CN1242009A - (Benzofuran) naphthopyrans, the compositions and (CO) polymer matrices containing them - Google Patents
(Benzofuran) naphthopyrans, the compositions and (CO) polymer matrices containing them Download PDFInfo
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Abstract
The present invention has for subjects novel compounds of the [benzofuran]naphthopyran type as well as the compositions and (co)polymer matrices containing them. Said compounds possess interesting photochromic properties.
Description
The present invention relates to especially to have the compounds of (cumarone) aphthopyrans class of photochromic property.Also relate to the photochromic composition and the photochromic ophthalmic 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 ticket 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 color (grey or tremble brown better) that can be accepted by the human consumer, and, be preferably in the eyeglass colour developing and the process of fading and can keep selected color,
-can keep the performance of feature 0-40 ℃ temperature range,
-because required object lens are expensive senior corrective lens, require the significantly long life-span.
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 chestnut brown color require use different colours in visible-range (promptly to have different maximum absorption wavelength (λ
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 stability in time 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-3,626,690, US-A-4,826,977, US-A-5,200,116, US-A-5,238,981, US-A-5,411,679, US-A-5,429,744,5,451,344, US-A-5,458,814, WO-A-9505382, FR-A-2,718,447 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 (cumarone) aphthopyrans has excellent especially photochromism.More particularly, they have high color developing, and λ max value is greater than the analogue of benzo or aphthopyrans.For some derivative, they have two strong absorption bands in visible-range.The molecule that this class itself is novel is well suited for mixing mutually with Lan Se and/or red and/or yellow complementary photochromic thing, so that obtain grey or brown color.
Therefore, first theme of the present invention relates to the compound with following general formula:
And derivative.Described derivative comprise have corresponding general formula and above-mentioned general formula-CH and-CH
2At least one substituent all compound is arranged on the carbon atom.In these derivatives, preferably on the α of pyranoid ring Sauerstoffatom carbon by dibasic derivative.Like this, above-mentioned α carbon can be unsymmetrical carbon.Therefore, compound of the present invention can be racemic mixture (generally) or the pure isomer with derivative of this asymmetric carbon.
In the first above-mentioned theme, the present invention relates to have the compound of following general formula (I):
In the formula:
R
1And R
2, identical or different, expression respectively:
-hydrogen,
-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;
Or
Two substituent R
1And R
2Constitute adamantyl, norcamphyl, fluorenylidene, two (C together
1-C
6) alkyl anthrylene or spiral shell (C
5-C
6) the cycloalkyl anthrylene; Described group is randomly by above-mentioned R
1, R
2: at least one listed in aryl or heteroaryl substituting group replaces;
R
3And R
4, identical or different, expression respectively:
-hydrogen;
-halogen atom, particularly fluorine, chlorine and bromine;
-contain the straight or branched alkyl of 1-12 carbon atom (better 1-6 carbon atom);
-contain the cycloalkyl of 3-12 carbon atom;
-contain the straight or branched alkoxyl group of 1-12 carbon atom (special 1-6 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 (better being selected from fluorine, chlorine and bromine);
-definition and above-mentioned R
1, 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
1, R
2In identical definition;
-amino or amido :-NH
2,-NHR ,-CONH
2,-CONHR,
Or
R, R ', R " have above-mentioned R respectively
1, R
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
1, R
2: the phenyl that at least one substituting group replaces in aryl or the heteroaryl definition;
M and n are respectively the integers of 0-4.
In the derivative of above-mentioned general formula (I), R in the general formula (I) preferably
1And/or R
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):
In the formula
R
1And R
2Represent respectively by at least one alkyl, alkoxyl group, dialkyl amido
The phenyl that replaces; Above-mentioned substituting group has R
1, R
2: corresponding substituent above-mentioned definition (referring to general formula (I)) in aryl or the heteroaryl definition;
And
R
4Expression hydrogen, contain 1-6 carbon atom the straight or branched alkyl, contain the straight or branched alkoxyl group of 1-6 carbon atom or above-mentioned aryl (referring to the middle R of general formula (I)
1, R
2: the definition of aryl).
In the substituting group of The compounds of this invention (compound of particularly above-mentioned general formula I and I1), 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 (cumarone) naphtho-pyrans compounds at first theme of the present invention; their structure comprises at least one polymerizable and/or crosslinkable reactive group, and described group is alkenyl (better being vinyl or allyl group), methacryloyl, acryl or epoxy group(ing) particularly.
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.
Homopolymer or multipolymer that another theme of the present invention comprises straight or branched, is made of The compounds of this invention to small part.
Equally, above-claimed cpd of the present invention 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 compound of the present invention without any special difficulty.Above-mentioned compound can make by general method:
Be about to the compound of following general formula (II):
Two phenyl can be optionally substituted in the formula, especially respectively by the substituent R of definition in the above-mentioned general formula (I)
3And R
4Replace;
With the propargyl alcohol derivative condensation that following general formula is arranged especially:
R in the formula
1And R
2Has the definition in the above-mentioned general formula (I);
(this condensation reaction can be carried out in the solvent of toluene or tetrahydrofuran (THF) and so in the presence of tosic acid, Mono Chloro Acetic Acid or acidic alumina and so on catalyzer);
Perhaps
In the presence of titanium tetraethoxide (IV) with the aldehyde derivatives condensation that following general formula is arranged especially:
R in the formula
1And R
2Has the definition (for example referring to EP-A-0563915) in the above-mentioned general formula (I).
