up to three groups each of which may include one, two or three oligomer groups R.
Examples of preferred oligomer groups include:
(Formula Removed)
wherein the monomer units are distributed randomly or in block form
(Formula Removed)
wherein 0 is alkyl or aryl and includes at least a portion of aryl groups
(Formula Removed)
wherein X and R2 and p are hereinbefore defined and x, -O- and y are the number of repeating units, and alkyl is C1 to C20 alkyl, preferably C1 to C10 alkyl such as methyl, ethyl, propyl, butyl, pentyl or hexyl. Preferably the compounds of the in-O-ention include at least one oligomer group wherein the number of monomer units (x or y+-O- in the abo-O-e examples) is at least 7 and are most preferably at least 10.
A further preferred oligomer group is a group of formula: Z
(Formula Removed)
wherein Z is an organic group, preferably an organic group selected from the group consisting of hydrogen, alkyl, optionally substituted alkyl, haloalkyl, cycloalkyl, optionally substituted cycloalkyl, hydroxy, amino, optionally substituted amino, alkoxy, aryloxy, aryl, optionally substituted aryl, carboxylic acid and derivati-O-es thereof. It is particularly preferred that Z is selected from the group consisting of isobutyl, iso-ocytl, cyclopentenyl, cyclohexyl and phenyl.
The most preferred oligomer groups contain at least 10 monomer units. The monomer units may be up to thirty or more units in length but we ha-O-e found the range of from 10 to 30 to be particularly suitable.
It will be appreciated by those skilled in the art that the presence and nature of the group X is dependent on the linker group. When the linker group is a bond and the oligomer is linked to a heteroatom such as nitrogen, then p is preferably zero.
Howe-O-er, when the group L-(R)n is attached to a carbon radical of the photochromic moiety, or a linker of formula Ha to Ilk then in the oligomer group R the integer, p is preferably 1.
The photochromic moiety may be chosen from a wide range of photochromic moieties known in the art. The most appropriate photochromic moieties for use in the compounds used in accordance with the in-O-ention are photochromies which undergo a molecular isomerism such as a cis-trans isomerism or pericyclic reaction such as 6Π, -6 atom, 6 π, - 5 atom processes and [2+2],[4+4] or [4+2] cycloadditions. The compositions of the in-O-ention (and in particular the oligomer chains) are belie-O-ed to pro-O-ide a nanoen-O-ironment to pro-O-ide a desired en-O-ironment which may lead to a more rapid transformation between the colour-producing chromophore and colourless state of the photochromies.
Photochromic oligomer adducts in accordance with the in-O-ention may comprise a photochromic moiety selected from the group consisting of:
chromenes such as those selected from the group consisting of naphthopyrans, benzopyrans, indenonaphthopyrans and phenanthropyrans;
spiropyrans such as those selected from the group consisting of spiro(benzindoline) naphthopyrans, spiro(indoline)benzopyrans, spiro(indoline)-naphthopyrans, spiroquinopyrans, and spiro(indoline)pyrans and spirodihydroindolizines;
spiro-oxazines such as those selected from the group consisting of
spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines,
spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines and spiro(indoline)- benzoxazines;
fulgidies, fulgimides;
anils;
perimidinespirocyclohexadienones;
stilbenes;
thioindigoids;
azo dyes; and
diarylethenes.
Examples of photochromic moieties may be selected from the group consisting of fulgide photochromic compounds, chromene photochromic compounds and spiro-oxazine photochromic compounds. A wide range of photochromic compounds of each of the classes referred to abo-O-e ha-O-e been described in the prior art and ha-O-ing regard to the teaching herein the skilled addressee will ha-O-e no difficulty in preparing a wide range of photochromic oligomer adducts. Examples of chromene photochromic compounds, fulgide photochromic compounds and spiro-oxazine photochromic compounds are described in US Patent No. 5776376.
The most preferred photochromic compounds are the chromenes and spiro-oxazines, specifically spiroindolene aroxazines.
Sprio-oxazines such as sprioindoline naphlhoxazines depiciod beiow are clear but in the presence of light undergo ring opening to gi-O-e a coloured form as shown:
(Formula Removed)
A further embodiment of the in-O-ention is a photochromic compound of formula
(Formula Removed)
wherein PC is a photochromic moiety particularly a spirooxazine of formula III, chromene of formula XX, fulgide/fulgamide of formula XXX or an azo dye of
formula XL and L, R, X and n and p are as hereinbefore defined. Formulae III, XX, XXX and XL are described below with reference to examples.
Preferred spiro-oxazines of the general formula III can be suitably used.
(Formula Removed)
In the general formula III, R3, R4 and Rs may be the same or different and are each an -alkyl group, a cycloalkyl group, a cycloarylalkyi group, an alkoxy group, an alklyleneoxyalkyl group, an alkoxycarbonyl group, a cyano, an alkoxycarbonylalkyl group, an aryl group, an arylalkyi group, an aryloxy group, an alkylenethioalkyl group, an acyl group, an acyloxy group or an amino group, R4 and R5 may together form a ring, and R3, R4 and R5 may optionally each ha-O-e a substituent(s). The substituent(s) can includes (include),, besides the abo-O-e-mentioned groups, halogen atom nitro group, heterocyclic group, etc. The group represented by moiety IlIa
is a substituted or unsubstituted bivalent aromatic hydrocarbon group or a substituted or unsubstituted bivalent unsaturated heterocyclic group. The group represented by moiety 1Mb
(Formula Removed)
is a substituted or unsubstituted bivalent aromatic hydrocarbon group or a substituted or unsubstituted bivalent unsaturated heterocyclic group. Specific examples of the bivalent aromatic hydrocarbon group are groups of 6 to 14 carbon atoms deri-O-ed from benzene ring, naphthalene ring, phenanthrene ring, anthracene ring or the like. Specific examples of the bivalent unsaturated heterocyclic group are groups of 4 to 9 carbon atoms deri-O-ed from furan ring, benzofuran ring, pyridine ring, quinoline ring, isoquinoline ring, pyrrole ring, thiophene ring, thiophene ring, benzothiophene ring or the like.
The substituents can be the same groups as mentioned abo-O-e with respect to R3, R4 and R5. In particular, a group represented by
NR6R7 (wherein R6 and R7 are each an alkyl group, an alkoxy yroup, an allyl group or the like, each of which may be substituted; and R6 and R7 may be bonded and cyclized with each other to form a nitrogen-containing heterocyclic ring) is preferable from the standpoint of high density of its de-O-eloped colour in the initial photochromic performance.
In a particularly preferred embodiment the photochromic compounds of the in-O-ention are of formula I-O-
(Formula Removed)
wherein R3, R4, R5, R8 R9, R10 and R11 are independently selected from the group consisting of hydrogen, alkyl, halo, haloalkyl, cycloalkyl, cycloarylalkyl, hydroxy, alkoxy, alkyleneoxyalkyl, alkoxycarbonyl, aryl, arylalkyl, aryloxy, alkylenethioalkyl, acyl, acyloxy, amino, NR6R7, cyano and the group L(R)n wherein at least one of R3, R8 and R9 is the oligomer group of formula L(R)n wherein L, R and n are hereinbefore defined and wherein there is more than one L(R)n group in the groups R8, R3, R4 and R5 and one or more R groups may optionally be linked together to form one or more bridging oligomers. The subscript m is an integer and may be 0, 1 or 2 wherein m fc 2 the groups may be independently selected.
In the compound of formula I-O- the total of the number of monomer units in oligomer substituents, (R)n, is at least 7 and preferably at least 12.
More preferably, the substituents R3 is selected from the group consisting of alkyl, cycloalkyl, cycloarylalkyl, alkyleneoxyalkyl, aryl, arylalkyl alkylenethioalkyl, and the group L(R)n and more preferably R3 is selected from alkyl, cycloalkyl, cycloarylalkyl, alkenyloxyalkyl, aryl, arylalkyl, and the group L(R)n and preferably R4 and R5 are indefinitely selected from alkyl, cycloalkyl and aryl.
R8 and R9 are independently selected from hydrogen and L(R)n; R10and R11 are independently selected from the group consisting alkyl, cycloalkyl, cycloarylalkyl, alkoxy, -NR6R7, cyano, alkyleneoxyalkyl, alkoxycarbonyl, aryl, arylalkyl, aryloxy, alkylenethioalkyl, aryl aryloxy and amino and most preferably R10 and R11 are independently selected from alkyl, cycloalkyl, alkoxy, NR6R7 and cyano; and
m is 0 or 1.
bxamples of the preferred fused aromatic ring groups of formula Ilia include Hla(i);
(Formula Removed)
wherein R9 and R11 are as hereinbefore defined.
Examples of the preferred fused aromatic ring group of formula lllb include lllb(i), lllb(ii), lllb(iii) and lllb(i-O-).
(Formula Removed)
Specific examples of the group of formula llla(i) include
(Formula Removed)
Specific examples of the group of formula lllb include


(Formula Removed)
One particularly preferred embodiment of the compounds of formula I-O- has the formula Iva
(Formula Removed)
The more preferred compounds of formula Iva are compcnds wherein P4 and R5 are preferably independently selected from the group consisting of C1 to C4 alkyl and the group wherein R4 and R5 link together to form a cycloalkyl of from 4 to 6 carbon atoms.
R8 and R9 are independently selected from the group consisting of hydrogen, halogen, cycloalkyl, cycloarylalkyl, hydroxy alkoxy, cyano, alkenyloxyalkyl, alkoxycarbenyl, aryl, aralkyi, aryioxy, alkylene, thioalkyi and the oligomer of
formula L(R)n wherein L, R and n are as hereinbefore defined;
R10 and R11 are independently selected from the group consisting of hydrogen, halogen, cycloalkyl, cycloarylalkyl, alkoxy, cyano, alkenyloxy; Ikyl, alkoxycarbonyl, aryl, arylalkyl, acyloxy and alkylenethioalkyl. Most preferably R10 and R11 are hydrogen; and at least one of R8 and R9 is the group L(R)n wherein the total numbei of monomer units in R is at least 10 and more preferably at least 12.
In order to pro-O-ide an increase in fade rate of the photochromic in a polymer (preferably a polymer of high Tg) article, the size of the polymer chain must be greater than a certain size. The minimum size will depend on the nature of the
oligomer chain and the linking group. It is belie-O-ed that the fade is significantly accelerated where a polymer chain may adopt a conformation in which a portion of the chain is adjacent the oxazine ring. Accordingly, linking groups which direct the oligomer chain across the molecule (such as the group of formula -O-I to -O-III comprising at least one polymer chain R in a portion otho to the link) may enable the minimum number of effecti-O-e monomer units to be reduced when compared with other linking groups.
Surprisingly, we ha-O-e found that a single substituent containing at least one oligomer chain may accelerate fade in a wide variety of polymers whereas in the case of at least two oligomer chains, each on opposite sides of the oxazine ring, the rate of fade of photochromic compounds in polymers may be reduced. Without wishing to be bound by theory, we belie-O-e that interaction between oligomer chains on opposite sides of the oxazine portion with the host polymer may restrict or constrain the photochromic molecule to reduce the rate of ring opening and closure of the spiro-oxazine.
Accordingly, in one preferred embodiment one of R3, R8 and R9 is L(R)n where the R groups together include at least 10 monomer units. Alternati-O-ely, R8 and at least one of R9 and R3 (preferably R9) is L(R)n and the two or more groups L(R)n contain at least 10 monomer units.

(Formula Removed)
uolua j to spunodiuoo p sa|diuexa oypads
(Formula Removed)
wherein (EO) is the group (CH2CH20). and PDMS (855) = polydimethylsiloxane with an a-O-erage molecular weight of 855 including a torn innl butyl dimethyl silane end group.
The more preferred compounds of the in-O-ention are of formula (I-O-b)
Further preferred compounds are pro-O-ided in Table 2 Table 2
(Table & Formula Removed) where the substituents are hereinbefore described and e-O-en more preferably R3 is C1 to C4 alkyl; C3 to C6 cycloalkyl, aryl, alkylaryl, arylalkyl and L(R)n; R5a and R5b are independently selected from C1 to C6 alkyl C3 to C6 cycloalkyl, aryl; R8 and R9 are selected from hydrogen, hydroxy, C1 to C6 alkoxy; R10 is selected from the group hydrogen, hydroxy, C1 to C6 alkoxy -NR6R7 wherein R6 and R7 are independently hydrogen, C1 to C6 alkyl and wherein R6 and R7 may together form a di-O-isional hydrocarbon chain of 4 to 6 carbon atoms.
As we ha-O-e discussed abo-O-e, in order to maximise the rate of colouration and fade in polar and non-polar polymers it is preferred that one of R3, R8 and R9 is L(R)n comprising at least 10, more preferably at least 12 monomer units and the other two of R3, R8 and R9 are other than L(R)n where L(R)n contains 7 monomer units.
In compounds where more than one of R3, R8 and R9 is L(R)n comprising at least -O- monomer units, the effect on the late of colouration and fade will depend to some extent on the oligomer and type of polymer. In cases where the polymer and oligomers are compatible, the rate of fade may be decreased and when the oligomer and resin are less compatible, the effect may be less or fade may be increased.
We ha-O-e found that for compounds of formula I-O- a (preferably I-O-b) if R8 and R9 are shorter chains or smaller substituents they are also useful in controlling the rate of fade though to a more limited extent.
In a further embodiment, the in-O-ention therefore pro-O-ides compounds of formula Iva (preferably I-O-b) wherein R8 and R9 are each selected from groups of formula I and groups of formula L(R)n as hereinbefore defined and the group LR11 wherein R11 is lower alkyl, lower haloalkyl, lower polyalkyleneoxy aryl and aryl(lower alkyl). The term lower is used to mean up to 6 carbon atoms in the chain and preferably up to 4.
In yet another embodiment we pro-O-ide an intermediate for preparation of compounds of the in-O-ention, the intermediate being of formula Iva and more preferably I-O-b wherein R8 and R9 are selected from XH wherein X is hereinbefore defined. Preferably R8 and R9 are the same.
Compounds of the in-O-ention may be prepared by reaction of intermediates va or -O-b and -O-I.
(Formula Removed)
One method for preparing compounds of the in-O-ention comprises reacting a methylene indolene of formula va or Fishers base or indoiium salt of foimula -O-b where J is halogen, particularly the iodide salt, wherein R13 is R9 and R14 is R3 with a nitrosohydroxy compound of formula -O-I to pro-O-ide a compound of the in-O-ention of formula '-O-.
Alternati-O-ely, a methylene indolene of formula va or indolium salt of formula -O-b may be reacted with a nitrosohydroxy compound of formula -O-I wherein R12 and R13 are independently selected from the group consisting of hydrogen and -XH and at least one of R12 and R13 is -XH to pro-O-ide an intermediate of formula -O-II.

