CN1241170A - 2-adamantyl benzopyrans, composition and (co)polymer matrixes contg. them - Google Patents
2-adamantyl benzopyrans, composition and (co)polymer matrixes contg. them Download PDFInfo
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Abstract
The present invention relates to novel benzopyran derivatives, substituted in position 2 with an adamantyl group as well as the compositions and (co)polymer matrices containing such derivatives. Said derivatives possess interesting photochromic properties.
Description
The present invention relates to especially to have the compounds of the 2-adamantyl benzo pyran of photochromic property.Also relate to photochromic composition and ophthalmology goods (as eyeglass) that contain above-mentioned compounds.
Because the influence of polychromatic light or monochromatic ray (as UV), photochromic compound can change color, and, when stopping photoirradiation, or under polychromatic light that is different from first kind of light or monochromatic influence, or in temperature and/or be different under first kind the polychromatic light or monochromatic influence, photochromic compound can recover its original color.
These photochromic compounds can be applicable to various fields, for example, be used to produce optical system, observation optical system, glass port, ornament, the bill element or be used to use up the information storage of learning into (coding) method of ophthalmic lens, contact lens, solar protection glasses, filter, camera optical system, photographic instrument optical system or other opticinstrument.
In the opticianry field, particularly in spectacles industry, comprise that the photochromic lens of one or more photochromic compounds must possess:
-high-transmittance when not having ultraviolet ray,
-low light transmission degree (high-color rendering energy) when terrestrial solar radiation,
-suitable the colour developing and the kinetics of fading,
-the tone (grey or brown better) that can be accepted by the human consumer, and, be preferably in the colour developing of eyeglass and the process of fading and can keep selected tone,
-can keep performance, promptly in the performance of 0-40 ℃ temperature range,
-because required object lens are expensive senior corrective lens, so the life-span is important.
In fact the characteristic of these eyeglasses is to be determined by contained active photochromic compound; In addition, these photochromic compounds must be compatible well with the organic or inorganic carrier that constitutes eyeglass.
And, it should be noted that grey or brown tone requirement use different colours (promptly has different maximum absorption wavelength (λ in visible-range
Maximum)) at least two kinds of photochromic things.Therefore, such mixing has also proposed other requirement to photochromic compound.Particularly the colour developing of the active photochromic compound of two or more blended and the kinetics of fading must be basic identical.To their permanent stability and with the consistency of plastics or inorganic carrier identical requirement is arranged also.
In the described many photochromic compounds of prior art, but referenced patents US-A-3,567,605, US-A-3,627,690, US-A-4,818,096, US-A-4,826,977, US-A-5,200,116, US-A-5,238,981, US-A-5,458,814 and the open No.36144 of research described in chromene or aphthopyrans.These compounds have following structural formula:
These compounds it is said and can satisfy above-mentioned requirements.In fact, these compounds have one or more desired essential propertys really, for example high light transmittance when not having UV-light and the high-color rendering energy when terrestrial solar radiation are not made the satisfied desired over-all properties of goods but present described all compounds do not have industrially scalable ground.
The applicant is surprised to find, and can reduce the λ max value of its colour developing form at the 2-of naphtho-or chromene bit strip adamantyl.The novel molecular energy of this class itself and Lan Se and/or purple and/or red complementary photochromic thing mix well, so that acquisition grey or brown tone.
Therefore, first theme of the present invention relates to the 1-benzopyran derivatives that is replaced by adamantyl at 2, and at least one straight or branched alkyl that adamantyl itself is randomly contained 1-6 carbon atom replaces.Above-mentioned adamantyl is 1 connection more fortunately.
Carbon on 2 of the above-mentioned 1-benzopyran derivatives (the band adamantyl is better with the carbon of diamantane-1-base) is asymmetric carbon.Therefore, derivative of the present invention generally is the form of racemic mixture.But, the pure isomer of said derivative also can account for major portion of the present invention.
In preferred examples of the present invention, the carbon on above-mentioned 2 also has second substituting group S (≠ hydrogen) except that above-mentioned adamantyl.Above-mentioned 2-adamantyl-2-S chromene has interesting especially photochromism.