The compound of above-mentioned general formula (II) can make by the known different synthetic routes of those skilled in the art, makes according to following two kinds of routes especially.
Indian Journal of Chemistry, Vol.13 has proposed following reaction scheme in September 1975, the 889-892 pages or leaves:
It is suitable for having substituent R
3And R
4
According to patent US-A-2, the another kind of route described in 893,986 in order to prepare general formula (II) compound, can make the reaction of naphthoquinones and methoxyphenol:
Above-mentioned methoxyphenol can be following type:
M=0,1,2 or 3
The applicant has prepared and has tested above-mentioned original chemical; Above-mentioned compound has good especially photochromism.More particularly, these novel compounds have high color developing, and λ max value is higher than the known aphthopyrans of similar structures.
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.At last after irradiation stops, its initial color of the very fast recovery of compound.
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 aphthopyrans derivative of tinting material blended ((cumarone) aphthopyrans) 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 aphthopyrans derivative of the present invention at least a above-mentioned aphthopyrans derivative 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 color, the mixture 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 photochromic compound.
Compound of the present invention (being particularly useful as 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 (the 0.01-5 weight % order of magnitude) 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 maximum 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 in 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, can exemplify as with photochromic thing in silicone oil, aliphatic series or aromatic hydrocarbon, dibasic 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 polyreaction then.Crano etc. (are published in Applied Photochromic Polymer Systems at article " Spiroxazines andtheir use in photochromic lenses ", the technology of these and other has been described Published by Blackie and Son Ltd., 1992).
According to variation of the present invention, photochromic thing can also be grafted 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, polythiourethane, 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 routine solution as noted above or dispersion composite with mixture that other products forms with the form of liquid or solid-state composition.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 0,562,915), spiro-pyrans or naphtho-spiro-pyrans (United States Patent (USP) 5,238,981) are with Luo oxazine (Crano etc., " Applied PhotochromicPolymer Systems, " Publisher, Blackie﹠amp; Son Ltd., 1992, Chapter 2).
These compositions of the present invention can also comprise:
-be used to regulate the non-photochromic colouring matter 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 a be (to contain (I) especially by The compounds of this invention to small part, (I1) (being total to) polymkeric substance and/or the reticulation of the Xing Chenging repeating unit of type), and/or at least a containing as The compounds of this invention defined above (particularly (I), (I1) 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 even inorganic-organic mixed material make.
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, data storing goods etc.
Embodiment synthetic and photochromic confirmation by following The compounds of this invention ((cumarone) aphthopyrans) further specifies the present invention.
Embodiment
Synthetic and the character of photochromic compound 1-3 of the present invention
Embodiment 1: compound (1) synthetic:
Step 1: in containing 200 milliliters of acetate of 1 milliliter of vitriol oil, make 15 grams 1,4-naphthoquinones and 9.7 gram 3-methoxyphenol back flow reaction 6 hours.This mixture is precipitated in 500 ml waters, filter again.This solid obtains the brown product of 19.4 grams with a large amount of water washings.
Step 2: in 60 milliliters of toluene, make the product and 5.1 that makes in the 5.2 gram steps 1 restrain two (right-p-methoxy-phenyl) propargyl alcohol back flow reaction 4 hours.Then this mixture is poured in 250 milliliters of 1N aqueous sodium hydroxide solutions.Recovery contains the organic phase of photochromic thing, purifies with silica gel column chromatography, and toluene is as eluent.Separate and obtain 1.47 gram products (1).
1H NMR spectrum has been confirmed its structure.
Synthetic 2: compound (2) synthetic:
Step 1: by 1,4-naphthoquinones and 3,5-syringol make corresponding aphthofurans alcohol by the method identical with embodiment 1.
Step 2: the compound that in containing 30 milliliters of toluene of catalytic amount tosic acid step (1) is made (4 gram) and two (p-methoxy-phenyl) propargyl alcohol (3 gram) refluxed 3 hours.With 1 gram sodium bicarbonate this mixture is neutralized then, recycle silicon glue column chromatography is purified, and toluene is as eluent.The cut that will contain photochromic thing is evaporated to dried, and the product of gained is placed in 100 milliliters of toluene and methanol (1/1) mixture and heats recrystallization.Obtain 600 milligrams of light brown products.
1H NMR spectrum has been confirmed its structure.
Embodiment 3: compound (3) and Comparative Examples C
1Synthetic:
Compound 3 and C have been synthesized by similar methods by corresponding synthon (synthon)
1, separate with silica gel chromatography and/or recrystallization method then.
Embodiment 4: the photochromism analysis
The synthetic product is dissolved in the methyl-phenoxide, and the monochromatic UV line with 365 nanometers shone 1 minute then.This solution shows that intensive is painted, and fades in the dark.The λ max of visible spectrum range lists in as in the following table.