(Formula Removed)
reacting the compound of formula -O-III with a compound of formula -O-II
(Formula Removed)
wherein J is a lea-O-ing group to form a compound of formula I-O- wherein at least
(Formula Removed)
Alternati-O-ely or in addition the compound of formula I-O- wherein R3 is L(R)n may be prepared by (a) reacting the compound of formula va or -O-b with a compound of formula -O-III to pro-O-ide a compound of formula va and -O-b where R14 is L(R)n and reacting the compound of formula -O-ia or -O-lb with a compound of formula -O-I to pro-O-ide a compound of formula I-O- wherein R3 is L(R)n.
Specific examples c! compounds of fcifuila -O-ill, include J L(R)n -O-.hei 3 J is chlorine, L is of formula I la to lie where p is O and R is any one of the R group examples (i) to (-O-) shown nbo-O-e.
Compounds of formula I-O- where L is a bond may additionally be prepared by using a toluene sulfonyl lea-O-ing group for example by reaction of the compound of formula IX
(Formula Removed)
with a compound of formula I-O- wherein at least one of R8 or R9 is XH and/or R3 is hydrogen to pro-O-ide a compound where one or more groups is alkoxylated.
Compounds of formula X

(Formula Removed)
X ha-O-ing a wide variety of the fused aromatic groups B may be prepared using the intermediate of formula -O-c.
(Formula Removed)
The fused aromatic group B and its substituents may be chosen to pro-O-ide the disused colour of the photochromic compound. Such compounds pro-O-ide a -O-ersatile mothod ot preparation of rapid fade cniro;ndolineoxazines.
Examples of suitable substituted methylene indolene compounds of formula va and -O-b include 5-amino indolene compounds described by Gale & Wiltshire (J. Soc. Dye and Colourants 1974, 90, 97-00), 5-amino methylene compourids described by Gale, Lin and Wilshire (Aust. J. Chem. 1977 30 689-94) and 5-
hydroxy compounds described in Tetrahedron Lett. 1973 12 903-6 and in US Patent 4062865.
One of the preferred groups of photochromies are the spiropyrans. Examples of spiropyrans include compounds of formula XIX and XX

(Formula Removed)
wherein in XIX the groups X, Y, Z and Q may be substituents including where one or more thereof form a carbocyclic ring optionally fused with aryl and the substituents R23 and R24 may be present in any ring; and wherein
B and B are optionally substitutedaryl and heteroaryl; and R22, R23 and R24 are independently selected from hydrogen; halogen; C1 to C3 alkyl; the group L(R)n; and the group of formula COW wherein W is OR25, NR26R27, piperidino or morpholino wherein R25 is selected from the group consisting of C1 to C,3 alkyl, phenyl, (C1 o C6 alkyl)phen-O-l, C1 to C6 alkoxyphenyl, phenyl C1 to C6 alkyl (C-j to C6 alkoxy)phenyl, C-i to C6 alkoxy C2 to G4 alkyl and the group L(R)n; R26 and K27 are each selected from the group consisting of C1 to C6 alkyl, C5 to C7 cycloalkyl, phenyl, phenyl substituted with one or two groups selected from C1 to C6 alkyl and C1 to C6 alkoxy and the group L(R)n; R22 and R23 may optionally from a carboxylic ring of 5 or 6 ring members optionally fused with an optionally substituted benzene and wherein at least one of the substituents selected from the group of substituents consisting of B and B", R22, R23, R24, R25, R26 and R27 is the group L(R)n.


When R22 and R23 are carbocyclic a preferred compound is of formula XX(d)

(Formula Removed)
where R22, R28 and R29 are as defined for R22 abo-O-e.
Preferably B and B' are independently selected from the group consisting of aryl optionally substituted with from 1 to 3 substituents, heteroaryl optionally substituted with from 1 to 3 substituents. The substituents where present are preferably selected from the group consisting of hydroxy, aryl, (C1 o C6) alkoxyaryl, (C1 to CQ) alkylaryl, chloroaryl (C3 to C7) cycloalkylaryl, (C3 to C7) cycloalkyl, (C3 to C7) cycloalkoxy, (C3 to C7) cycloalkoxy, (C1 to C6) alkyl, aryl (C1 to C6) alkyl, aryl (C1 to Ce) alkoxy, aryloxy, aryloxyalkyl, aryloxy (C1 to C6) alkoxy, (C1 to C6) alkylaryl, (C1 to C6) alkyl, (C1 to C6)) alkoxyaryl, (C1 to C6) alkyl, (C1 to C6) alkoxyaryl, (d to C6) alkyl, (C1 to C6) alkoxyaryl, (C1 to C6) alkoxy, amino, N-(C1 to C6) alkyl ipirazino, N-aryl piperazino, indolino, piper '"no, aryl pipersillins, morpho'ino, thiomorpholino, tetr~hydro quinolino
NR29R30 wherein R29 and R30 are independently selected from the group selected from C1 to C6 alkyl, pl.enyl, C5 to C7 cycloalkyl and the group wherein R29 and R30 form a linking group of 4 or 5 linking groups comprising methylene groups and optionally containing one or two hetero atoms and optionally further substituted by C1 to C3 alkyl and the group L(R)n.
R22 is selected from the group consisting of hydrogen, C1 to C6 alkyl; COW where
W is OR25 wherein R25 C1 to C6 alkyl; and the group NR26R27; wherein R26 and R27 are independently C1 to C6 aikyl; and the group L(R)n.
Particularly referred naphthopyran compounds are of formula XX(a)
(Formula Removed)
wherein R20 and R21 are independently selected from the group consisting of hydrogen, hydroxy, alkoxy, amino, alkylamino, dialkylamino and L(R)n;
R22 is the group COW where W is C1 to C6 alkoxy or the group L(R)n;
R23 is selected from the group consisting of hydrogen and NR26R27 where R26 are independently selected from the group consisting of C1 to C6 alkyl and where R26 and R27 may together form an alkylene group of 4 to 6 carbon atoms;
R24 is hydrogen or the group L(R)n; and wherein at least one of R22 and R24 is L(R)n.
Specific example of the naphthopyran compounds of formula XX(a) include those shown in Table 3:
(Table Removed)
Compounds of formula XX wherein R23 and/or R24 comprise the oligomer group L(R)n may be prepared from a suitably substituted acetophenone, benzophenone or benzaldehyde of formula XXI(a). In this process the compound of formula XXI(a) (or a polyhydroxy compound where more than one substituent is required) is reacted with an oligomer esterified toluene sulfonate of formula XXI to pro-O-ide the corresponding oligomer ether of formula XXI(b). The aromatic oligomer ether of formula XXI(b) is reacted with an ester of succinic acid such as the dialkyl succinate of formula XXI(c). A Stobbe reaction produces the condensed half ester of formula XXII which undergoes cyclo dehydration in the presence of acidic anhydride to form the naphthalene oligomer ether of formula XXIII. This compound of formula XXIII may be reacted with acid such as hydrochloride acid and an anhydrous alcohol such as mushanol to form the cornos ponding naphthol shown in formula XXI-O- which is in turn coupled with the propargyl alcohol of formula XX-O- to form the oligomer substituted naphthopyran of the in-O-ention of formula XX(b).
(Formula Removed)
Alternati-O-ely, compounds of formula XX(c) in which at least one of the germinal phenyl groups is substituted by an oligomer may be prepared from the benzophenone of formula XXI(f). In this process the benzophenone substituted
with the appropriate hydroxyl groups is reacted with the oligomer ester of toluene sulfonate of formula XXI(e) to form the corresponding oligomer substituted benzophenone of formula XXI(g). The corresponding propargal alcohol of formula XX-O-(a) is prepared from the benzophenone by reaction with sodium acetylide in a sol-O-ent such as THF. This propargal alcohol of formula XX-O-(a) is coupled with the appropriate substituted naphthol of formula XXI-O-(b) to form the oligomer substituted naphthopyrane of formula XX(c).
(Formula Removed)
A further option for forming oligomer substituted pyrans of the in-O-ention of formula XX(d) in which the oligomer is present in the 5-position of the naphthopyran may utilise the corresponding carboxylated naphthol of formula XXIII(a). In such a process the naphthol of formula XXIII(a) is reacted with an appropriate oligomer of formula XXI(d) (particularly where linking group L comprising oxygen) to pro-O-ide an oligomer ester of formula XXI-O-(a). The oligomer naphthol ester of formula XXI-O-(a) may be reacted with propargyl alcohol of formula XX-O- to pro-O-ide the naphtholpyran of formula XX(d) in which the oligomer is present in the fi-O-e position.

(Formula Removed)
In a further alternati-O-e compounds of formula xx wnerein R- comprises the oligomer L(R)n may be formed by reacting a compound of formula XX(e) with an acid chloride or anhydride substituted oligomer to pro-O-ide a compound of formula:
(Formula Removed)
Examples of fulgides and fulgimides include compounds of formula XXX and more preferably XXXa:
(Formula Removed)
wherein
Q is selected from the group consisting of optionally substituted aromatic, optionally substituted heteroaromatic (where said aromatic/heteroaromatic may be mono or polycyclic aromatic/heteroaromatic);
R30, R32 and R33 are independentlyselected from the group consisting of a C1 to C4 alkyl, C1 to C4 alkoxy phenyl, phenuxy mono- and di(C1-C4) alkyl substituted phenyl or phen(C1-C4)alkyl and R32 and R32 optionally together form a fused benzene which may be further substituted;
A is selected from the group consisting of oxygen or =N-R36, in which R36 is C1-C4 alkyl or phenyl,
B' is selected from the group consisting of oxygen or sulfur;
R and R35 independently represents a C1-C4 alkyl, phenyl or phen(Cr C4) alkyl or one of R34 and R35 is hydrogen and the other is one of the aforementioned groups, or R34R35represents an adamantylidine group;
and wherein at least one of R30, R31, R32, R35 and R36is the group L(R)n.
When B is NR30 then A1 is generally oxygen.
Specific examples of compounds of formula XXX include those shown in the
following Table 4:

(Table Removed)
The fulgides and fulgimides comprising oligomer substituents in accordance
with the in-O-ention may be particularly as In in molecular switches.
The fulgides and fulgimides of formula XXX may be formed in accordance with procedures similar to those described in US Patent 4,220,708. Fulgides of formula XXX(a) in which the group A- is oxygen may be prepared from fi-O-e membered heterocycle of formula XXX by reaction with an ester of succinic acid of formula XXXII wherein R37 is a residue of an alcohol, by a Stobbe condensation reaction. Hydrolysing the half ester product of XXXIII formed in the reaction pro-O-ides the diacid of XXXIII wherein R37 is hydrogen. Heating of the diacid of formula XXXIII yields the succinic anhydride product of formi la XXXIII(a). The Stobbe condensation may be carried out by refluxing in t-butai ol containing potassium t-butoxide or with sodium hydride in anhydrous toluei e.
Compounds of the in-O-ention of formula XXX(b) in which A- of formula XXX IS N-36 may be prepared from the compound of XXX(a) by heating the anhydride and a primary amine R36NH2 to produce the corresponding half amide which can in turn be cyclised to form the imide of formula XXX(b) for example by heating with an acid chloride or acid anhydride. Alternati-O-ely the half ester Stobbe condensation product of formula XXX can be con-O-erted to the imide of XXX(b) by reaction with a compound of formula R36NHMgBr to produce the corresponding succinamic acid which may be dehydrated with an acid chloride to pro-O-ide the compound of formula XXX(b). Compounds of formula XXX(b)
(Formula Removed)
wherein R36 comprises an oligomer group are particularly preferred.
(Formula Removed)
Compounds of formula XXXI wherein R30 includes the oligomer L(R)n may be prepared by reaction of an oligomer acid chloride such as (XXX-O-) with the appropriate furon in the presence of a Lewis acid catalyst (such as tin tetrachloride):

(Formula Removed)
Fulgimide compounds of formula XXX in which
A' is the group of formula XXX-O-I may be prepared by reaction of an amine with a free nucleophilic group such as 4-hydroxyaniline with the corresponding fulgide of formula XXX where A' is oxygen to pro-O-ide the intermediate fulgimide ha-O-ing a free nuclophilic group such as hydroxy (eg formula XXX-O-II) and reaction of the free nucleophilic of the fulgimide with the oligomer acid chloride or anhydride (such as formula XXX-O-) to pro-O-ide the oligomer substituted fulgimide of (eg formula XXX-O-I).
(Formula Removed)
The compounds of the in-O-ention tend to be oils. This makes them more soluble in monomers and polymer matrices. It also means they are less likely to crystallise in the matrix, thus this may ailow higher loading of dyes and may also pre-O-ent the crystallisation that may occur with con-O-entional photochromic dyes.
Photochromic compounds of the in-O-ention comprising a dialkyl siloxane Dligomer may be prepared by anionic polymerization of the appropriate halo-substituted photochoromic moiety.
For example a chlorinated photochromic may be functionalised with a dialkyl siloxane as follows:

(Formula Removed)
An alternati-O-e method for oligomer growth on a photochromic moiety is the
ATRP and RAFT method or other li-O-ing polymer growth methods.
This general method of growing oligomers from li-O-ing initiation sites on the
photochromic moiety pro-O-ides a controlled growth process which may be
adapted to use with a wide range of photochromic moieties. Furthermore it will
be understood that a range of li-O-ing polymerisation methods including anionic,
ATRP and RAFT may be chosen depending on the types oligomers to be
prepared.