In above-mentioned first aspect, the present invention relates to have the chromene of following general formula (I):
In the formula:
R
1Be adamantyl, at least one straight or branched alkyl that it is randomly contained 1-6 carbon atom replaces; Above-mentioned adamantyl better is connected 1 and goes up (better R
1=
); R
2Be:
-contain 1-12 carbon atom the straight or branched alkyl,
-contain 3-12 carbon atom cycloalkyl,
-aryl or heteroaryl, in its basic structure, at least one heteroatoms that contains 6-24 carbon atom or 4-24 carbon atom and be selected from sulphur, oxygen and nitrogen; At least one substituting group of randomly selected next group freely of above-mentioned basic structure replaces:
+ halogen atom, particularly fluorine, chlorine and bromine;
+ contain the straight or branched alkyl of 1-6 carbon atom;
+ contain the straight or branched alkoxyl group of 1-6 carbon atom;
+ contain the straight or branched haloalkyl or the halogenated alkoxy of 1-6 carbon atom, particularly this class fluoro-alkyl;
+-NH
2Base;
+-NHR base, R represent to contain the straight or branched alkyl of 1-6 carbon atom;
-aralkyl or heteroaralkyl, its alkyl is a straight or branched, contains 1-4 carbon atom, its aryl and heteroaryl have above-mentioned definition; Above-mentioned aralkyl better is phenyl (C
1-C
4) alkyl;
R
3To R
6, identical or different, expression respectively:
-hydrogen;
-halogen atom, particularly fluorine, chlorine and bromine;
-contain the straight or branched alkyl of 1-12 carbon atom;
-contain the cycloalkyl of 3-12 carbon atom;
-contain the straight or branched alkoxyl group of 1-12 carbon atom;
-haloalkyl, halogenated cycloalkyl, halogenated alkoxy are equivalent to above-mentioned alkyl, cycloalkyl, alkoxyl group respectively, are replaced by at least one halogen atom (being selected from fluorine, chlorine and bromine especially);
-definition and above-mentioned R
2In identical aryl or heteroaryl;
-aralkyl or heteroaralkyl, its alkyl is a straight or branched, contains 1-4 carbon atom, its aryl and heteroaryl have above-mentioned R
2In identical definition;
-amino or amido :-NH
2,-NHR ,-CONH
2,-CONHR,
R, R ', R " have above-mentioned R respectively
2: amine substituent definition in aryl or the heteroaryl definition;
--OCOR
7Or-COOR
7Group, R
7The expression contain the straight or branched alkyl of 1-6 carbon atom or contain the cycloalkyl of 3-6 carbon atom, randomly by above-mentioned R
2: the phenyl that at least one substituting group replaces in aryl or the heteroaryl definition;
Or
-R
3, R
4, R
5, R
6In at least two groups randomly condense, constituting phenyl, naphthyl, pyridyl, benzo pyridyl, furyl, benzofuryl, indenyl or indoles group, this group is randomly by one or more identical or different above-mentioned R that have
3-R
6The substituting group of identical definition replaces; The group of non-condensed as mentioned above.
In the derivative of above-mentioned general formula (I), R in the general formula (I) preferably
2Be the derivative of aryl or heteroaryl, the basic structure of above-mentioned aryl or heteroaryl is selected from phenyl, naphthyl, xenyl, pyridyl, furyl, benzofuryl, dibenzofuran base, N-(C
1-C
6) alkyl carbazole, thienyl, benzothienyl, dibenzothiophene base.
Particularly preferred The compounds of this invention has following general formula (I1) and (I2):
In the formula
.R
1Be diamantane-1-base,
.R
2Expression by at least one alkyl, alkoxyl group, general formula is
The phenyl that replaces of dialkyl amido; Above-mentioned substituting group has above-mentioned R
2: corresponding substituent definition in aryl or the heteroaryl definition;
. naphthyl is randomly by above-mentioned R
3-R
6At least one group described in one of definition replaces.
In the substituting group of 1-benzopyran derivatives of the present invention (being preferably the compound of above-mentioned general formula I, I1 and I2), there are some to contain and/or form at least one polymerizable and/or crosslinkable reactive group.Exist these reactive groups to suit.Therefore; comprise above-mentioned 2 1-benzopyran derivatives that replaced by adamantyl at first theme of the present invention; their structure comprises at least one polymerizable and/or crosslinkable reactive group, and described group particularly alkenyl is better as vinyl or allylic, methacryloyl, acryl or epoxy group(ing).