Table 1
These measuring results show that the λ max value of The compounds of this invention is higher than 5,6 similar compounds that do not condense cumarone at aphthopyrans.In addition, it is slow slightly to observe the kinetics of fading of The compounds of this invention.Therefore, these compounds are well suited for and have identical fade dynamic (dynamical) blue look and/or red and/or yellow complementary photochromic thing mixing, preparation grey or brown color.
Claims (13)
1. the compound of following general formula:
And derivative, they are replaced by two on the α of pyranoid ring Sauerstoffatom carbon.
2. compound as claimed in claim 1 is characterized in that they have following general formula (I):
In the formula:
R
1And R
2, identical or different, expression respectively:
-hydrogen,
-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;
Or
Two substituent R
1And R
2Constitute adamantyl, norcamphyl, fluorenylidene, two (C together
1-C
6) alkyl anthrylene or spiral shell (C
5-C
6) the cycloalkyl anthrylene; Described group is randomly by above-mentioned R
1, R
2: at least one listed in aryl or heteroaryl substituting group replaces;
R
3And R
4, 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;
-definition and above-mentioned R
1, 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
1, R
2In identical definition;
-amino or amido :-NH
2,-NHR ,-CONH
2,-CONHR,
Or
R, R ', R " have above-mentioned R respectively
1, R
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
1, R
2: the phenyl that at least one substituting group replaces in aryl or the heteroaryl definition;
M and n are respectively the integers of 0-4.
3. compound as claimed in claim 1 or 2 is characterized in that R in the general formula (I)
1And/or R
2Be 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. as each described compound in the above-mentioned claim, it is characterized in that they have following general formula (I1):
In the formula
R
1And R
2Represent respectively by at least one alkyl, alkoxyl group, dialkyl amido-
The phenyl that replaces; Described substituting group has R in the claim 2
1, R
2: corresponding substituent definition in aryl or the heteroaryl definition;
And
R
4Represent in hydrogen, the straight or branched alkyl that contains 1-6 carbon atom, the straight or branched alkoxyl group that contains 1-6 carbon atom or the claim 2 R
1, R
2: the aryl described in the definition of aryl.
5. as each described compound 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, particularly 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 the described compound of at least a claim 5.
7. photochromic compound is characterized in that it comprises each described compound 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 compound among each described 1-benzopyran derivatives 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 compound 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 compound 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, polythiourethane, 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 compound 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 eyeglass.
13. glass port and/or opticinstrument is characterized in that it comprises:
Each described compound 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 97180899 CN1242009A (en) | 1996-12-23 | 1997-12-10 | (Benzofuran) naphthopyrans, the compositions and (CO) polymer matrices containing them |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR96/15851 | 1996-12-23 | ||
| CN 97180899 CN1242009A (en) | 1996-12-23 | 1997-12-10 | (Benzofuran) naphthopyrans, the compositions and (CO) polymer matrices containing them |
| US60/038,359 | 1998-02-13 |
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|---|---|
| CN1242009A true CN1242009A (en) | 2000-01-19 |
Family
ID=5177950
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97180899 Pending CN1242009A (en) | 1996-12-23 | 1997-12-10 | (Benzofuran) naphthopyrans, the compositions and (CO) polymer matrices containing them |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1976963B (en) * | 2004-04-30 | 2011-01-12 | 澳大利亚聚合物有限公司 | Photochromic compositions and articles comprising polyether oligomers |
| CN103172878A (en) * | 2012-09-07 | 2013-06-26 | 东北师范大学 | Synthesis method of silicon-based photochromic elastomer containing naphthol pyran and having cross-linked structure |
| CN104016996A (en) * | 2014-06-04 | 2014-09-03 | 上海甘田光学材料有限公司 | Novel benzopyran photo-chromic derivative |
| CN108279233A (en) * | 2018-01-23 | 2018-07-13 | 苏州大学 | Microreactor and its preparation method and application based on liquid micrometer motor |
-
1997
- 1997-12-10 CN CN 97180899 patent/CN1242009A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1976963B (en) * | 2004-04-30 | 2011-01-12 | 澳大利亚聚合物有限公司 | Photochromic compositions and articles comprising polyether oligomers |
| CN103172878A (en) * | 2012-09-07 | 2013-06-26 | 东北师范大学 | Synthesis method of silicon-based photochromic elastomer containing naphthol pyran and having cross-linked structure |
| CN103172878B (en) * | 2012-09-07 | 2014-10-01 | 东北师范大学 | Synthesis method of silicon-based photochromic elastomer containing naphthol pyran and having cross-linked structure |
| CN104016996A (en) * | 2014-06-04 | 2014-09-03 | 上海甘田光学材料有限公司 | Novel benzopyran photo-chromic derivative |
| CN108279233A (en) * | 2018-01-23 | 2018-07-13 | 苏州大学 | Microreactor and its preparation method and application based on liquid micrometer motor |
| CN108279233B (en) * | 2018-01-23 | 2020-06-30 | 苏州大学 | Micro-reactor based on liquid micro-motor and preparation method and application thereof |
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