Examples of azo dyes include compounds of formula XI
(Formula Removed)
wherein:
R40 and R41 are independently selected from the group consisting of hydrogen, C1 to C6 alkyl, C1 to C6 alkoxy, -NR42R43 wherein R42 and R43 are as defined for R26 and R27 aryl (such as phenyl) aryl substituted with one or more substituents selected from C1 to C6 alkyl and C1 to C6 alkoxy, substituted d to C6 alkyl wherein the substituent is selected from aryl and C1 to C6 alkoxy, substituted C1 to C6 alkoxy wherein the substituent is selected from C1 to C6 alkoxy aryl and aryloxy.
Specific examples of aZO dyes include the following compounds of formula XL
(Formula Removed)
The compounds of the in-O-ention tend to be oils. This makes them more soluble in monomers and polymer matrices, t so m.ans they are less likely to crystallise in the matrix, thus this may allow higher loading of dyes and may also pre-O-ent the crystallisation that may occur with con-O-entional photochromic dyes.
The compounds of the in-O-ention ha-O-e their own built-in nanoen-O-ircrment because the dye can ne-O-er be separated from a fa-O-ourable oligomer.
The compounds of the in-O-ention may contain one or more photochromic dyes. The compounds of the in-O-ention may also be used in mixtures with con-O-entional photochromies.
The use of compounds of the in-O-ention allows tne Taae speea 01 tne photochromic to be changed without changing its colour. Thus it allows the tuning of fade speed for different coloured dyes. This is important to get a consistent colour when fading occurs. Thus, if a blue dye of a particular speed is needed, modification can be made to include an oligomer of an appropriate length in accordance with the in-O-ention.
The photochromic compounds (or compositions containing same) of the present in-O-ention may be applied or incorporated into a host material by methods known in the art. Such methods include dissol-O-ing or dispersing the compound in the host material. The compound may be melt blended with the host matrix.
Imbibation of the photochromic compound into the host material, by immersion, thermal transfer, or coating, and incorporation of the photochromic layer as part of a separation layer between adjacent layers of the host material. The term "imbibation" or "imbibe' is intended to mean and include diffusion of the photochromic compound alone into the host material, sol-O-ent assisted diffusion, absorption of the photochromic compound into a porous polymer, vapor phase transfer, and other such transfer mechanisms. For example:
(a) The photochromic compounds (or compositions containing same) of
the present in-O-ention can be mixed with a polymerizable composition that, upon
curing, produces an optically clear polymeric host material and the
polymerizable composition can be cast as a film, sheet or lens, or injection
molded or otherwise formed into a sheet or len
(b) The photochromic compounds of the present in-O-ention can be dissol-O-ed or dispersed in water, alcohol or other sol-O-ents or sol-O-ent mixtures and then imbibed into the solid host material by immersion for from se-O-eral minutes to se-O-eral hours, eg, 2-3 minutes to 2-3 hours for the host material in a bath of such solution or dispersion. The bath is con-O-entionally at an elevated temperature, usually in the range of 50°C to 95°C. Thereafter, the host materlal is remo-O-ed from the bath and dried;
(c) The photochromic compounds (and compositions containing the same) may also be applied to the surface of the host material by any con-O-enient manner, such as spraying, brushing, spin-coating or dip-coating from a solution
or dispersion of the photochromic material in the presence of a polymeric binder. Thereafter, the photochromic compound is imbibed by the host material by heating it, eg, in an o-O-en, for from a minute to se-O-eral hours at temperatures in the range of from 80°C to 180°C.;
(d) In a variation of the abo-O-e imbibation procedure, the photochromic compound or composition containing the same can be deposited onto a temporary support, or fabric, which is then placed in contact with host material and heated, eg, in an o-O-en;
(e) The photochromic compounds can be dissol-O-ed or dispersed in a transparent polymeric material which can be applied to the surface of the host in the form of a permanent adherent film or coating by any suitable technique such as spraying, brushing, spin-coating or dip-coating;
(f) The photochromic compounds can be incorporated or applied to a transparent polymeric material by any of the abo-O-e mentioned methods, which can then be placed within the host material as a discrete layer intermediate to adjacent layers of a host material(s);
(g) The photochromic adduct of the in-O-ention may be incorporated into a dye composition by ball milling with a carrier to disperse it in a binder matrix. Such a composition may be used as an ink, for example in ink jet printing and suitable (PC) moieties may be chosen to allow security markings on documents to be -O-isible on exposure to UV light used in photocopy;
(h) The photochromic compound may be compounded with suitable resins and the resin melted to shape it to form a film, for example by blow moulding or to form more complex extruded shapes, e.g. oy injection moulding and/or blown structures.
The transfer method is described, inter alia, in the documents U.S. Pat. Nos. 4,286,957 and 4,880,667. In this technique, a surface of the transparent polymer substrate is coated with a layer of a varnish containing the photochromic substance to be incorporated. The substrate, thus coated, is then treated thermally in order to cause the photochromic substance to migrate >nto the substrate.
It is a significant advantage of the adduct photocnromic OT me in-O-ention mai they are relati-O-ely stable e-O-en at elevated temperature. In contrast attempt made to impro-O-e fade results using unsaturated functional groups result in compounds which polymerise at elevated temperature and must generally be stored to a-O-oid premature polymerisation.
The present in-O-ention is more particularly described in the following examples which are intended as illustrati-O-e only since numerous modifications and variations therein will be apparent to those skilled in the art.
Examples of host materials that may be used with the photochromic compounds of the present in-O-ention include polymers, i.e., homopolymers and copolymers of polyol(allyl carbonate) monomers, homopolymers and copolymers of polyfunctional acrylate monomers, polyacrylates, poly(alkylacrylates) such as poly(methylmethacrylate), cellulose acetate, cellulose triacetate, celluslose acetate propionate, cellulose acetate butyrate, poly-O-inyl ace' * e), poly(-O-inylalcohol), poly(-O-inylchloride), poly(-O-inlylidene chloride), polyurethanes, polycarbonates, poly(ethylene-terephthalate), polystyrene, copoly(styrene-methylmethacrylate), copoly(styrene-acrylateonitrile), poly(-O-inylbutryal), and homopolymers and copolymers of diacylidene pentaerythritol, particularly copolymers with polyol(allylcarbonate) monomers, e.g. diethylene glycol bis(allyl carbonate), and acrylate monomers. Transparent copolymers and blends of the transparent polymers are also suitable as host materials.
The host material may be an optically clear polymerized organic material prepared from a polycarbonate resin, such as the carbon; ite-linked rosin deri-O-ed from bisphenol A and phosgene which is sold under the trademark LEXAN; a poly(methylmethacrylate), such as the material sold under the trademark PLEXIGLAS; oolymerizates cellulose butyrate, polystyrene and copolymers of styrene with methyl methacrylate, -O-inyl acetate and acrylonitrile, and cellulose acetate butyrate.
Polyol (allyl carbonate) monomers which can be polymerised to form a transparent host material are the allyl carbonates of linear or branched aliphatic glycol bis(allyl carbonate) compounds, or alkylidene bisphenol bis(allyl carbonate) compounds. These monomers can be described as unsaturated polycarbonates of polyols, eg glycols. The monomers can be prepared by procedures well known in the art, eg, US Pat. Nos. 2,370,567 and 2,403,113. The polyol (allyl carbonate) monomers can be represented by the graphic formula:
(Formula Removed)
wherein R is the radical deri-O-ed from an unsaturated alcohol and is commonly an allyl or substituted allyl group, R' is the radical deri-O-ed from the polyol, and n is a whole number from 2-5, preferably 2. The allyl group (R) can be substituted at the 2 position with a halogen, most notably chlorine or bromine, or an alkyl group containing from 1 to 4 carbon atoms, generally a methyl or ethyl group. The R group can be represented by the graphic formula:
(Formula Removed)
wherein R0 is hydrogen, halogen, or a C1-C4 alkyl group. Specific examples of R include the groups: allyl 2-chloroalyl, 2-bromoa!y (Formula Removed)
R' is the polyvalent radical deri-O-ed from the polyol, which can be an aliphatic or aromatic polyol that contains ?, 3, 4 or 5 hydroxy gimips. Typically, the polyol contains 2 hydroxy groups, ie a glycol or bisphenol. The aliphatic polyol can be linear or branched and contain from 2 to 10 carbon atoms. Commonly, the aliphatic polyol is an alkylene glycol ha-O-ing from 2 to 4 carbon atoms or a
poly(C2-C4) alkylene glycol, ie ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, or diethylene glycol, triethylene glycol etc.
In a further embodiment, the in-O-ention pro-O-ides a photochromic article comprising a polymeric organic host material selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bismethacrylate), poly(ethoxylated bisphenol A dimethacrylate) thermoplastic polycarbonate, poly-O-inyl acetate), poly-O-inylbutyral, polyurethane, and polymers of members of the group consisting of diethylene glycol bi(allylcarbonate) monomers, diethylene glycol dimethacrylate monomers, ethoxylated phenol bismethylacrylate monomers, diisopropenyl benzene monomers and ethoxylated trimethylol propane triacrylate monomers, and a photochromic amount of a compound of the in-O-ention.
The polymeric organic host material is selected from the group consisting of
polyacrylates, polymethacrylates, po!y(C-i-C12) alkyl methacrylates,
polyoxy(alkylene methacrylates), poly(alkoxylates phenol methacrylates),
cellulose acetates, cellulose triacetate, cellulose acetate propionate, cellulose
acetate butyrate, poly-O-inyl acetate), poly-O-inyl alcohol), poly-O-inyl chloride)
poly(-O-inylidene chloride), thermoplastic polycarbonates, polyesters,
polyurethanes, polythiourethanes, poly(ethylene terephthalate), polystyrene, poly(alpha methylstyrene), copoly(styrene-methylmethacrylate), copoly(styrene-acrylonitrile), poly-O-inylbutyral and polymf s of members of the g The pho'ochromic article may comprise a pulymeric organic material which i; a homopolymer or copolymer of monomer(s) selected from the group consisting of acrylates, methacrylates, methyl mathacrylate, ethylene glycol bis methacrylate, ethoxylated bisphenol A dimethacrylate, -O-inyl ncet? te, -O-inylbutyral, urethane, thiourethane, diethylene glycol bis(aliyl carbon; te),
diethylene glycol dimethacrylate, diisopropenyl benzene, and ethoxylated trimethyl propane triacrylates.
The photochromic composition of the in-O-ention may contain the photochromic compound in a wide range of concentrations depending on the type of photochromic moiety and its intended application. For example in the case of inks in which high colour intensity is required a relati-O-ely high concentration of up to 30 wt% photochromic may be required. On the other hand it may be desirable in some cases such as optical articles to use photochromies in -O-ery low concentrations to pro-O-ide a relati-O-ely slight change in optical transparency on irradiation. For example, as low as 0.01 mg/g of host resin may be used. Generally the photochromic resin will be present in an amount of from 0.01 mg/g of host resin up to 30 wt% of host resin. More preferably the photochromic compound will be present in an amount of from 0.01 mg/g to 100 mg/g of host matrix and still more preferably from 0.05 mg/g to 100 mg/g of host matrix.
The photochromic article may contain the photochromic compound in an amount of from 0.05 to 10.0 milligram per square centimetre of polymeric organic host material surface to which the photochromic substance(s) is incorporated or applied.
The compounds of the In-O-ention may be used in those applications in which the organic photochrome substances may b polymeric organic materials. Coating compositions may be used to produce -O-erification marks on security documents, e.g. documents such as banknotes, passport and dri-O-er' licenses, for which authentication or -O-erification of authenticity may be desired. Security documents, for indicating exposure to light during photocopying.
Throughout the description and claims of this specification, use of the word "comprise" and variations of the word, such as "comprising" and "comprises", is not intended to exclude other additi-O-es, components, integers or steps.
The discussion of documents, acts, materials, de-O-ices, articles and the like is included in this specification solely for the purpose of pro-O-iding a context for the present in-O-ention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present in-O-ention as it existed in Australia before the prioi.ty date of each claim of this application.
Examples
Note on poly(ethylene glycol) {PEG} methyl ethers and
polydimethylsiloxane oligomers and naming of compounds.
The PEG mono methyl ethers are supplied with an a-O-erage molecular weight. For example the Aldrich Chemical Company supplies them with a-O-erage number molecular weights such as 350, 750 etc which approximately but rot Succinic acid mono-PEG(350) ester
(Formula Removed)
Poly(ethylene glycol) methyl ether (ie PEG(350) ca 7-PEG unit, Mn ca. 350 g/mol) ( 20 g, 57.1 mmoles) was dissolved in 50 mL of dichloromethane together with succinic anhydride (5.7 g, 57 mmoles), methanol (100 mg) and dimethylaminopyridine (50 mg) at room temperature under argon. Triethylamine (7.9 mL, 5.7 g, 57.1 mmole) was added dropwise. The reaction was stirred at room temperature for one day and then refluxed for one hour. The reaction was worked up by dilution with dichloromethane, then washed with 2 M HCI and then brine before evaporation under vacuum to give a clear oil as product (19 g, 74%). 1H NMR (CDCl3) δ 2.55 (s,4H, C=O-CH2CH2-C=O), 3 25 (s, 3H, methyl), 3.45 (mult, 2H), 3.55 (s, 22H, PEGs), 3.60 (mult, 2H, CH2CH2-OC=O), 4.15 (mult, 2H, CH2-OC=O) ppm. 13C NMR (CDCl3) 28.8 & 29.1 (succinyl methylenes), 58.9 (-OCH3), 63.8 & 68.3 (CH2CH2-OC=O), 70.4 (most PEG units), 71.8 (-CH2-O-CH3), 172.2 (ester), 175.0 (acid) ppm.
Succinic acid mono-PEG(750) ester
Succinic aciu mono-PEG(/'50) ester was synthesised in a similar manner to succinic acid mono-PEG(350) ester. Yield 79%. 1H NMR (CDCl3) δ 2.50 (s, C-O-CH2CH2-C=O), 3.25 (s, methyl), 3.50 (s, PEGs), 4.10 (mult, CH2-OC=O) ppm. 13C NMR (CDCl3) 28.7 & 29.0 (succinyl methylenes), 58.9 (-OCH3), 63.7 and 68.9 (CH2CH2~OC=Q), 70.4 (most PEG units), 71.8 (-CH2-O-CH3), 1/2.1 (ester), 174.4 (acid) ppm.

Succinic acid chloride mono-PEG(350) ester
(Formula Removed)
The succinic acid mono-PEG(350) ester (9 g, 20 mmoles) was dissol-O-ed in dichloromethane (10 mL) at room temperature under argon and thionyl chloride (3.5 mL) was added dropwise and the reaction stirred for 5 days and then heated at 50-70 °C for 2 hours. The reaction was evaporated under vacuum for one hour at 60 °C. The oil was pure acid chloride (9.22 g, 98%). 1H NMR (CDCl3) δ 2.55 (t, 2H, CH2-C=O-CI), 3.17 (t, 2H, 0-C=O-CH2), 3.31 (s, 3H, methyl), 3.50 (mult, 2H), 3.60 (s, 22H, PEGs), 4.22 (mult, 2H, CH2-OC=O) ppm. 13C NMR (CDCl3) 29.3 & 41.7 (succinyl methylenes), 59.0 (-OCH3), 64.2 & 68.9 (CH2CH2-OC=O), 70.5 (most PEG units), 71.9 (-CH2-O-CH3), 170.9 (ester), 172.9 (acid chloride) ppm.
Succinic acid chloride mono-PEG(750) ester
Succinic acid chloride mono-PEG(750) ester was synthesised iri the same manner as described for succinic acid chloride mono-PEG(350) ester. Yield 98%. 1H NMR (CDCl3) δ 2.52 (t, CH2-O0-CI), 3.03 (t, 2H, 0-C=O-CH2), 3.16 (s, methyl), 3.34 (small mult), 3.44 (s, 22H, PEGs), 3.51 (small mult.), 4.06 (mult, CH2-OC=O) ppm.
Numbering of spiro-oxazines
(Formula Removed)
This moiety will be referred to hereinafter by the abbre-O-iation "SOX".
The examples are described in part with reference to the drawings (see Examples 8, 23 and 24).
In the drawings:
Figure 1 is a thin film analysis in polymethyl methacrylate matrix comparing the absorbance of the photochromic dyes of Examples 2, 5 and CE1 with the parent dye.
Figure 2 is the normalised absorbance of compositions referred to in Figure 1.
Figure 3 is a thin film analysis graph comparing the absorbance o-O-er time of photochromic dyes of CE1, Example 5 and Example 2 with the parent dye in a polystyrene matrix.
Figure 4 is a thin film analysis graph sharing the normalised absorbance of the system referred to in Figure 3.
Figure 5 is an ROE experiment referred to in Example 1.
Figure 6 is an ROE experiment of the compound of Example 5.
Figure 7 is an ROE nmr experiment pro-O-iding e-O-idence of nano solvaiion/encapsuldtion in the compound ot Example 5.
Figure 8 is an absorbance graph showing colouration and fade speeds of compound of Example 5.
Figure 9 is a normalised absorbance gra..h of the test oet up referred to in Figure 8.
Figure 10 is an absorbance graph showing the colouration and fade speed of the compound of Example 16.
Figure 11 is a normalised absorbance graph of the set up referred to in Figure 10.
Figure 12 is an absorbance graph showing the colouration and fade speed of the compound of Example 20.
Figure 13 is a normalised absorbance graph of the set up described for Figure 12.
Figure 14 is an absorbance graph showing the colouration and fade speed of the dyes of Example 5 and CE3.
Figure 15 is a normalised absorbance graph of the set up described for Example 14.
Figure 16 is an absorbance graph comparing the rate of colouration and fade of the dye of Example 9 with the "Spectrolite -O-elocity Transitions" product.
Example 1
9'-(PEG(350)-succinyl)-1,3,3-trimethylspiro[indoiine-2,3'-[3h]naphtha[2,1 b][1,4]oxazine] (PEG(350)-suc-SOX)
(Formula Removed)
9'-Hydroxy-1 ,3,3-trimethylspiro[indoline-2,3'-[3H]naphtha[2,1 -b][1,4]oxazine] (1.95 g, 5.67 mmoles) and triethylamine (0.857 g, 1.18 mL, 8.5 mmoles) were added together in dichloromethane (30 mL) and then the succinic acid chloride mono-PEG(350) ester (3.19 g, 6.8 mmol) in dichloromethane was added dropwise to the solution at room temperature under argon protection. When the reaction was complete it was worked up by dilution with dichloromethane, washing -O-with dilute sodium hydroxide, dilute HCI, and brine before final drying with magnesium sulphate to gi-O-e a dark brown oil (4 g) which was purified by column chromatography to gi-O-e a brown oil. 1H NMR (CDCl3) δ 1.33 (s, 6H, C(CH3)2), 2.75 (s, 3H, N-CH3), 2.82 & 2.94 (mults, 4H, C=O-CH2CH2-C=O), 3.35 (s, 3H, O-CH3), 3.53 (mult, 2H, CH2-O-CH3), 3.63 (s, PEG units), 3.71 (mult, 2H, CH2CH20-C=O), 4.30 (mult, 2H, CH2CH20-C=O), 6.58 (d, J = 7.6 Hz, 5-H), 6.82-7.27, 7.59-7.79, 8.23 (d, H = 2.7 Hz, 7-H) ppm.
Example 2
9'-(PEG(750)-succinyl)-1,3,3-trimethylspiro[indoline-2,3'-[3H]naphtha[2,1-b][1,4]oxaziae] (PEG(750)-suc-SOX)
(Formula Removed)
9'-(PEG(750)-succinyl)-1,3,3-trimethylspiro[indoline-2,3'-[3H]naphtha[2,1-b][1,4]oxazine] was synthesised in the same manner as 9'-(PEG(350)-succinyl)-1,3,3-trimethylspiro[indoline-2,3'-[3H]naphtha[2,1-b][1,4]oxazine] using succinic acid chloride mono-PEG(750) ester in place of succinic acid chloride mono-PEG(350) ester to gi-O-e 76% yield of product. The 1H NMR spectrum looked the same as 9'-(PEG(350)-succinyl)-1,3.3-trimethylspiro[indoline-2,3'-[3H]naphtha[2,1-b][1,4]oxazine] except it had a correspondingly larger singlet for the PEG units at 3.63 ppm. 1H NMR (CDCl3) δ 1.33 (s, 6H, C(CH3)2), 2.75 (s, 3H, N-CH3), 2.82 & 2.94 (mults, 4H, C=O-CH2CH2-C=O), 3.35 (s, 3H, O-CH3), 3.53 (mult, 2H, CH2-O-CH3), 3.63 (s, PEG units), 3.71 (mult, 2H, CH2CH2O-C=O), 4.30 (mult, 2H, CH2CH2O-C=O), 6.58 (d, J = 7.6 Hz, 5-H), 6.82-7.27, 7.59-7.79, 8.23 (d, H = 2.7 Hz, 7'-H) ppm.
Example 3
Part (a)
5,9'-Dihydroxy-1,3,3-trimethylspiro[mdoline-2,3'-[3H]naphtha[2,1 -b][1,4]
oxazine]
(Formula Removed)
5-Hydroxy-1,2,3,3-tetramethyIindolium iodide (1.65 g, 5.2 mmoles) was dissol-O-ed in methanol (10 mL) and buLnone ;5 rnL) and piperidine (0 5 (Formula Removed)
5,9'-Di(PEG(350)-succinyl)-1,3,3-trimethylspiro[induline-2,3'-[3H]naphtha[2,1-b][1,4]oxazine] (BisPEG (350)-suc)-SOX)
(Formula Removed)
5,9'-Di(PEG(350)-succinyl)-1,3,3-trimethylspiro[indoline-2,3'-[3H]naphtha[2,1-b] [1,4]oxazine] was made in the same way as 9'-(PEG(350)-succinyl)-1,3,3-trimethylspiro[indoline-2,3'-[3H]naphtha[2,1-b][1,4]oxazine using 2 molar equivalents of succinic acid chloride mono-PEG(350). The product was a brown oil (90% yield). 1H NMR (CDCl3) δ 1.00 (s, 3H, methyl), 1.13 (s, 3H, methyl), 2.38 (s, 3H, N-methyl), 2.49 (mult, 8H, C=O-CH2CH2-C=O), 3.10 (s, 6H, O-CH3;, 3.40 (s, ca 12-14 full PEG units + 2 x 1/2PEG units), 4.12 (s, 4H, CH2CH20-C=O), 6.18 (d, J = 8.2 Hz, 5-H), 6.73-7.0 (mult, aromatic), 7.2-7.6 (mult, aromatic), 8.55 & 8.82 (s, naphthyl aromatic) ppm.
Example 4
Poly(dimethylsiloxane) monocarboxydecoyl chloride terminated