Therefore, the The compounds of this invention of the above-mentioned type can be regarded as has identical or different character, can react the monomer that forms homopolymer and/or multipolymer mutually or with other comonomer.Above-mentioned homopolymer and/or multipolymer have photochromic functional group (as long as the monomer of the invention described above has above-mentioned photochromic functional group), and have macromolecular mechanical property.
Straight or branched, constitute another theme of the present invention by homopolymer or the multipolymer that 1-benzopyran derivatives of the present invention constitutes to small part.
Equally, above-mentioned 1-benzopyran derivatives also can be regarded linking agent as, and it has can have photochromism or not have to form between the polymer chain of photochromism the response function of bridged bond.The reticulation that makes so also constitutes another theme of the present invention.
Prepare 1-benzopyran derivatives of the present invention without any special difficulty.Above-mentioned derivative can make by general method, promptly by on 2, hydrogen and phenol that is randomly replaced and propargyl alcohol derivative condensation are arranged on 3,4,5 and/or 6, above-mentioned propargyl alcohol derivative is replaced and is randomly replaced by another substituting group by adamantyl at 1, and at least one straight or branched alkyl that above-mentioned adamantyl is randomly contained 1-6 carbon atom replaces.
This synthetic route is classical, and has been documented in the above-mentioned prior art reference.The compounds of this invention (general formula I, R in the formula
1=diamantane-1-yl) synthetic route diagram is as follows:
This condensation reaction can be carried out in the solvent of toluene or tetrahydrofuran (THF) and so in the presence of sulfonic acid, Mono Chloro Acetic Acid or acidic alumina and so on acid catalyst.
The applicant has prepared and has tested above-mentioned original 1-benzopyran derivatives; Above-mentioned derivative has good especially photochromism.More particularly, these novel compounds have high color developing, and λ max value is lower than similar known compound: on 2 with the 1-benzopyran derivatives of two aryl.
In others, these compounds can be compatible with the carrier base material of organic polymer or inorganic materials, and above-mentioned organic polymer or inorganic materials can be included in base-material and the coating.
In solution or polymer base material, compound of the present invention is colourless or color slightly in the initial period, and compound can show dense color rapidly under the light source irradiation of UV light (365nm) or sunlight class.After irradiation stopped, compound recovered its initial color at last.
Another theme of the present invention relates to the application of the compound of the invention described above as photochromic agent.In other words, the applicant proposes at this:
-by the novel photochromic compound that mixes separately, mutually and/or form with the above-mentioned 1-benzopyran derivatives of tinting material blended of at least a another kind of photochromic compound and/or at least a non-photochromic;
-novel photochromic composition, it contains at least a (being total to) polymkeric substance and/or the reticulation that comprises at least a above-mentioned 1-benzopyran derivatives of the present invention at least a above-mentioned 1-benzopyran derivatives and/or the structure.These photochromic compositions can comprise at least a another kind of photochromic compound and/or the tinting material and/or at least a stablizer of at least a non-photochromic.
Above-mentioned another kind of photochromic compound, non-photochromic tinting material, stablizer are the known prior art products of those skilled in the art.
In the present invention, if be used for producing grey or brown tone, the mixture of the photochromic compound of the mixture of special recommendation photochromic compound of the present invention and/or photochromic compound of the present invention and another kind of prior art.
Compound of the present invention (being preferably photochromic compound) can be used in the solution.Therefore, this compound dissolution can be obtained photochromic solution in the organic solvent of toluene, methylene dichloride, tetrahydrofuran (THF) or ethanol and so on.The solution that obtains generally is water white.When by terrestrial solar radiation, they show dense color, and when placing them in the local time that solar radiation must be lacked, in other words, they can recover its colourless state during no longer by UV irradiation.In general, it is painted to use very the product of small concentration (0.01-5% weight amount level) to obtain intensive.
Compound of the present invention also can be used as the photochromic material that is dispersed in polymer base material or its surface.In fact, the most significant purposes of The compounds of this invention is that photochromic thing is evenly dispersed in polymkeric substance, multipolymer or the polymeric blends, perhaps is evenly dispersed on its surface.(being total to) polymer base material that contains the photochromic thing of the present invention (at least a unbound state, (being total to) polymkeric substance and/or the photochromic thing reticulation form and/or the photochromic composition form) constitutes another theme of the present invention.
The implementation method that can be used to obtain this base-material is diversified.In the method that those skilled in the art understood, for example can quote with photochromic thing in silicone oil, aliphatic series or aromatic hydrocarbon, polyvalent alcohol suspension or solution or from another kind of polymer base material photochromic thing is diffused to (being total to) polymkeric substance.According to the character of polymer base material, this diffusion is generally carried out under 50-200 ℃, continues 15 minutes to several hours.Another kind of technical application is included in sneaks into photochromic thing in the polymerisable material formula, this mixture is coated in the surface or places mould, carries out copolymerization then.Crano etc. (are published in Applied Photochromic Polymer System at article " Spiroxanzines and their usein photochromic lenses ", the technology of these and other has been described Publishedby Blackie and Son Ltd., 1992).
Version according to the inventive subject matter can also be grafted to photochromic thing on (being total to) polymkeric substance.Therefore, the present invention also relates to at least a above-mentioned photochromic thing grafted (being total to) polymkeric substance.Therefore, term " (being total to) polymer base material that contains at least a photochromic thing of the present invention " is meant that the base-material of above-mentioned photochromic thing is contained on portion within it or its surface and with above-mentioned photochromic thing grafted base-material.
The better polymerization thing examples of material that photochromic compound of the present invention is applied aspect optics comprises following products:
-polyacrylic acid or alkyl methacrylate polymer, cycloalkyl, aryl or aralkyl (single, double, three or four) ester, can be randomly by halo or comprise at least one ether and/or ester and/carbonic ether and/or carbamate and/or thiocarbamate and/or urea and/or amide group
-polystyrene, polyethers, polyester, polycarbonate (as the polycarbonate of dihydroxyphenyl propane, the polycarbonate of diallyl glycol ether), polyurethane(s), polyepoxides, polyureas, urethane, poly-sulfo-ammonia ester, polysiloxane, polyacrylonitrile, polymeric amide, aliphatic series or aromatic polyester, vinyl polymer, cellulose acetate, cellulosetri-acetate, cellulose acetate propionate or polyvinyl butyral acetal
The multipolymer of-two or more type monomers or above-mentioned mixture of polymers, be preferably polycarbonate-polyurethane, poly-(methyl) acrylate-urethane, polystyrene-poly (methyl) acrylate or polystyrene-poly vinyl cyanide, preferably the mixture of polyester and polycarbonate or poly-(methyl) acrylate.
The consumption of photochromic thing depends on the deepening degree of requirement in (being total to) polymer base material.General its consumption is 0.001-20 weight %.Photochromic compound of the present invention can use separately, or uses to form liquid or solid-state composition, routine solution as noted above or dispersion composite with the mixture with other products formation.Therefore, the composition that constitutes a theme of the invention described above comprises that compound of the present invention and other can provide dark color for example grey or brown complementary photochromic compound, and described color is as desired for the public in the application of glasses or sunglasses industry.These complementary photochromic compounds are known to one skilled in the art, and existing in the literature the description, as chromenes (United States Patent (USP) 3,567,605; 5,238,981; World patent 94 22,850; European patent 562,915), and spiro-pyrans or naphthospiropans (United States Patent (USP) 5,238,981) are with Luo oxazine (Crano etc., " Applied Photochromic Polymer System, " Ed.Blackie﹠amp; Son Ltd., 1992, Chapter 2).
These compositions of the present invention can also comprise:
-be used to regulate the non-light-induced variable tinting material of tone;
-and/or one or more stablizers, as oxidation inhibitor;
-and/or one or more uvioresistant photo etchings;
-and/or one or more antifree radical agents;
-and/or one or more photochemical excitation attitude deactivators.
These additives can obviously improve the weather resistance of described composition.