(Formula Removed)
Poly(dimethylsiloxane) monocarboxydecyl (MCR-B11 ABCR Mw ca 105G)) (4 g, 4 nimole) was dissoived in 10 mL of dichloromethane, thionyl chloride (2 mL) was added and the reaction heated under argon o-O-ernight. The reaction was worked up by evaporation of sol-O-ent and thionyi chloride under vacuum and mild heating (40°C) to gi-O-e 3.77g (94%) of -O-ery pale amber oil. 1H NMR (CDCl3) δ 0.0 (s, Si-Me), 0.45 (m, CH2), 0.8 (t, J = ca. 6.6 Hz, CH3), 1.2 (s, CH2), 1.6 (pent, 2H, CH2-CH2-COCI), 2.8 (t, J = 7Hz, 2H, CH2-CH2-COCI). 13C NMR (CDCl3) δ 0.18, 1.05, 1.18, 1.78, 13.8, 18.0, 18.3, 23.2, 25.07, 25.5, 26.4, 28.5, 29.1, 29.4, 29.48, 33.4, 47.1 (CH2-COCI), ,73.7 (COCI) ppm.
Example 5
9'-(PDMS(855)-undecoyl)-1,3,3-trimethylspiro[indoline-2,3'-[3h]naphtha[2,1-b][1,4] oxazine]
(Formula Removed)
9'-Hydroxy-1,3,3-trimethylspiro[indoline-2,3'-[3H]naphtha[2,1 -b][1,4]oxazine] (1g, 2.9 mmoles) and triethylamine (0.9 mL, 655 mg, 6.5 mmoles) were added together in dichloromethane (20 mL) and then poly(dimethylsiloxane) monocarboxydecoyl chloride terminated (3.0 g, 2.8 mmol) in dichloromethane was added dropwise to the solution at room temperature under argon protection. The reaction was monitored by tic (DCM or ethenhexane 1:1) and way completed after a few hours. The reaction was worked up by washing with water, brine ( plus a little of -O- dilute HCI to break the emulsion), dried (MgS04) before evaporation to a dark liquid. The oil was chromatographed on silica with ethenhexane (1:3) to gi-O-e 2.1 g ( 52%) of pale brown green oil as the desired product. A second slower fraction (200 mg) was obtained that was spectroscopically similar to the product except it had a -O-inyl (terminal) group and had much less DMS content. 1H NMR (acetone-d6) δ = 0.09 (d, J = 1.8 Hz, Si-Me), 0.10 (d, J = 1.83 Hz, Si-Me), 0.12 (d, J = 1.8 Hz, Si-Me), 0.13 (s, Si-Me), 0.6 (mult., 4H, alkyl), 0.90 (mult., 4H, alkyl), 1.3-1.4 (mult, 22H, 9,10-H, alkyl, CH2-CH3), 1.50 (mult, 2H, 'c'-H\ 1.80 (pent, J = 7.3 Hz), 2H, 'b'-H), 2.68 (t, J = 7.3 Hz, 2H, 'a'-H), 2.77 (s, 3H, 8-H), 6.65 (d, J == 7.8 Hz, 7-H), 6.87 (t, J = 7.3 Hz, 5-H), 7.03 (d, J = 8.5 Hz, 5'-H), 7.14 (d, J = 7.3 Hz, 4-H), 7.19 (apparent t, 2H, 6 & 8'-H), 7.80 (d, J = 9.3Hz, 6'-H), 7.82 (s, 2'H), 7.86 (d, J = 8.6Hz, 7'-H), 8.23 (d, J = 2.3 Hz, 10'-H) ppm. MS (FAB), M+ 1368 (100%) (corresponds to 11 DMS units in oligomer), 1145.9 (90%)(corresponds to 8 DMS units in oligomer), 1591.4 (85%)(corresponds to 14 DMS units in oligomer, 923.6 (corresponds to 5 DMS units in oligomer), 1813.5 (corresponds to 17 DMS units in oligomer). Peaks for all other oligomer lengths between 4-19 DMS
units were also obser-O-ed in a small bell cur-O-e distribution centred around 11 DMS units (12 MDS 40% of M+ with other peaks being smaller).
(Formula Removed)
Example 6
9'-((1 -{lsobutyl)-POSS)-3-propyl)-succinyl)-1,3,3-trimethylspiro[indoline-2,3'-[3h]naphtha[2,1 -b][1,4]oxazine]
(Formula Removed)
9-(Monocarboxy-succinyl)-1.3.3-trimethylspiroIindoline-2,3'-[3h]naphtha[2,1-b] [1,4] oxazine (0.62 g 1.8 mmoles), hydroxypropylisobutyl-POSS (1.58 g 1.8 mmoles), dimethylaminopyridine (33 mg, 0.2 mmoles) were dissol-O-ed in dichloromethane (15 mL) and then dicyclohexylcarbodiimide (0.4 g, 1.8 mmoles) in dichloromethane was added slowly o-O-er fi-O-e minutes. The solution was refluxed under argon for 4-5 hours until tic analysis showed no starting spirooxazine was present. Product was identified on tic as a fast mo-O-ing band (ether:hexane 1:1 rf ca. 0.8). The reaction was worked up by dilution with dicholoromethane (to 100 mL), cooling and filtering off the precipitated dicyclohexyl urea. The solution was washed with water, brine, dried and evaporated to gi-O-e a white solid. This was chromatographed on silica (ethenhexane 1:3) until the fast mo-O-ing light blue band was eluted. The sol-O-ent was evaporated from the collected band to gi-O-e a white/pale green/blue solid (0.86 g, 37%). The column was eluted with ether:hexane (1:1) to gi-O-e two more bands. These were evaporated to gi-O-e a smear and a non-photochromic solid. The material was purified by re-O-erse phase chromatography to gi-O-e a crystalline material that displayed photochromism in the crystalline state. It turned blue when irradiated with ultra -O-iolet light. MS (IE) 1302 (M+., 100%). 8 * 0.65 (14H, dd J 2.19, 6.95), 0.75 (2H, t J 8.23), 0.98 (42H, bs), 1.34 (3H, s), 1.36 (3H, s), 1.75-1.97( 9H, m), 2.77 (3H, s), 2.80 (2H, t J 6.40) 3.0 (2H, t J 6.40), 4.12 (2H, t J 6.79), 6.66 (1H, d J 7.68), 6.87 (1H, dd J 0.73, 7.32), 7.05 (1H, d J 8.78), 7.15 (1H, d J 7.32), 7.17-7.22 (2H, m), 7.82 (1H, d J 8.78), 7.83 (1H, s), 7.88(1 H, d J 3.78), 8.26 (1H, d J 2.38) ppm.
Example 7
A simple screen for examining photochromic speed was carried out as follows: A small quantitiy of the photochromic compound was dissol-O-ed in THF to gi-O-e a concentration of ca 25 mmol per millilitre. This solution was then dropped onto normal photocopy paper (brand "Reflex") to gi-O-e a spot of about 1-2 cm in diameter. This was allowed to dry. The spot was then irradiated with a hand held UV light (365 nm) and the spot would colorize and then decolorize when the UV light was remo-O-ed. When spots of the parent SOX, CE1, Example 1, and Example 2 were examined simultaneously it was ob-O-ious to the eye that the Example 1 and Example 2 decolourised in less than 15 seconds whereas
the con-O-entional dyes (parent SOX and CE1) were still decolourising after 5 minutes. In addition, the con-O-entional dyes would fatigue after 3-4 hours such that no colouration was obser-O-ed after about 4 hours. Howe-O-er, the Example 1 and Example 2 dyes were protected from fatigue for an extended period. Typically, photochromism was obser-O-ed for at least a week.
Example 8
Steady state UV--O-isible absorption measurements in Table 5 were collected using a varian Cary 50 UV-visible Spectrophotometer. The instrument allows for the in-situ excitation of samples and hence the study of "real-time" changes in absorption of solutions and films. The Cary 50 is equipped with a thermostatted peltier sample holder allowing an operating temperature range of -10D-100DC.

(Figure Removed)
Figure 17 Instrumental setup for irradiation and absorption measurements of photochromic samples. A number of filters can be integrated into the system to select for ranges of wa-O-elengths exciting the sample. Equally, a
monochromator can also be incorporated between the 2 lenses to selert fr r wa-O-elength.
Samples were photoexcited by exposure to a 150 W Xei.on Arc lamp. The excitation wa-O-elength range was restricted to approximately 300-400 nm and abo-O-e 650 nm by the use of two optical filters, WG 320 and 9863 (see Fig. 18). A water filter was also used to reduce thermal heating of the sample.
Films of the photochromic compounds (approximately 0.3 g.L-1) were cast from a 4% w/-O- solution of polymer dissol-O-ed in a suitable sol-O-ent onto glass slides and air dried. Films were approximately 100 Dm thick.
Film samples were mounted in the spectrophotometer with a particular geometry (see Fig. 19). The face of the film was pointing away from the detector to minimise scattered excitation light saturating the detector. Another cut-off filter (GG495) was used immediately in front of the detector to further minimise scattered UV light reaching the detector.

(Figure Removed)
Figure 18: Transmission spectra of the filters employed in the experimental setup.
(Figure Removed)
Figure 19: Top -O-iew of the Cary 50 sample holder and experimental setup geometries for films.
Samples were allowed to thermally equilibrate at each temperature for about fi-O-e minutes before scans were performed.
The absorbance (A0), the half li-O-es for discolouration (t1/2, sec) and the three quarter li-O-es (t.3/4,S) for discolouration for se-O-eral photochromic compounds in different polymer films are gi-O-en in Table 5. T1/2 is the time taken for the optical density to reduce by half from the initial maximum optical density of the coloured from when UV irradiation is stopped. T3/4 is time taken for the optical density to reduce by three quarters from the initial maximum optical density of the coloured form of the dye from when UV irradiation is stopped.
Table 5