According to relevant with the application of The compounds of this invention on the other hand, the invention still further relates to the ophthalmology goods, the goods of glasses or sunglasses industry for example, these goods comprise at least a compound of the present invention, and/or at least aly form (being total to) polymkeric substance by The compounds of this invention and/or reticulation (better contains (I) to small part, (I1) and (I2) repeating unit of type), and/or at least a to contain as The compounds of this invention defined above (better be (I), (I1) and (I2) composition compound), and/or at least a aforesaid base-material, described base-material is by the organic polymer material that is mixed with at least a The compounds of this invention, or inorganic materials or inorganic-organic mixed material are made.
In practice, the modal goods that the present invention relates to are photochromic glasses eyeglass or sun glasses eyeglass, pane (buildings, locomotive, automotive glazing), opticinstrument, decorated articles, prevent sunlight goods, information storage goods etc.
Embodiment synthetic and photochromic confirmation by following The compounds of this invention (2 benzofuran derivative that replaced by adamantyl) further specifies the present invention.
Embodiment
Synthetic and the character of photochromic compound 1-4 of the present invention
Embodiment 1: compound (1) synthetic:
Step 1: during by 0 ℃ in THF the reaction synthesis of phenyl adamantyl ketone of diamantane chloride of acid and phenyl-magnesium-bromide.Productive rate behind the purifying is 41%.
Step 2:, be hydrolyzed then and, make 1-adamantyl-1-phenyl-propargyl alcohol with toluene extraction by the reaction of acetylene lithium (diamine complexes) in DMSO and phenyl adamantyl ketone.Productive rate is 90%.
Step 3: in 30 milliliters of toluene of the tosic acid that contains catalytic amount, make the compound that makes in the step 2 (3.2 gram) and 6-methoxyl group-beta naphthal (1.74 gram) back flow reaction 1 hour.With 0.5 gram sodium bicarbonate neutralization medium, carry out chromatographic separation as eluent at silicagel column with toluene more then.Product carries out recrystallization in the mixture of methyl alcohol/diisopropyl ether.Obtain 300 milligrams compound (1) (referring to table 1), be white powder.
1H NMR spectrum has been confirmed the structure of this product.In the solution of THF, the color of this solution by colourless yellowing, is faded rapidly at shady place under sunlight.
Embodiment 2: compound (2) synthetic:
Step 1: by preparing compound 2 by 4.2 gram 1-adamantyl-1-phenyl-propargyl alcohols and 2.3 gram 1-naphthols with the used same procedure of compound 1.These two kinds of reagent refluxed 15 minutes in the dimethylbenzene of the tosic acid that contains catalytic amount.Separate in the enterprising circumstances in which people get things ready for a trip spectrum of silicagel column then, productive rate is 11%.
Embodiment 3 and 4: the compound of synthetic The compounds of this invention (3) and (4) and Comparative Examples C1 and C3
By the compound (see table 1 and 2) of similar methods, compose separation and/or carry out recrystallization in the enterprising circumstances in which people get things ready for a trip of silicagel column then by corresponding synthol examination synthetic compound 3 and 4 (seeing table 2) and Comparative Examples C1 and C3.
Embodiment 5: compound is attached in the polyacrylic ester
General step: 5 milligrams of all cpds are dissolved in (Akzo company sells with trade(brand)name Diacryl 121) in the tetraethoxy bisphenol a dimethacrylate respectively.This solution also contains 40 milligram 2,2 '-azo two (2-methylbutyronitrile).Then with the degassing of this solution,, pour diameter then into and be 8 centimetres and thickness and be in 2 millimeters the glass lens mould with the argon gas inflation.Then this mould was put 12 hours in 70 ℃ of baking ovens.After pouring out, obtain the inflexible transparent lens.Under solar light irradiation, this glass shows dense purple rapidly, and it becomes colourless again to put back to shady place again.Photochromic properties is listed in the table below in 1 and 2.For the ease of comparing, the performance of the compound of the prior art of structural similitude is also listed in following table 1 and 2.After xenon lamp irradiation 15 minutes, record ultraviolet-visible spectrum and the λ max that measures main visible light bands of a spectrum.
Table 1: the compound that makes by beta naphthal
Table 2: the compound that makes by the 1-naphthols
These embodiment show, replace phenyl can reduce the λ max of photochromic thing with adamantyl.In addition, it is slow slightly that we observe the compound of the present invention kinetics of fading.Therefore, these compounds can be well with have the identical dynamic (dynamical) blue look and/or purple and/or red complementary photochromic thing of fading and mix preparation grey or brown tone.