(Table Removed)
Examples of the control of the fade speed by choice of oligomer and matrix can be seen in Table 5. Rows 3 and 4 show the fade enhancement of spirooxazine photochromic agents functionalised by polar polyethylene gycol (PEG) chains of increasing length respecti-O-ely. Example 2 shows enhanced fade speed relati-O-e to reference compounds in rows 1 and 2 in poly(methyl methacrylate), poly(styrene) and poly(carbonate). Furthermore it is apparent that the longer the oligomer length, the better the encapsulation effect with Example 2 (row 4) fading faster than Example 1 (row 3) in all three polymers. PEG(750) has approximately 16 PEG units while PEG(350) has approximately 7. In this case of Example 2 the fade speed has almost become independent of the host matrix.
The encapsulation effect can be seen clearly in the case of Example 3 (Table 5 row 6). Here the fade speed in poly(styrene) is significantly faster than poly(methylmethacrylate) as the PEG chains will be incompatible with the polystyrene matrix and coil close to or encapsulate the photochromic. The
poly(styrene) fade speed is slmilar to rat of Example 1 Ho wever. in poiymethyl methacrylate the PEG chains of Example 3 are more compatible with the matrix and the T1/2 fade speed slows to be significantly slower as Example 1. The bis-propylate-SOX also shows this effect with a short alkyl chain. Here the non-polar alkyl chain will be incompatible with polar poly(methyl methacrylate) matrix but more compatible with non-polar poly(styrene) and so fade speed is much slower in poly(styrene). Both Example 3 and bis-propyl-SOX show -O-ery slow fade speed in polycarbonate.
Kinetic cur-O-es
The following kinetic cur-O-es (Figures 1 to 4) were obtained using different films and under different conditions to those used for acquiring the data in Table 5.
The experimental set up used is described in Example 24. The cur-O-es show the dramatic effect of the PDMS oligomer attached to a photochromic dye on fade speed of the photochromic dye It pro-O-ides solution-like kinetic beha-O-iour not pre-O-iously obser-O-ed for a photochromic dye in a polymer matrix. It allows rapid colouration to a constant maximum optical density followed by a rapid fade on cessation of irradiation. Similar effects are found with the PEG oligomer in Example 2 (SOX-suc-PEG(750)). When it is placed in a matrix that the PEG will ha-O-e some incompatability [ie polystyrene] the PEG then is more available to solvate the photochromic dye and a fast fade is obser-O-ed. CE1 (SOX-propylate) is electronically identical to both the Example 5 (SOX-undec-PDMS(855)) and Example 2 (SOX-suc-PEG(750)) and shows dramatically slower colouration and fade kinetics as there is no oligomer to pro-O-ide a fa-O-ourable switching en-O-ironment.
The following cur-O-es (Figure 1 to 4) show the colouration and fade performance of the Example 2 (SOX-suc-PEG(750)), Example 5 (SOX-undec-PDMS(8b5)) in comparison with the electronically identical SOX-Propylate and parent dye (no substituents) in polymethylmethacrylate) and poly(styrene) respecti-O-ely. They show that the PDMS oligomer allows the dye to rapidly colourise and achie-O-e a maximum optical density within tens of seconds. Con-O-entional dyes like the CE1 (SOX-propylate) (which is electronically identical to the Example 5 (SOX-undec-PDMS(855)) and parent SOX (1,3-dihydro-1,3,3-trimethyl-spiro[2H-dole-2,3'-[3Hl-naphth[2,1-b][1,4]oxazine]) typically colourise slowly and continue to do so e-O-en after 100 seconds.
The normalised fade cur-O-es focus on the fade kinetics. It is ob-O-ious to the eye that the Example 5 (SOX-undec-(PDMS(855)) undergoes fade far faster than any of the con-O-entional dyes and reaches low if not actually 0.0 absorbance within a minute whereas the con-O-entional dyes still ha-O-e significant absorbance after 1000 sees and longer.
The PDMS is pro-O-iding a highly mobile local en-O-ironment for switching beha-O-iour. Without wishing to be bound by theory it is thought that its incompatibility with the matrix allows it to aggregate near or around the dye and
so pro-O-ides protection from the rigidity of the bulk matrix. This occurs in poly(styrene), poly(methylmethacrylate) and poly(carbonate) where it shows the same beha-O-iour in all the matrices. The beha-O-iour of the dye is similar to that obser-O-ed in solution. It shows rapid coloration with an initial o-O-ershoot and then rapidly reaches a constant optical density, shows un-damped kinetic beha-O-iour and then rapid fade when irradiation stops.
Example 9
5-(PDMS(855)-undecoyl)-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine]
(Formula Removed)
5-(PDMS(855)-undecoyl)-1,3,3-trimethylspiro[indoline-2,343H]napth[2,1-b][1,4]oxazine] was synthesised according to the procedure for the preparation of 9'-(PDMS(855)-undecoyl)-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1 -b] [1,4]oxazine] (Example 5) using 5-hydroxy-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine] in place of 9'-hydroxy-1,3,3-trimethylspiro [indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine], column chromatography (silica) 1: 20, ethyl acetate : hexane (51 %). 1H NMR (C2D60) δ* 0.1 (bs), 0.58 (4H, m), 0.89 (4H, m), 121-1.52 (242H, m), 1.72 (2H, m) 2.f-5 (2H t, J 7 31), 2.76 (3H, s), 6.63 (1H, d, J 9.14), 6.88 (1H, d, J 2.19), 6.92 (1H, d, J 2.19), 7.07 (1H, d, J 8.77), 7.42 (1H, dd, J 8.41, 1.46), 7.59 (1H, dd, J 8.41, 1.46), 7.74-7.88 (3H, m), 8.85 (1H, d, J 8.41) ppm. 13C NMR (C2D6O) δ≠ 172.8, 151.5, 146.1, 145.6, 144.8, 137.8, 131.8, 131.2, 130.4, 128.7, 127.8, 125.0, 122.4, 121.5, 117.5, 116.5, 107.9, 99.8, 52.5, 34.7, 34.2, 30.3, 30.1, 30.0, 27.1, 26.2, 25.7, 25.6, 24.0, 20.9, 18.9, 18.6, 14.2, 1.4 ppm.
Example 10
6'-Cyano-5-(PDMS(855)-undecoyl)-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1 -b][1,4]oxazine]
(Formula Removed)
6,-Cyano-5-(PDMS(855)-undecoyl)-1)3,3-trimethylspiro[indoline-2,3,-[3H]napth
[2,1-b][1,4]oxazine] was synthesised according to the procedure for the
preparation of 9'-(PDMS(855)-undecoyl)-1,3,3-trimethyispiro[indoline-2,3'-
[3H]napth[2,1-b][1,4]oxazine] (Example 5) using 6'-cyano-5-hydroxy-1,3,3-
trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine] in place of 9'-hydroxy-
1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine], column
(Formula Removed)
chromatography (silica) 1: 20, ethyl acetate : hexane (68 %). 1H NMR (C2D6O)
δ= 0.11 (bs), 0.60 (4H, m), 0.90 (3H, m), 1.24-1.51 (24H, m), 1.72 (2H, m), 2.56 (2H, t, J 7.31), 2.78 (1H, s), 6.65 (1H, d, J 9.5), 6.91 (1H, s),), 6.94 (1H, s), 7.63-7.83 (3H, m), 8.04 (1H, s), 8.10 (1H, d, J 8.04), 8.71 (1H, d, J 8.04) ppm. 13C NMR (C2D60) δ = 172.8, 155.4, 145.9, 145.8, 144.0, 137.4, 131.5, 129.3, 127.7, 125.5, 124.4, 123.5, 121.7, 117.4, 116.6, 111.8, 108.2, 100.2, 71.7, 53.0, 34.7, 34.3, 30.3, 30.1, 30.1, 27.1, 26.2, 25.7, 25.6, 24.0, 20.9, 18.9, 18.6, 14.2, 1.5 ppm.
Example 11
(Formula Removed)
5-Methoxy-9'-(PDMS(855)-undecoyl)-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1 -b][1,4]oxazine]
5-Methoxy-9'-(PDMS(855)-undecoyl)-1,3,3-trimethylspiro[indoline-2,3-
[3H]napth[2,1-b][1,4]oxazine] was synthesised according to the procedure for
the preparation of 9'-(PDMS(855)-undecoyl)-1,3,3-trimethylspiro[indoline-2,3'-
[3H]napth[2,1-b][1,4]oxazine] (Example 5) using 5-methoxy-9'-hydroxy-1,3,3-
trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine] in place of 9'-hydroxy-
1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1 -b][1,4]oxazine], column
chromatography (silica) 1: 20, ethyl acetate : hexane (75 %). 1H NMR (C2D6O) δ≠ 0.10 (bs), 0.59 (4H, m), 0.90 (3H, m), 1.24-1.55 (22h, m), 1.79 (2H ,m), 2.69 (3H, s), 2.80 (3H, s) , 3.77 (1H, s), 6.57 (1H, d, J 8.77), 6.73 (1H, d, J 2.19), 6.81 (1H, d, J 2.19), 7.04 (1H, d, J 8.77), 7.18 (1H, dd, J 8.77, 2.19), 7.77-7.92 (3H, m), 8.22 (1H, d, J 2.19) ppm. 13C NMR (C2D60) δ* 172.5, 155.5, 151.8, 151.0, 145.7, 142.6, 138.2, 132.7, 130.9, 130.2, 128.1, 123.8, 120.5, 117.2, 113.7, 112.7, 110.0, 108.4, 100.1, 56.1, 52.7, 34.8, 34.3, 30.4, 30.2, 30.2, 27.1, 26.3, 25.7, 24.1, 20.9, 19.0, 18.6, 14.2, 1.5 ppm.
Example 12
2-(9'-(PDMS(855)-undecoyl)oxy-ethyl ester)-1,3,3-trimethylspiro[indoline-
2,3"-[3H]napth[2,1 -b][1,4]oxazine]
(Formula Removed)
SOX-ethoxy-undec-PDMS(855) Ex. 12
2~(9'- (PDMS(855)-undecoyl) oxy-ethyl ester)-1,3,3-trimethylspiro[indoline-2,3'-[iH]napth[2,1-b][1,4]oxakiine] was synthesised according to the procedure for the preparation of 9'-(PDMS(855)-undecoyl)-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine] (Example 5) using 2-(9'-oxyethanol)-1,3,3,-trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine] in place of 9'-hydroxy-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine]. 1H NMR (C2D6O) δ= 0.10 (bs), 0.58 (4H, m), 0.89 (3H, m), 1.24-1.49 (22H, m), 1.78 (2H ,m), 2.51 (2H, t, J 7.31), 2.68 (2H, t, J 7.31), 2.77 (3H, s), 6.65 (1H, d, J 7.68), (3.73 (1H, dd, J 1.96), 7.04 (1H, d, J 8.77), 7.10-7.24 (3H, m), 7.75-7.93 (3H, m), 8.23 (1H, d, J 2.56) ppm. 13C NMR (C2D60) δ= 170.3, 152.0, 151.0, 136.7, 132.6,
130.9, 130.2, 128.8, 128.1, 122.3, 120.7, 120.5, 117.2, 113.7, 108.0, 99.7, 52.5, 34.8, 34.2, 30.3, 30.2, 30.1, 29.9, 29.8, 28.7, 27.1, 26.2, 25.8, 25.7, 24.0, 21.0, 18.9,18.6,14.8, 14.2, 1.4 ppm.
Example 13
5-methyl carboxylate-6-(PDMS(855)-undecoyl) -2,2-bis(4-methoxyphenyl)-2tf-napthol[1,2-fc] pyran
(Formula Removed)
A solution of the poly(dimethylsiloxane) monocarboxydecoyl chloride (0.78 g, 7.34 x 10-4 mol) in dichloromethane (5 mL) was slowly added to a solution of 5-methyl carboxylate-6-hydroxy-2,2-bis(4-dimethoxyphenyl)-2H-naptho[1,2-6] pyran (0.29 g, 6.2 x 10"4 mol) and triethylamine (0.12 g, 1.22 mmol) in dichloromethane (10 mL) The solution was stirred at room temperature under N2 for 2 hour. Water (20 mL) was added and the solution was extracted, dichloromethane (3 x 20 mL), followed by removal of the sol-O-ent in vacuo then chromatography (silica, 5 :1 hexane/^thyl acetate) to gi-O-e a red -O-iscous oil (0.89) g, 96%). 1H NMR (C2D60) δ=O.10 (bs), 0.59 (4H, m), 0.90 (3H, m), 1.34 (24H, m), 1.77 (2H, m), 2.74 (2H, t, J 7.68), 3.75 Example 14
5-Methyl carboxylate-6-(PDMS(855)-undecoyl)-2,2-(4-methoxyphenyl)-2H-
napthol[1,2-b]pyran
(Formula Removed)
5-Methyl carboxylate-6-(PDMS(855)-undecoyl)-2,2-(4-methoxyphenyl)-2H-
napthol[1,2-b] pyran was synthesised according to the procedure for 5-methyl carrboxyIate-6-poly(dimethylsiloxane)-underyl-2,2 bis(4-methoxyphenyl)-2H-napthol[1,2-b] pyran (Example 13) using 5-methyl carboxylate-6-hydroxy-2,2-(4-methoxyphenyl)-2H-naptho[1,2-5]pyran in place of 5-methyl carboxylate-6-hydroxy-2,2-bis(4-dimethoxyphenyl)-2H-naptho[1,2-b]pyran. 1H NMR (C2D6O)
δ=O.09 (bs), 0.58 (4H, m), 0.89 (4H, m), 1.35 (22H, m), 1.77 (2H ,m), 2.75 (2H, t, J 7.31), 3.75 (3H, s), 3.93 (3H, s), 6.46 ( 1H, d, J 10.23), 6.88 ( 2H, d, J 8.77), 6.99 (1H, d, J 10.23), 7.21-7.42( 3H, m), 7.47 ( 2H, d, J 8.77), 7.51- 7.74 (4 H, m), 7.85 ( 1H, d, J 7.67), 8.45 ( 111, d, J 7.67) ppm. 13C NMR (C2D6O)
δ=172.2, 166.3, 160.2, I46.7, 145.9, 140.4, 137.4, 130.0, 129.1, 129.0, 128.8, 128.6, 128.4, 128.3, 127.4, 127.1, 123.5, 123.0, 121.9, 120.9, 114.4, 114.3, 83.6, 55.5, 52.8, 34.3 30.4, 30.2, 30.2, 29.9, 27.1, 26.2, 25.5, 24.0, 18.9, 18.6, 14.2, 1.5 ppm.
Example 15
5-Methyl carboxylate-6-(PDMS(855)-undecoyl)-2,2-bis(4-
dimethylaminophenyl)-2H-napthol[1,2-b]pyran

(Formula Removed)
5-Methyl carboxylate-6-(PDMS(855)-undecoyl)-2,2-bis(4 dimethylaminophenyl)-2H-napthol[1,2-b] pyran was synthesised according to the procedure for 5-methyl carboxylate-6-poly(dimethylsiloxane)-undecyl-2,2-bis(4-methoxyphenyl)-2H-napthol[1,2-b] pyran (Example 13) using 5-methyl carboxylate~6-hydroxy-2,2-bis(4-dimethylaminophenyl)-2H-naptho[1,2nb]pyran in piace of 5-methyl carboxylate-6-hydroxy-2,2-bis(4-dimethoxyphenyl)-2H-naptho[1,2-b]pyran. 1H NMR (C2D60) δ=O.10 (bs), 0.59 (4H, m), 0.89 (3H, m), 1.34 (24H, m), 1.77 (2H, m), 2.73 (2H, t, J 7.31), 2.89 (12H, s), 3.92 (3H, s), 6.33 (1H, d, J 10.05), 6.68 ( 4H, d, J 8.95), 6.89 ( 1H, d, J 10.05), 7.32 (4H, d, J 8.95), 7.50-7.69 (2H, m), 8.37 ( 1H, d, J 8.41) ppm. 13C NMR (C2D60) δ=172.3, 166.5, 150.9, 147.1, 139.9, 133.4, 130.9, 128.5, 128.4, 128.3, 128.2, 127.1, 123.3, 123.1, 121.0, 120.9, 114 3, 112.6, 84.0, 52.8, 40.5, 34.3, 30.4, 30.2, 30.2, 29.9, 27.1, 20.2, 25.5, 24.0, 18.9, 18.6, 14.2, 1.5 ppm.
xample 16
5-(Carboxylic acid 2- (PDMS(855)-undecoyl)-oxy-ethyl ester)-9-
(dimethylamino)-2,2- (4-dimethylaminophenyl)-2tf-napthol[1,2-b] pyran
(Formula Removed)
5-(Carboxylic acid 2-(PDMS(855)-undecoyl)-oxy-ethyI ester)-9-(dimethylamino)-
2,2- (4-dimethylaminophenyl)-2H-napthol[1,2-b] pyran was synthesised
according to the procedure for 5-methyl carboxylate-6-poly(dimethylsiloxane)-
undecyl2,2-bis(4-methoxyphenyl)-2H-napthol[1,2-b] pyran (Example 13) using
5-(carboxylic acid 2-hydroxy-ethylester)-9-(dimethylamino)-2,2-(4-
dimethylaminophenyl)-2H-napthol[1,2-b] pyran in place of 5-methyl carboxylate-6-hydroxy-2,2-bis(4-dimethoxyphenyl)-2H-naptho[1,2-b]pyran. 1H NMR (C2D60) δ=O.11 (bs), 0.58 (4H, m), 0.88 (3H, m), 1.30 (24H, m), 1.61 (2H ,m), 2.36 (2H m), 2.81 (6H, s), 2.87 (6H, s), 4.48 (2H, m), 4.54 (2H, m), 5.73 (1H,s), 6.20 ( 1H, dd, J 9.87, 2.92), 6.46-6.69 ( 2H, m), 7.02-7.48 ( 8H, m), 7.60 (1H, d, J 10.96), 7.74(1 H, d, J 10.23), 8.15( 1H, s) ppm.
Example 17
5-(Carboxylic acid 2- (PDMS(855)-undecoyl)-oxy-ethyl ester)-9-
(dimethylamino)-2,2-bis (4-dimethylaminophenyl)-2H-napthol[1,2-b] pyran
(Formula Removed)
5-(Carboxylic acid 2-(PDMS(855)-undecoyl)-oxy-ethyl ester)-9-(dimethylamino)-2,2- (4-dimethylaminophenyl)-2H-napthol[1,2-b]pyran was synthesised according to the procedure for 5-methyl carboxylate-6-poly(dimethylsiloxane)-undecyl 2,2-bis(4-methoxyphenyl)-2H-napthwl[1,2-b] pyran (Example 13) using 5-(carboxylic acid 2-hydroxy-ethyl ester)-9-(dimethyiamino)-2,2- bis(4-dimethylaminophenyl)-2H-napthol[1,2-b] pyran in place of 5-methyl carboxylate-6-hydroxy-2,2-bis(4-dimethoxyphenyl)-2H-naptho[1,2-b]pyran. 1H NMR (C2D60) δ=(C2D60) 0.12 (bs), 0.58 (4H, m), 0.91 (3H, m), 1.31 (24H, m), 1.62 (2H ,m), 2.35 (2H m), 2.88 (12H, s), 3.13 (6H, s), 3.92 (3H, s), 4.40 - 4.59 (4H, m), 6.28 (1H, d, J 10.05), 6.66 (4H, d, J 8.95), 7.23 (1H, dd, J 9.14, 2.56), 7.36 ( 5H, d, J 10.05 ), 7.72 (1H, d, J 9.14), 7.90 (1H, s). 13C NMR (C2D60) δ=173.0, 137.4, 151.1, 150.7, 148.1, 1'H.I, 130.M, 129.9, 129.8, 128.4, 126.1, 125.7, 122.5, 120.2, 117.4, 116.4, 112.6, 100.4, 82.8, 63.2, 62.7, 41.8, 40.5, 34.6, 34.3, 30.4, 30.2, 27.1, 26.2, 25.8, 24.0, 18.9, 18.6, 14.2, 1.4 ppm.
Example 18
9'-(PDMS(1077)propyl-ethoxy-succinyl)-1,3,3-trimethylspiro[indoline-2,3'-[3H]naphtha[2,1 -b][1,4]oxazine]
(Formula Removed)
9'-(Monocarboxy-succinyl)-1,3,3-trimethylspiro[indoline2,3,-[3h]naphtha [2,1-b][1,4] oxazine as prepared in Example 6 (0.6 g 1.35 mmoles) was dissol-O-ed in dichloromethane, then monocarbinol terminated polydimethylsiloxane (MCR-C12 from ABCR) (1.76 g, 1.1 equivalents, FW ca 1180) and dimethylaminopyridine (0.135 mmoles 0.1 me, 16 mg) were added. Then dicyclohexylcarbodiimide (0.306 g, 1.1 equi-O-, 1.485 mmoles) in dichloromethane was added dropwise. The reaction was allowed to stir at room temperature. Tic analysis indicated a rapid reaction with no starting spirooxazine obser-O-ed after 1 hour. The reaction was filtered and evaporated then chromatographed on silica with hexane:ether (1:1) to gi-O-e 1.3 g of clear bluish green oil. 1H NMR (acetone-d6) δ = 0.09 (s, Si-Me), 0.5 (mult, 2H, alkyl) 1.62 (mult, Indole methyls and oligomer CH2-Si), 1.4-1.8 (mult, alkyl oligomer), 2.77 (s, 3H, 8-H), 2.82 (mult succinic CH2), 3.00 (mult, succinic CH2), 3.44 (t, J = 7.2 , 2H,), 3.65 (apparent t, J = ca. 5 . 2H), 4.25 (apparent t, J - ca. 5 , 2H), 6.65 (d, J = 7.8 .. 7-H), 6.87 (t, J = 7.3 , 5-H), 7.04 (d, J = 8.5 , 5'-H), 7.14 (d, I = 7.3 , 4-H), 7.22 (apparent t, 2H, 6 & 8'-H), 7.81 (d. J = 9.3 . 6'-H), 7.82 (s, 2'\ i), 7.88 (d, J = 8.6 , 7'-H), 8.25 (d, J = 2.3 , 10'-H) ppm.
(Formula Removed)
Example 19
5,9'-Di(PDMS(855)-undecoyl)-1,3,3-trimethylspiro[indoline-2,3' [3H]naphtha[2,1 -b][1,4]oxazine]
(Formula Removed)
This was made in the same manner as described for Example 3 except poly(dimethylsiloxane) monocarboxydecyl chloride was used in place of succinic acid chloride mono-PEG(350). After addition of poly(dimethylsiloxane) monocarboxydecyl chloride (synthesised in Example 4) to a dichloromethane solution of 5,9-dihydroxy-1,3,3-trimethy!.spiro[indoline2,3,-[3H]naphtha[2,1 -b] [1,4]oxazine with trieihyl amine the reaction was let stir for about 1 hour. The reaction was worked up by washing with water and brine, The dichloromethune was evaporated to gi-O-e 2.5 g of crude product. This was purified by column chromatography (silca, ethenhexane 2:1) to gi-O-e 1.4 g of brown oil. 1H NMR (acetone-d6) δ = 0.13 (s, Si-methyl), 0.6 (mult., alkyl), 0.90 (mult., alkyl), 1.3-1.4 (mult, gem dimethyl groups + other aliphatic) 2.1-2.4 (mult, alkyl), 2.7 (s, 3H, N-
CH3), 6.5-7.5 (mult, aromatic), 7.5-8.2 (mult, aromatic). Photochromic dye signals are -O-ery small due to the relati-O-ely large amount of PDMS. The methyl groups on the dye pro-O-ide the clearest signals.
Example 20
PDMS(855)-undecoyl 2-(4-phenylazo-phenoxy) ester
(Formula Removed)
4-Phenylazophenol (0.127 g, 0.6 mmoles) was dissol-O-ed in ether (5-10 mL) and triethylamine (0.1 mL) was added. Then a solution of poiy(dimethylsiloxane) monocarboxydecoyi chloride terminated (prepared as Example 4) (0.73 g) dissol-O-ed in dichloromethane was added dropwise at room temperature. The reaction was stirred at room temperature for two hours and monitored by tic (ether). The reaction was worked up by dilution with ether and washing with water and then brine. The organic layer was evaporated and chromatographed on silica with ether to gi-O-e an orange oil (200 mg).
(Formula Removed)
Example 21
9'-(Stearoyl)-1,3,3-trimethylspiro[indoline2,3'-[3h]naphtha[2,1-
b][1,4]oxazine
(Formula Removed)
9'-Hydroxy-1,3,3-trimethylspiro[indoline2,3'-[3H]naphtha[2,1 -b][1,4] oxazine] (0.405 g, 1.2 mmoles) and triethylamine (0.32 mL, 234 mg, 2.32 mmoles) were added together in dichloromethane (20 mL) and stearoyi chloride (456 mg, 1.5 mmol) in dichloromethane was added dropwise to the solution at room temperature under argon protection. The reaction was stirred for one hour and tic showed reaction had completed. The reaction was worked up by washing with water, drying (MgSO4) and evaporation to gi-O-e 450 mg of crude product. The sample was recrystallized from 80-100°C petroleum ether to gi-O-e 300 g (42%) of white solid. 1H NMR (methylene chloride-d2) δ 0.88 (t, 3H, c'-H), 1.28 (s, -CHz-), 1.34 (s, methyl), 1.78 (mult, 2H, 'b'), 2.61 (t, J = 7.3 , 'a'), 2.74 (s, 3H, N-methyl), 6.57 (d, J = 7.7 , 7-H), 6. 92 (t, J = 7.4 , 5-H), 7.03 (d, J = 8.1 , 5'-H), 7.09 (d, 4-H), 7.10 (dd, J = 8.8 & 2.1 , 8'-H), 7.20 (t of d, J = 7.7 & 1.3 , 6-H), 7.69 (d, J = 8.8 , 6'-H), 7.74 (s, 2'-H), 7.77 (d, J = 9.0 , 7'-H), 8.23 (d, J = 2.1 , 10'-H) ppm. MS (El): m/z 610.4 ( M+ ,60%) δ95.4 (15), 329 (20), 185 (10), 159.1 (100), 144.1 (15). MS (HR) m/z 610.4134 (C40H54N2O3 requires 610.4134).
Example 22
9'- (2,2,3,3,4,4,5,5,6,6,7,7.8,8,9,9,10,10,11,11,11 -Heneicosafluoro-1 -undecyl-
succinyl)-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1 -b][1,4]oxazine]
(Formula Removed)
5 g (9 mmol) Of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heneicosafluoro-1-undecanol, 0.91 g of triethyl amine, 0.90 g succinic anhydride, 50 mg methanol and 25 mg DMAP were added to 60mL diethyl ether/dichloromethane(6:1). The reaction was stirred o-O-ernight at 40°C. Then the product was washed with 0.5 M HCI, water and then brine and dried with MgS04. 3.9 g of a pink solid- 66% yield.
Step 2
4 g Of fluonnated succinic acid prepared in step 1 was added to 70 mL diethyl ether/ dichloromethane solution (6:1). Then 1.83 g of thionyl chloride was added dropwise. The reaction was left to stir o-O-er forty eight hours and then refluxed for four hours. The final product was rotary evaporated to remo-O-e the thionyl chloride to gi-O-e 3.8 g of yellow solid.
Step 3
1.5 g Of 9'-Hydroxy-1,3,3-trimethylspiro[indoline-2,343H]napth[2,1-b][1,4] oxazine] and 0.66 g triethylamine were added to 90 mL diethyl ether/dichloromethane solution (5:1). Then 3.5 g of fluonnated acid chloride in 10 mL diethyl ether was added, dropwise under argon. The reaction was refluxed for three hours. Completion of the reaction was confirmed by tlc (3:1 ether, hexane). The reaction was washed with water, brine and MgSO4 and then rotary evaporated. The final product was purified using column chromatography ( 3:1 ether, hexane). 1.9 g Of yellow powder was obtained. 1H NMR (acetone-d6) δ=1.33 & 1.35 (s, 6H, gem dimethyls), 2.77 (s, 3H, N-methyl), 2.85 & 3.05 (mults, 4H, succinic hydrogens), 4.90 (t, J - 14.3 , 2H, CH2CF2), 6.65 (d, J = 7.7 , 1H, 7-H), 6. 86 (t of d , J = 7.4 , J = 0.7 , 1H, 5-H), 7.04 (d, J = 9.0 , 5'-H), 7.1-7.72 (mult, 3H, 4-H, 8'-H, 6-H), 7.80 (d, J = 9.0 , 6'-H), 7.82 (s, 1H, 2'-H), 7.88 (d, J= ca 8.7 , 1H, 7'-H), 8.25 (u, J= 1.8 , 10'-H) ppm.
Comparati-O-e Example CE1
9'-Propionate-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine]
(Formula Removed)
A magnetically stirred solution of 9'-hydroxy-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine] (91.0 g, 2.91 mmol) in dichlormethane (50 mL) was treated with triethylamine (0.84 mL, 0.61 g, 6.03 mmol) followed, dropwise, by a solution of propionyl chloride (0.54 mL, 0.58 g, 6.27 mmol) in dichlormethane (20 mL). The resulting solution was stirred under N2 at room temperature for 30 minutes. Water (100 mL) was added and the solution extracted with dichloromethane (3 x 50 mL). Removal of the sol-O-ent in vacuo followed by flash chromatography (silica gel, 1:5 (ethyl acetate :hexane)) ga-O-e the title compound as a green solid (1.11 g, 95%). 1H NMR (CDCl3) δ 1.32 (3H, t, J = 7.31 ), 1.35 (6H, s), 2.57 (2H, q, J= 7.31 ), 2.76 (3H, s), 6.58 (d, J = 7.7 , 1H, 7-H), 6. 91 (t, J = 7.3 , 1H, 5-H), 6.99 (d, J = 8.8 , 5'-H), 7.09 (d, J = 7.3 ,1H, 4-H), 7.13 (d of d, J = 8.0 & 2.2 , 1H, 8'-H), 7.21 (t of d, J = 7.7 & 1.5 , 1H, 6-H), 7.66 (d, J = 8.7 , 6'-H), 7.75 (s, 1H, 2'-H), 7.73 (d, J = 8.7 , 1H, 7'-H), 8.23 (d, J = 2.6 , 10'-H) ppm.
Comparati-O-e Example CE2
5-Propionate-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1 -
b][1,4]oxazine]
(Formula Removed)
5Propionate-1 ,3,3trimethylspiro[indo!ine-2,343H]napth[2,1-b][1,4]oxazine] was synthesised according to the procedure for the preparation of 9'-propionate-1,3,3-trimethylspironndoline-2,3'-[3H]napth[2,3-b][1,4]oxazine] (CE1) using 5 hydroxy-1,3,3, -trimethylspiro[indoline-2,3,-[3H]napth[2,1-b][1,4]oxazine] in place of 9'-hydroxy-1,3,3, -trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine] (51%). 1H NMR (C2D6O) δ= 1.19 (3H, t, J 7.31), 1.33 (3H, s), 1.38 (3H, s), 2.57
(2H, q, J 7.31), 2.76 (3H, s), 6.64 (1H, d, J 8.77), 6.91 (1H, dd, J 7.31, 2.19), 6.93 (1H, s), 7.08 (1H, d, J 8.77), 7.42 (1H, dd, J 8.41, 1.46), 7.59 (1H, dd, J 8.41, 1.46), 7.75-7.88 (3H, m), 8.57 (1H, d J 8.41) ppm. 13C NMR (C2D6O) δ= 173.6, 151.6, 146.1, 145.6, 144.9, 137.8, 131.8, 131.2, 130.4, 128.7, 127.9, 125.0, 123.9, 122.3, 121.5, 117.5, 116.6, 108.0, 99.8, 52.5, 30.0, 27.9, 25.6, 20.8, 9.4 ppm.
Comparati-O-e example CE3
6'-Cyano-5-propionate-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1-
b][1,4]oxazine].
(Formula Removed)
6'-Cyano-5-propionate-1,3,3-trimethylspiropndoiine-2,3-[3H]napth[2,1-b][1,4] oxazine] was synthesised according to the procedure for the preparation of 9' propionate-1,3,3,-trimethylspiro[indoline-2,3'-[3H]napth[2,1 -b][1,4]oxazine] (CE1) using 6'-cyano-5-hydroxy-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine] in place of 9'-hydroxy-1,3,3, -trimethylspirotindoline-2,3-[3H]napth[2,1-b][1,4]oxazine] (51%). 1H NMR (C2D6O) δ= 1.19 (3H, t, J 7.31), 1.34 (3H, s), 1.39 (3H, s), 2.58 (2H, q, J 7.31), 2.78 (3H, s), 6.66 (1H, d, J 8.95), 6.91 (1H, dd, J 7.31, 2.19), 6.95 (1H, s), 7.60-7.82 (3H, m), 8.05 (1H, s), 8.09 (1H, d, J 7.68), 8.70 (1H, d J 7.68) ppm. 13C NMR (C2D6O) δ= 173.6, 155.5, 146 9, 144.0, 137.5, 131.5, 129.4, 129.3 127.7, 127.6, 127 6, 125.5, 1214, 123.4, 121.7, 117.4, 116.6, 111.7,108.2, 100.3,53.0,30.0,27.9,25.6,20.8,9.4 ppm.
Comparati-O-e example CE4
5-Methoxy-9'-propionate-1,3,3, -trimethylspiro[indoline-2,3'-[3H]napth[2,1 -
b][1,4]oxazlne]
(Formula Removed)
5-Methoxy-9'-propionate-1 ,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2, 1 -
b][1,4]oxazine] was synthesised according to the procedure for the preparation
of 9'-propionate-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1 -b][1,4]oxazine]
(CE1) using 5-methoxy-9'-hydroxy-1,3,3-trimethylspiropndoline--2,3'-
[3H]napth[2,1-b][1,4]oxazine] in place of 9'-hydroxy-1,3,3-trimethylspiro [indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine] (62%). 1H NMR (C2D6O) δ= 1.24 (3H, t, J 7.68), 1.30 (6H, bs), 2.69 (2H, q, J 7.68), 3.80 (3H, s), 6.72-6.93 (3H, m), 7.05 (1H, d, J 9.14), 7.19 (1H, dd, J 8.77, 2.19), 7.78 (1H, s), 7.79 (1H, d, J 7.68), 8.24 (1H, d, J 2.56) ppm. 13C NMR (C2D60) δ= 173.4, 152.2, 151.0, 146.6, 145.7, 138.4, 136.0, 132.7, 131.0, 130.2, 128.1, 123.5, 121.9, 120.5, 117.2, 115.3, 113.7, 113.2, 100.4, 56.4, 52.6, 32.7, 28.1, 25.8, 20.9, 9.4 ppm.
Comparati-O-e example CE5
2-(9'-Oropionic acid oxy-ethyl ester)-1,3,3, -trimethylspiro[indoline-2,3'-
[3H]napth[2,1 -b][1,4]oxazine]
(Formula Removed)
2-(9'-Propionic acid oxy-ethyl ester)-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine] was synthesised according to the procedure for
the preparation of 9'-propionate-1,3,3-tritnethylspiro[indoline-2,3-O- [3H]napth[2,1-b][1,4]oxazine] (CE1) using 2-(9'-oxyethanol)-1,3,3-trimethylspiro[indoline-2,3'-[3H]napth[2,1-b][1,4]oxazine] in place of 9'-hydrox-O--1,3,3-trimethylspiro [indoilne-2,3-[3H]napth[2,1-b][1,4]oxazine]. 1H NMR (C2D60) δ = 1,1 (3H, t, J 7.68), 1.33 (3H, s), 1.35 (3H, s), 2.38 (2H, q, J 7.50), 2.77 (3H, s), 4.42 (2H, t, J 4.08), 4.51 (2H, t, J 4.08), 6.65 (1H, d, J 7.68), 6.83-6.93 (2H, m), 7.08 (1H, d, 8.97), 7.11-7.23 (2H, m), 7.70 (1H, d, / 8.78), . .76 (1H, d, J8.78), 7.80 (1H, s), 7.95(1 H, d, J 1.83) ppm.
Comparati-O-e example CE6
5-Methyl carboxylate-6-propionic acid ester-2,2-bis(4-methoxyphenyl)-2H-
naptho[1,2-b]pyran
(Formula Removed)
A mechanically stirred solution of 5-methyl carboxylate-6-hydroxy-2,2~bis(4-dimethoxyphenyl)-2H-naptho[1,2-b]pyran (0.50 g, 1.07 mmol) and triethylamine (0.24 g, 2.35 mmol) in dichloromethane (10mL) was treated dropwise with a solution of propionyl chloride (0.19 g, 2.02 mmol) in dichloromethane (10 mL). The resulting solution was stirred at room temperature under N2 for 30 minutes. Water (50 mL) was added and the solution was extracted with dichloromethane (3 x 50 mL). Removal of the sol-O-ent in vacuo followed by column chromatography (silica, eluent hexane/ethyl acetate 3/1) ga-O-e the title compound as an red solid (0.51 g, 91%). 1H NMR (C2D60) δ=1.26 ( 3H, t, J 7.68), 2.76 ( 2H, q, J 7.68), 3.72 (6H, s) 3.94 (3H, s), 6.39 (1H, d, J 10.05), 6.88 ( 2H, d, J 8.77), 6.99 ( 1H, d, J 10.05, 7.45 (1H, d, J 8.77), 7.51-7.71 ( 2H, m), 7.88 (1H, d, J 8.41), 8.42 ( 1H, d, J 7.86) ppm. 13C NMR (C2D60) δ=173.1,
166.4, 160.1, 146.7, 140.4, 137.7, 130.3, 128.9, 128.8, 128.6, 128.3, 127.1,
123.4, 123.0, 121.6, 120.8, 114.4, 83.5, 55.5, 52.9, 27.8, 9.4 ppm.
Comparati-O-e example CE7
5-Methyl carboxylate-6-propionic acid ester-2,2-(4-methoxyphenyl)-2H-
naptho[1,2-b]pyran
(Formula Removed)
5-Methyl carboxyIate-6-propionic acid ester-2,2-(4-dimethoxyphenyl)-2H-naptho[1,2-b]pyran was synthesised according to the procedure for 5-methyl carboxylate-6-propionic acid ester-2,2-bis(4-dimethoxyphenyl)-2H-naptho[1,2-frjpyran (CE6) using 5-methyl carboxylate-6-hydroxy-2,2-(4-dimethoxyphenyl)-2H-naptho[1,2nb]pyran in place of 5-methyl carboxylate-6-hydroxy-2,2-bis(4-dimethoxyphenyl)-2H-naptho[1,2-b]pyran. This pro-O-ided an orange solid (79%). 1H NMR (C2D60) δ=1.29 ( 3H, t, J 7.49), 2.78 ( 2H, q, J 7.49), 3.68 (3H, s), 3.95 (3H, s), 6.46 (1H, d, J 10.05), 6.88 ( 2H, d, J 8.77), 7.07 (1H, d, J 10.05), 7.20-7.44 (3H, m), 7.51 ( 2H, d, J 8.77), 7.55-7.71 (4H, m), 7.91 (1H, d, J 8.56), 8.50 ( 1H, d, J 8.77) ppm. 13C NMR (C2D60) δ=173.2, 166.4, 160.2, 146.8, 146.0, 140.6, 137.4, 130.1, 129.2, 129.1, 129.0, 128.7, 128.5, 128.4, 127.5, 127.2, 123.6, 123.1, 122.0, 120.8, 114.5, 114.4, 83.7, 55.6, 53.0, 27.9, 9.6 ppm.
Comparati-O-e example CE8
5-(Carboxylic acid 2-methyl ester)-9-(piperdino)-2,2-(4-dimethylaminophenyl)-2H-napthol[1,2-b]pyran
(Formula Removed)
James Robinson Midnight Grey was used as supplied. NMR and mass specUal analysis suggested a structure gi-O-en abo-O-e. The structure abo-O-e is the best fit with the spectral data and the information in US Patent 6,387,512.
Comparati-O-e example CE9
5-Methyl carboxyiate-6-propionic acid ester-2,2-bis(4-
dimethylaminophenyl)-2H-naptho[1,2-b)]pyran
(Formula Removed)
5-Methyl carboxylate-6-propionic acid ester-2,2-bis(4-dimethylaminophenyl)-2H-naptho[1,2-b]pyran was synthesised according to the procedure for 5-methyl carboxylate-6-propionic acid ester-2,2-bis(4-dimethoxyphenyl)-2H-naptho[1,2-b]pyran (CE6) using 5-methyl carboxylate-6-hydroxy-2,2-bis(4-dimethylaminophenyl)-2H-naptho[1,2-b]pyran in place of 5-methyl carboxylate-6-hydroxy-2,2-bis(4-dimethoxyphenyl)-2H-naptho[1,2-b]pyran. This pro-O-ided a pale blue solid (85%). 1H NMR (C2D6O) δ=1.25 ( 3H, t, J 7.49), 2.75 ( 2H, q, J 7.49), 2.88 (12H, s), 3.92 (3H, s), 6.33 ( 1H, d, J 10.05), 6.67 ( 4H, d, J 6.67), 6.90 ( 1H, d, J 9.89), 7.33 (4H, d, J 8.95), 7.50-7.68 (2H, m), 7.83 ( 1H, d, J 7.68), 8.38 ( 1H, d, J 7.68) ppm. 13C NMR (C2D60) δ=173.1, 166.5, 150.9, 150.9, 147.1, 139.9, 136.0, 133.4, 131.0, 128.5, 128.4, 128.2, 127.1, 123.4, 123.1, 120.9, 114.3, 112.6, 84.0, 52.8,40.5, 27.7, 9.4 ppm.
Comparati-O-e Example CE10
Propionic acid 4-phonylazo-phenyl ester
(Formula Removed)
4-Phenylazophenol (0.25 g, 1.26 mmoles) was dissol-O-ed in ether (5-10 mL) and triethylamine (0.26 mL) was added. Then propanoyl chloride (0.14 g 1.5 mmoles) in ether (1 mL) was added dropwise at room temperature . The mixture was stirred and reaction was rapidly completed. The reaction mixture was washed with water, dilute acid and brine and dried with magnesium sulfate. The sol-O-ent was evaporated to gi-O-e 0.23 g (72 %) of product. 1H NMR
(Formula Removed)
(CDCl3) δ= 1.16 (3H, t, J = 7.7 ), 2.40 (2H, q J= 7.7 ), 7.25 (2H, m), 7.40-7.58 (3H, m), 7.88-8.0(4H, m) ppm.
Example 23
NMR experimental observation of nanoencapsulation
The two dyes described in Example 1 and Example 5 were examined by 1H NMR spectroscopy to determine whether the attached oligomer was interacting with the photochromic dye in a manner that was consistent with nanosolvation/nanoencapsuation. This was carried out by dissol-O-ing the dye in deutero acetone and irradiating the dye with UV light. ROE (Rotational O-O-erhausen Enhancement) experiment were performed while the dye was in the coloured state. ROE is a technique similar to NOE (Nuclear O-O-erhausen Enhancement) but is modified for use in large molecules. The technique allows the through space proximity of hydrogens to be determined. Selected hydrogens are irradiated (with radio frequency) and other hydrogens are obser-O-ed to see if they are enhanced. If another hydrogen is close enough, then energy is transferred to it from the irradiated hydrogen.
It was found that PEG oligomer of Example 1 does coil near or around the dye. This is shown in the ROE experiment (see top spectrum of Figure 5) where energy irradiated into the first CH2 group of the first PEG unit was transferred to
the marked hydrogens on the other side of the molecule. This transfer is e-O-idenced by an enhancement of the signaL due to those hydrogens. For this to happen those hydrogens must be in close proximity to the hydrogen being irradiated. Thus the PEG is coiling near or around the dye rather than being tost into the sol-O-ent. In the clear form there is a weaker association. Thus when in a lens en-O-ironment it can be expected that the PEG chains will similarly coil near/around the dye molecule and so pro-O-ide a fa-O-ourable switching en-O-ironment. The bottom two spectra of Flgure 5 are con-O-entional spectm of the molecule in solution obtained by subtraction and normally.
Similarly for the dyes of Example 5 with the PDMS oligomer it was shown that the oiligomer coils around the molecule. (Figures 6 and 7) In the ROE
experiment, energy transfer was obser-O-ed between the mid methylenes and endgroup of the PDMS chain with the central H of the coloured form of the spirooxazine (figure 6). Energy transfer was also obser-O-ed between the mid methylenes of the undecyl portion of the oligomer and the 4 hydrogen on the indole (figure7). Thus the PDMS chain must be highly localised around the spirooxazine. There is a similar but weaker association in the clear form.
These experiment show that the oligomers are not only localised around the dye molecule but wrap around the dye to varying degrees with interactions between the oligomer and the far side of the dye obser-O-ed, and in the case of the PDMS oligomer there are multiple sites of interaction. This nanoencapsulation would be expected to be greater in the rigid en-O-ironment of a polymer matrix where the mobility of the surrounding host medium (in this case the host polymer) is much less.
Example 24
Photochromic beha-O-iour of dyes cast in a cure polymer matrix
Table 6 gi-O-es the fade speed results for the example dyes that were cast in to test lenses directly.
The following is a standard formulation and testing procedure which we used to
essess the performance of many photochromic compounds of the innventiion. The test is referred to in the specification and claims as "the standard photochromic cast test".
The monomer mix consisted of 16 g of 2,2'-bis[4-methacryloxyethoxy)phenyl]propane known as Nouryset 110, 4 g of polyethylenglycol 400 dimethacrylate known as NK ester 9G and 80mg (.4%) of AI8N. This is referred to though out as the "monomer mix A ". The dye was mixed into the monomer then placed into small moulds. The moulds consisted of a small silicon or -O-iton o-ring (14.5 mm internal diameter, width 2.6 mm). This was stuck to a microscope slide using cyanoacrylate glue. The monomer mix was poured into the mould and another microscope slide was placed on top and
air bubbles were excluded. The two plates were clipped together and the sample heated at 75°C for 16 hours. The lens was reco-O-ered and was typically 14.2 mm in diameter and 2.6 mm thick and weighed about 0.5 g.
All measurements were performed on a custom built optical bench similar to that described for the thin film observations in Example 8. The bench consisted of Cary 50 Bio UV--O-isible spectrophotometer fitted with a Cary peltier accessory for temperature control, a 280W Thermo-Oriel xenon arc lamp, an electronic shutter, a water filter acting as a heat sink for the arc lamp, a Schott WG-320 cut-off filter and a Hoya U340 band-pass filter. The solution samples were placed in quartz cUVettes and solid samples were placed at 45 degree angle to both UV lamp and light path of spectrophotometer. The resulting power of UV light at the sample was measured using an Ophir Optronics Model AN/2 power meter gi-O-ing 25 mW/cm2.
The change in absorbance was measured by placing the appropriate sample in the bleached state and adjusting spectrophotometer to zero absorbance. The samples were then irradiated with UV light from the xenon lamp by opening the shutter and measuring the change in absorption. The absorption spectra were recorded for both the bleached and activated (coloured) state. The wa-O-elength of the maxima in absorbance was then recorded and used for the monitoring of kinetics of activation and fade. Test lens samples were activated with 1000 seconds UV exposure.
Table 6
Photochromic beha-O-iour of dyes cast into a cured polymel matrix of monomer mix A consisting of 4:1 2,2'-bis[4-(methac(yloxyethoxy)phenyl]propane and poly(ethylglycol (400) dimethacrylate.
(Table Removed)
can be seen in all examples that the presence of a polydimethylsiloxane oligomer, polyethylgylcol oligomer or perfluorinated alkane oligomer gave significantly faster fade speed as measured by T1/2 or T3/4. T1/2 is the time taken for the optical density to reduce by half irom the initial maximum optical donsity of the coloured from when UV irradiation is stopped. T3/4 is time taken for the optical density to reduce by three quarters from the initial maximum optical density of the coloured form of the dye. In all those cases except for Example 6 (and Example 21), the reduction in T1/2 ranges from 40% to 95 % and T3/4 by 60% to 99% as compared to the electronically identical comparison examples that do not have the oligomer. The following points are illustrated by these examples:
1. It is extremely surprising and unexpected to find that the addition of a relatively large substituent such as a PDMS oligomer (ca 1000g mwt) would cause the dyes to switch faster than the correspondingly
electronically identical dye with only a propylate substituent (29g mwt) in a rigid polymer matrix.[ Note that this matrix is not tuned to encourage photochromic performance. This tuning is typically done by addition of other monomers that 'soften' the entire matrix and so compromise physical properties of the lens to some extent] Example 5 is typical. Note the rapid colouration and overshoot of example 5 as compared to CE1. (Figures 8 and 9). The dyes are electronically identical yet the dye with the oligomer (Example 5) not only fades faster but does so by a large margin with the TV2 and T3/4 reduced by 79% and 96% respectively as compared to the comparison dye (CE1) in the identical matrix .
The position of attachment of the oligomer makes no substantial difference to the dyes performance. They are all much faster than their corresponding comparison dyes. (See kinetic data for Examples 5, 9, 13, and 16 and corresponding comparative examples).
The nature of the linking group between the oligomer and dye has no apparent effect on the fade speed. They are all much faster than their comparison dyes See kinetic data for example 5, 12 and 18 and corresponding comparative examples.
The nature of the linear of PDMS oligomer has little effect on the fade
performance with examples 5 and 18 with them significantly out performing CE1 although the PDMS oligomers and linking groups are different.
Example 6 with the POSS subslituent is different among the PDMS dyes. The POSS group is relatively rigid (i.e. high Tg) as compared to linear PDMS oligomers. Example 6 was a solid where as the dyes with linear PDMS oligomers are oils or low melting point solids. Its T1/2 is much the same as the comparison dye but its T3/4 is significantly faster. This is likely to be due to the free volume that the large POSS group would create around it. It is thought that it is because of this free volume that the solid state crystalline photochromism observed in Example 6 occurs.
The concept of low Tg oligomers improving switching speed and fade speed in particular is applicable for any photochromic dye that involves a structural molecular rearrangement with spiro-oxazines (Examples 2, 5, 6, 9,10,11,12, 18, 23), chromenes (13, 14, 15, 16, 17) (Figures 10 and 11) and the azo (Example 20)(Figures 12 and 13) dyes all shown to have a fade speed enhancement in their thermal reverse reactions to the coloured state. Thus this is a generic "bolt-on" solution for fade speed enhancement than does not alter the colour of the dye.
The addition of a high Tg oligomer such as stearyl (Example 21) gave slower fade speeds. This further illustrates the need for low Tg oligomers for fast fade speed and high Tg oligomer for slow fade speed.
The Tg of the oligomer is maybe more important than its compatibility but compatibility stiil contributes to fade speed. Example 2 which possess a long PEG chain of ca 16 units would be expected to have some compatibility with the monomer mix A which contains poly(ethyleneglycol) dimethacrylate. However fast fade is still observed although not as fast as the PDMS example 5 (Figures 8 and 9).
The kinetic results of examples as a whole, illustrate the control over photochromic performance that can be oiained without altering the electronic nature of the dye. This is very important as it means no change in the colour occurs yet its fade speed can be greatly changed. Note the three fade speed obtained for the electronically indentieal dyes Example 5, CE1 and Example 21. Ty2 ranges from 3 second to 32 seconds (one order of magnitude) and T3/4 ranges from 7 second to 441 seconds (one and half orders of magnitude).
The electronic nature of the dye not only affects the observed colour of the open form but can affect the switching speed. The oligomer can not change that part of the switching speed of the dye that is due to the electronic nature of the dye. For example, Example 10 is an inherently
slow switching dye even in solution. The low Tg oligomer (ie PDMS) simply provides a near-solution like environment to allow the due to switch as fast as it can. Example 9 switches much faster than Example 10. That is due to the different electronic nature of the two dyes. But Example 10 still switches much faster than the electronically identical comparison dye CE3 and that is the effect of the low Tg nanoenvironment of the PDMS oligomer.
Importance of the attachment of the oligomer.
It was shown that the oligomer must be attached to the dye for the fast fade effect to occur. Example 5 and CE 1 were cast into separate lenses as before. A third test lens containing 1.18 mg CE5 and 1.44 mg of 10 cst PDMS in 1.1321 g of monomer mix A was also prepared. This lens was slightly hazy. It was clearly shown that the dye with the oligomer attached (Ex. 5) showed fast coloration and fade where as both the CE5 and the CE5 + PDMS lens showed essentially the same slow kinetics (Figures 14 and 15). This also illustrates the great efficiency of the methodology of the attachment of the low Tg oligomer to the dye. Because the dye cannot be separated from its highly localised low Tg environment, very little is needed in the lens. As only small amounts of dye are needed to obtain the photochromic effect logically only a small amount of oligomer are added the formulation. However in order to get improved fade speed with conventional dyes comparatively very large amounts of "soft" monomer need to be ack'ed to the bulk host rratrix Thus the bulk mechanical properties of the lens are degraded.
Comparison between photochomic dyes and a sonenercial phmochron c lens.
The improved kinetic performance of these modified photochromic dyes as compared to the state of the art is illustrated in the 16. Example 9 was cast in the monomer mix A (4:1 Nouryset 110:NK ester 9G) and compared to the premium fast fade photochromic lens "Sepctralite Velocity Transtionstm". The improvement in performance of the photochromic -PDMS conjugate over the current commercial lens is clear. Example 9 gave near-square wave performance that matched the light on light off cycles and returned to near 0.0
absorbance each cycle. The commercial lens gave a saw tooth response and returned to 0.4 absorbance (ca. 40% transmission) before each next light-on cycle. It must be noted that the host matrix containing example 9 is not optimised for photochromic response where as the commercial lens is. The compounds of this invention represents a significant and large advance on existing technology.
Example 25
The imbibition experiment was carried out by contacting the lens sample to the dye of Example 1 and paraffin oil mixture for three hours at 130°C. The lens was then cleaned with acetone when the lens was cooled to room temperature. The lens was photochromic when sufficient dye diffused into the lens.
Example 26. Fatigue Resistance test.
The fatigue test was carried out by exposing the lens (made from monomer mix A and the appropriate dye example) sample to an accelerated weathering condition then evaluating the change of lens colour before and after the fatigue. The weathering condition is equivalent to two years actual wearing of the lens in everyday life. The lens samples indoor colour shift and intensity change as well as the activated colour shift and intensity change are used to rate the sample fatigue property. It was shown that the PDMS chain did not significantly degrade photochromic dye fatigue resistance in a ophthalmic lens formulation by comparing results obtained from Example 13 and Comparative Example 6.