Claims (13)
1. 1-benzopyran derivatives is characterized in that they are replaced by adamantyl at 2, and at least one straight or branched alkyl that adamantyl itself is randomly contained 1-6 carbon atom replaces, and described adamantyl is 1 connection more fortunately.
2. 1-benzopyran derivatives as claimed in claim 1 is characterized in that described chromene represents with following general formula (I):
In the formula:
R
1Be adamantyl, at least one straight or branched alkyl that it is randomly contained 1-6 carbon atom replaces; Above-mentioned adamantyl better is connected on 1;
R
2Be:
-contain 1-12 carbon atom the straight or branched alkyl,
-contain 3-12 carbon atom cycloalkyl,
-aryl or heteroaryl, in its basic structure, at least one heteroatoms that contains 6-24 carbon atom or 4-24 carbon atom and be selected from sulphur, oxygen and nitrogen; At least one substituting group of randomly selected next group freely of above-mentioned basic structure replaces:
+ halogen atom, particularly fluorine, chlorine and bromine;
+ contain the straight or branched alkyl of 1-6 carbon atom;
+ contain the straight or branched alkoxyl group of 1-6 carbon atom;
+ contain the straight or branched haloalkyl or the halogenated alkoxy of 1-6 carbon atom, particularly this class fluoro-alkyl;
+-NH
2Base;
+-NHR base, R represent to contain the straight or branched alkyl of 1-6 carbon atom;
Base, R ' and R "; identical or different; that expression contains the straight or branched alkyl of 1-6 carbon atom respectively; as or to represent that with the nitrogen-atoms that is connected 5-7 unit encircles; that these rings can comprise at least one other the heteroatoms that is selected from oxygen, sulphur and nitrogen, described nitrogen-atoms randomly by R base, contain the straight or branched alkyl replacement of 1-6 carbon atom;
-aralkyl or heteroaralkyl, its alkyl is a straight or branched, contains 1-4 carbon atom, its aryl and heteroaryl have above-mentioned definition;
R
3To R
6, identical or different, expression respectively:
-hydrogen;
-halogen atom, particularly fluorine, chlorine and bromine;
-contain the straight or branched alkyl of 1-12 carbon atom;
-contain the cycloalkyl of 3-12 carbon atom;
-contain the straight or branched alkoxyl group of 1-12 carbon atom;
-haloalkyl, halogenated cycloalkyl, halogenated alkoxy are equivalent to above-mentioned alkyl, cycloalkyl, alkoxyl group respectively, are replaced by at least one halogen atom that is selected from fluorine, chlorine and bromine;
-definition and above-mentioned R
2In identical aryl or heteroaryl;
-aralkyl or heteroaralkyl, its alkyl is a straight or branched, contains 1-4 carbon atom, its aryl and heteroaryl have above-mentioned R
2In identical definition;
-amino or amido :-NH
2,-NHR ,-CONH
2,-CONHR,
R, R ', R " have above-mentioned R respectively
2: amine substituent definition in aryl or the heteroaryl definition;
--OCOR
7Or-COOR
7Group, R
7The expression contain the straight or branched alkyl of 1-6 carbon atom or contain the cycloalkyl of 3-6 carbon atom, randomly by above-mentioned R
2: the phenyl that at least one substituting group replaces in aryl or the heteroaryl definition;
Or
-R
3, R
4, R
5, R
6In at least two groups randomly condense, constituting phenyl, naphthyl, pyridyl, benzo pyridyl, furyl, benzofuryl, indenyl or indoles group, this group is randomly by one or more identical or different above-mentioned R that have
3-R
6The substituting group of identical definition replaces; The group of non-condensed as mentioned above.
3. 1-benzopyran derivatives as claimed in claim 1 or 2 is characterized in that R in described general formula (I)
2Be the derivative of aryl or heteroaryl, the basic structure of described aryl or heteroaryl is selected from phenyl, naphthyl, xenyl, pyridyl, furyl, benzofuryl, dibenzofuran base, N-(C
1-C
6) alkyl carbazole, thienyl, benzothienyl, dibenzothiophene base.