We Claim:
1. A photochromic polymeric composition comprising.
(a) a polymer matrix and
(b) in the range of from 0. 01 mg/g of the polymer matrix up to 30% by weight of the polymer matrix of a photochromic compound comprising a photochromic moiety and at least one pendent group comprising at least one oligomer selected from the group consisting of polyether oligomers, polyalkylene oligomers, polyfluoroalkylene oligomers, polyfluoroalkylenyloxy oligomers, polydi (C1 to C10 hydrocarbyl)siloxane oligomers, polysilicic acid oligomers and derivatives thereof, poly(ZSi(OH)3) oligomers and derivates thereof, poly (ZSiCI3) oligomers, poly(ZSi(OMe)3) and mixtures thereof wherein Z is selected from the group consisting of hydrogen, alkyl haloalkyl, cycloalkyl, hydroxyl, amino, alkoxy, aryloxy, aryl and carboxyl; and
wherein the photochromic compound is not reactive with the matrix so that it does not become covalently tethered to the polymer matrix
2 A photochromic composition as claimed in claim 1, wherein the polymer matrix has a Tg of at least 50°C.
3 A photochromic composition as claimed in claim 2, wherein the polymer matrix has a Tg of at least 70°C.
4 A photochromic composition as claimed in claim 1, wherein the oligomer comprises at least 5 monomer units.
5 A photochromic composition as claimed in claim 1, wherein the oligomer comprises at least 7 monomer units.
5 A photochromic composition as claimed in claim 1, wherein the
photochromic compound is of formula I:
(Formula Removed)
wherein
PC is a photochromic moiety;
R is an oligomer chain selected from the group consisting of polyether
oligomers, polyalkylene oligomers, polyfluoroalkylene oligomers, polydi(C1
to C4 alkyl)siloxane oligomers and mixtures thereof;
L is bond or linking group;
n is an integer from 1 to 3;
m is an integer from 1 to 3; and
wherein the total number of monomer units in the oligomer R is at least 5.
7. A photochromic composition as claimed in claim 6, wherein the linking group and oligomer together provide a longest chain length of at least 12 atoms.
8 A photochromic composition as claimed in claim 7, wherein the longest
chain length is at least 15 atoms.
9. A photochromic composition as claimed in claim 6, wherein the photochromic moiety is selected from the group consisting of.
chromenes;
spirooxazines;
spiropyrans;
fulgides.fulgimides;
anils;
perimidinespirocyclohexadienones;
stilbenes;
thioindigoids;
azo dyes; and
diarylethenes.
10. A photochromic composition as claimed in claim 9 wherein the
photochromic moiety is selected from the group consisting of
napthopyrans, benzopyrans, indenonaphthopyrans, phenanthropyrans,
spiro(benzindoline) naphthopyrans, spiro(indoline)-benzopyrans, spiro(indoline)
naphthopyrans, spiroquinopyrans, spiro(indoline)pyrans; spirooxa-zines,
spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines,
spiro(benzindoline)-pyridobenzoxazines, spiro(benzindoline)naphthoxazines and spiro(indoline)-benzoxazines.
11 A photochromic composition as claimed in claim 4, wherein the at least one oligomer is selected from groups of formula la:
(Formula Removed)
wherein
X is selected from oxygen, sulphur, amino, substituted amino and C1-C4
alkylene;
p is 0 or 1;
q is the number of monomer units and is at least five;
R1, which may be the same or different, are selected from the group
consisting of:
C2to G4 alkylene such as ethylene, propylene and butylene;
halo C2 to C4 alkylene such as perfluoroethylene, perfluoropropylene, and
perfluorobutylene;
C2to C4 alkyleneoxy;
C2to C4 haloalkyleneoxy;
di (C2to C4 alkyl) silyloxy; and
R2 is selected from hydrogen, C1 to C6 alkyl and C1 to C6 haloalkyl,
hydroxyl, optionally substituted amino, optionally substituted aryl, carboxylic
acid and derivates thereof.
12 A photochromic polymeric composition as claimed in claim 1, wherein the
oligomer comprises at least 5 di(C1 to C4 alkyl) silyloxy monomeric units.
13 A photochromic polymer composition as claimed in claim 1, wherein the
oligomer includes at least 5 monomeric units selected from the group consisting of
alkylenyloxy, perfluoroalkylene and perfluoroalkylenyloxy monomeric units.
14. A photochromic composition as claimed in claim 1, wherein the polymer matrix comprises at least one polymer selected from the group consisting of poly (vinyl acetate); polyurethanes; polycarbonates; polyethylene-terephthalates; polystyrene; copoly(styrene-methylmethacrylate); copoly(styrene-acrylonitride); polyvinyl butyral); and polymers of one or more monomers selected from the group consisting of alkylcarbonate, multifunctional acrylate, multifunctional methacrylate, acrylate, methacrylate, methyl methacrylate, cellulose acetate cellulose triacetate, cellulose acetate propionate, nitrocellulose, cellulose acetate butyrate, vinylalcohol, vinylchloride, vinylidene chloride and diacylidene pentaerythritol.
15. A photochromic polymeric composition as claimed in claim 1, wherein the photochromic compound is incorporated in the polymeric matrix by application to a surface of a polymer matrix which is at least partially cured.
16. A photochromic polymeric composition as claimed in claim 1, wherein the photochromic compound is blended with the polymeric matrix or monomer and/or prepolymer precursors of the polymeric matrix
17. A photochromic polymeric composition as claimed in claim 1 in the form of an optical lens or surface coating thereof.
18. A photochromic composition as claimed in claim 1, wherein the fade half life is changed by at least 20% compared with a corresponding composition in the
absence of the oligomer.
19. A photochromic composition as claimed in claim 1, wherein the fade half life is reduced by at least 40% compared with a corresponding composition comprising the photochromic compound without the oligomer.
20. A photochromic composition as claimed in claim 1, wherein t3/4 is at least 40% reduced compared with a corresponding composition wherein the photochromic compound does not contain the oligomer.
21. A photochromic composition as claimed in claim 1, wherein the photochromic compound comprises a photochromic moiety and a plurality of pendent groups comprising at least one oligomer wherein the oligomer group comprising at least one are located at least one on each side of said photochromic moiety whereby the rate of fade of the photochromic composition is reduced by at least 20% compared with a corresponding composition comprising the photochromic compound without the pendent groups comprising at least one oligomer.
22. A photochromic composition as claimed in claim 1, wherein at least one oligomer have increased the fade half life of the photochromic composition when compared with a corresponding composition comprising the photochromic compound without the oligomer(s).
23. A photochromic polymeric composition comprising a polymer matrix and a photochromic compound which is an adduct comprising a photochromic moiety and at least one pendent group comprising at least one oligomer selected from the group consisting of polyalkylene oligomers, polyfluoroalkylene oligomers polydi(C1 to C10 hydrocarbyl)siloxane oligomers and mixtures thereof.
24. A photochromic composition comprising a polymer matrix and a

photochromic compound which is an adduct comprising a photochromic moiety and at least one pendent oligomer comprising a polydi(C1 to C4 alkyl)siloxane oligomer.
25. A photochromic composition as claimed in claim 24, wherein the fade half life is changed by at least 20% compared with a corresponding composition in the absence of the oligomer.
26. A photochromic composition as claimed in claim 24, wherein the oligomer comprises at least 5 dialkylsilyloxy monomer units.
27. A photochromic composition as claimed in claim 24, wherein the photochromic compound is represented by the formula:
(Formula Removed)
wherein
PC is a photochromic moiety;
R is a polydi(C1 to C4 alkyl)siioxane oligomer;
L is a bond or linking group;
n is an integer from 1 to 3;
m is an integer from 1 to 3; and wherein the total number of monomer units in the oligomer R is at least 7.
28 A photochromic composition as claimed in claim 24, wherein the photochromic moiety is selected from the group consisting of:
chromenes;
spirooxazines;
spiropyrans;
fulgides, fulgimides;
anils;
perimidinespirocyclohexadienones;
stilbenes; thioindigoids; azo dyes; and diarylethenes.
29. A photochrome composition as claimed in claim 24, wherein the at least
one pendent oligomer is selected from groups represented by formula la:
(Formula Removed)
wherein
X is selected from oxygen, sulphur, amino, substituted amino and C1-C4
alkylene;
p is 0 or 1 ;
q is the number of monomer units and is at least 5;
R1 is selected from di(C1 to C4alkyl)silyloxy; and
R2 is selected from hydrogen, C1 to C6 alkyl, C1 to C6 haloalkyi, hydroxyl, optionally substituted amino, optionally substituted aryl, carboxylic acid and derivates thereof.
30. A photochromic composition as claimed in claim 24, wherein the polymer
matrix comprises at least one polymer selected from the group consisting of poly
(vinyl acetate); polyurethanes; polycarbonates; polyethylene-terephthalates;
polystyrene; copoly(styrene-methyl-methacrylate); copoly(styrene-acrylonitride);
polyvinyl butyral); and polymers of one or more monomers selected from the
group consisting of alkylcarbonate, multifunctional acrylate, multifunctional
methacrylate, acrylate, methacrylate, methyl methacrylate, cellulose acetate,
cellulose triacetate, cellulose acetate propionate, nitrocellulose, cellulose acetate
butyrate, vinylalcohol, vinylchloride, vinylidenechloride and diacylidene
pentaerythritol.
31. A photochromic polymeric composition as claimed in claim 24 in the form of an optical lens or surface coating thereof.
32. A photochromic composition as claimed in claim 24, wherein the polydi(C1

to C4 alkyl)siloxane oligomer group is a polydimethylsiloxane oligomer.
33. A photochromic composition as claimed in claim 24, wherein at least one oligomer is selected from the group consisting of polyether oligomers, polyalkylene oligomers, polyfluoroalkylene oligomers, polyfluoroalkylenyloxy oligomers and polydi(C1 to C10 hydrocarbyl)siloxane oligomers.
34. A photochromic article comprising a photochromic composition as claimed in any one of claims 1 to 33.

Documents:

2044-delnp-2005-abstract.pdf

2044-DELNP-2005-Assignment (21-10-2009).pdf

2044-DELNP-2005-Claims.pdf

2044-delnp-2005-complete specification (as-files).pdf

2044-delnp-2005-complete specification (granted).pdf

2044-delnp-2005-Correspondence Others-(04-07-2012).pdf

2044-delnp-2005-Correspondence Others-(08-06-2012).pdf

2044-DELNP-2005-Correspondence-Others (21-10-2009).pdf

2044-delnp-2005-correspondence-others.pdf

2044-delnp-2005-correspondence-po.pdf

2044-DELNP-2005-Description (Complete).pdf

2044-DELNP-2005-Drawings.pdf

2044-DELNP-2005-Form-1 (21-10-2009).pdf

2044-delnp-2005-form-1.pdf

2044-delnp-2005-Form-15-(08-06-2012).pdf

2044-delnp-2005-form-18.pdf

2044-DELNP-2005-Form-2 (21-10-2009).pdf

2044-DELNP-2005-Form-2.pdf

2044-delnp-2005-form-3.pdf

2044-delnp-2005-form-5.pdf

2044-delnp-2005-form-6 (21-10-2009).pdf

2044-DELNP-2005-GPA (21-10-2009).pdf

2044-delnp-2005-GPA-(04-07-2012).pdf

2044-delnp-2005-GPA-(08-06-2012).pdf

2044-delnp-2005-gpa.pdf

2044-delnp-2005-pct-210.pdf

2044-delnp-2005-pct-304.pdf

2044-delnp-2005-petition-137.pdf


Patent Number 245383
Indian Patent Application Number 2044/DELNP/2005
PG Journal Number 03/2011
Publication Date 21-Jan-2011
Grant Date 17-Jan-2011
Date of Filing 13-May-2005
Name of Patentee ADVANCED POLYMERIK PTY. LTD.
Applicant Address 32 BUSINESS PARK DRIVE,NOTTING HILL VICTORIA 3168,AUSTRALIA
Inventors:
# Inventor's Name Inventor's Address
1 EVANS RICHARD ALEXANDER 7 PACKHAM CRESCENT,GLEN WAVERLEY,VICTORIA 3158,AUSTRALIA
2 SKIDMORE MELISSA ANN 51 BENT STREET,MCKINNON VICTORIA 3204,AUSTRALIA
3 YEE LACHLAN HARTLEY UNIT 2,22 PATON STREET,WOY WOY, NEW SOUTH WALES 2256,AUSTRALIA
4 HANLEY TRACEY LEE 124 FALLONS ROAD,WEROMBI, NEW SOUTH 2570,AUSTRALIA
5 LEWIS DAVID ANDREW 36 NIXON STREET,MARION,SOUTH AUSTRALIA 5043,AUSTRALIA
PCT International Classification Number C09K 9/02
PCT International Application Number PCT/AU2003/001453
PCT International Filing date 2003-11-03
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2002952454 2002-11-04 Australia
2 2003903133 2003-06-20 Australia