4. each described 1-benzopyran derivatives as in the above-mentioned claim is characterized in that their are with general formula (I1) with one of (I2) represent:
In the formula
R
1Be diamantane-1-base,
R
2Expression is by at least one alkyl, alkoxyl group, dialkyl amido
The phenyl that replaces; Described substituting group has the R described in the claim 2
2: corresponding substituent definition in aryl or the heteroaryl definition;
And naphthyl is randomly by the R described in the claim 2
3-R
6At least one group described in one of definition replaces.
5. as each described 1-benzopyran derivatives in the above-mentioned claim; the structure that it is characterized in that them comprises at least one polymerizable and/or crosslinkable reactive group; described reactive group is selected from alkenyl, better is vinyl or allyl group, methacryloyl, acryl and epoxy group(ing).
6. (being total to) polymkeric substance and/or the reticulation that makes by polymerization and/or the crosslinked at least a monomer that constitutes by at least a 1-benzopyran derivatives as claimed in claim 5.
7. photochromic compound is characterized in that it comprises each described 1-benzopyran derivatives and the photochromic compound of at least a other type and/or the mixture of at least a non-photochromic tinting material among the mixture of each described 1-benzopyran derivatives among each described benzofuran derivative among the claim 1-5 or at least two kinds of claim 1-5 or at least a claim 1-5.
8. photochromic composition is characterized in that it contains:
(being total to) polymkeric substance and/or reticulation described in each described 1-benzopyran derivatives and/or at least a claim 6 among-at least a claim 1-5,
-and photochromic compound and/or at least a non-photochromic tinting material and/or at least a stablizer of optional at least a other type.
9. (be total to) polymer base material, it is characterized in that it contains:
Each described 1-benzopyran derivatives among the-at least a claim 1-5,
-and/or at least a claim 6 described in (being total to) polymkeric substance and/or reticulation,
-and/or the described composition of at least a claim 8.
10. base-material as claimed in claim 9 is characterized in that described (being total to) polymkeric substance is selected from as next group:
-polyacrylic acid or alkyl methacrylate polymer, cycloalkyl, aryl or aralkyl (single, double, three or four) ester, can be randomly by halo or comprise at least one ether and/or ester group and/carbonate group and/or carbamate groups and/or thiocarbamate base and/or urea groups and/or amide group
-polystyrene, polyethers, polyester, polycarbonate, polyurethane(s), polyepoxides, polyureas, urethane, poly-sulfo-ammonia ester, polysiloxane, polyacrylonitrile, polymeric amide, aliphatic series or aromatic polyester, vinyl polymer, cellulose acetate, cellulosetri-acetate, cellulose acetate propionate or polyvinyl butyral acetal
The multipolymer of-two or more type monomers or above-mentioned mixture of polymers.
11. glasses or solar protection goods is characterized in that it contains:
Each described 1-benzopyran derivatives among the-at least a claim 1-5,
-and/or at least a claim 6 described in (being total to) polymkeric substance and/or reticulation,
-and/or the described composition of at least a claim 8,
-and/or at least a claim 9 or 10 described base-materials.
12. goods as claimed in claim 11 is characterized in that it is made of lens.
13. glass port and/or opticinstrument is characterized in that it comprises:
Each described 1-benzopyran derivatives among the-at least a claim 1-5,
-and/or at least a claim 6 described in (being total to) polymkeric substance and/or reticulation,
-and/or the described composition of at least a claim 8,
-and/or at least a claim 9 or 10 described base-materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97180898 CN1241170A (en) | 1996-12-23 | 1997-12-10 | 2-adamantyl benzopyrans, composition and (co)polymer matrixes contg. them |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR96/15850 | 1996-12-23 | ||
| US60/038,357 | 1997-02-13 | ||
| CN 97180898 CN1241170A (en) | 1996-12-23 | 1997-12-10 | 2-adamantyl benzopyrans, composition and (co)polymer matrixes contg. them |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1241170A true CN1241170A (en) | 2000-01-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97180898 Pending CN1241170A (en) | 1996-12-23 | 1997-12-10 | 2-adamantyl benzopyrans, composition and (co)polymer matrixes contg. them |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1241170A (en) |
-
1997
- 1997-12-10 CN CN 97180898 patent/CN1241170A/en active Pending
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