CN101503484B - Method for synthesizing photochromic cross-linked polymer containing naphthyl hydroxide pyran group - Google Patents
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Abstract
The invention belongs to a synthetic method of an organic/polymeric material, in particular relates to a synthetic method of photochromic crosslinked polymers containing naphthol pyran groups. The synthetic method comprises the following steps: firstly preparing diphenyl ketone containing different groups, then converting carbonyl in the obtained diphenyl ketone into hydroxyl and alkynyl, allowing the hydroxyl and the alkynyl to react with naphthol to prepare naphthol pyran molecules, and finally grafting a methacrylic acid polymerization unit to the naphthol pyran molecules to form a polymeric monomer containing three polymerization units. During the reaction process, an acetate group is adopted for protecting the hydroxyl and unprotected after synthesizing the naphthol pyran molecules. After the monomer is obtained, a free radical polymerization method can be adopted, in the method, a single monomer or synthesized different monomers are polymerized with other monomers, thus obtaining various photochromic crosslinked polymers. The synthetic method fills a gap of research on the crosslinked polymers containing the naphthol pyran monomers at home and abroad and provides a new application prospect for photochromic materials.
Description
Technical field
The invention belongs to the synthetic method of organic/polymer materials, particularly a kind of synthetic method that contains the cross-linked polymer of naphthols pyrans photochromic group.
Background technology
Photochromism (Photochromism) is meant that a compound can carry out specific chemical reaction under the optical radiation that is subjected to certain wavelength, obtain the product of novel texture, because the variation of structure causes its absorption spectrum generation obvious variation (colour-change).Product can return to the structure formation of original compound again under the optical radiation of another wavelength or under the effect of heat.This under the effect of light, the phenomenon that reversible color change can take place compound is called photochromism
[1]Photochromic compound and polymkeric substance thereof are a kind of new function materials, can be widely used in fields, forward position such as optical information storage, light-switching device and photoswitch
[1-5]Because photochromic material has huge potential using value, scientific workers are in this field, comprise that aspects such as the performance characterization of the design of novel material and preparation, material and preparation of devices have all done a large amount of work
[5]Polymkeric substance has better film-forming properties than organic molecule, and the photochromic material general requirement is used in modes such as film, fiber, sheet and pearls, so photochromic polymer has more advantage than small molecules photochromic compound in the device manufacturing
[6]Can make photochromic polymer higher photochromic effective concentration be arranged by rational design, avoid simultaneously crystallization that monomer forms easily again, be separated and the shortcomings such as formation of concentration gradient than monomeric compound
[7]Therefore, scientists is in the organic molecule photochromic material of the synthetic premium properties of design, further development difficulty is bigger and the photochromic polymer material of excellent property makes the research of photochromic polymer become the field, a forward position of functional polymer research
[8]
The naphthols pyrans is the photochromic group of a class excellent property, and researcher has carried out the photochromic property that various modifications improve the naphthols pyrans to its molecular structure, as anti-resistive etc. to colour killing of variable color efficient, colour killing speed and discoloration member.But up to the present, we have only seen two about containing the report of naphthols pyrans monomer-polymer
[9-10]And material is not carried out completely sign with system, more not about the report of naphthols pyrans photochromic cross-linked polymer material, thereby contain naphthols pyrans photochromic cross-linked polymer and may provide the material of the light functional polymer with distinguishing feature and excellent property for this research field.
[1]R.S.Becker，J.Michl，J.Am.Chem.Soc，1966，88，5931-5933.
[2]J.C.Crano.R.J.Guglilmetti.Organic?Photochromic?and?ThermochromicCrmounds，Plenum.New?York?1999.
[3]F.M.Raymo，S.Giordani.Proc.Natl.Acad.Sci.USA，2002，99(8)，4941-4944.
[4]H.Durr，H.Boaslaurent，Photochromisn：Molecules?and?Systems，Elsevier，Amsterdam，1990.
[5]M.Irie，Chem.Rew.2000，100，1685-1716；G.Berkovic，V.Krongauz，Chem.Rew.2000，100，1741-1754；S.Kawata，Y.Kawata.Chem.Rew.2000，100，1777-1788.
[6]E.Kim，S.Y.Cho，Mol.Cryst.Liq.Cryst.，2002，377，385-390.
[7]A.J.Myles，N.R.Brandda，Macromolecules，2003，36，298-303.
[8]V.Mol.Cryst.Liq.Cryst.，1994，246，339-346.
[9]H.Faubl，G.G.Carlson，PCT?WO?030866，2001.
[10]B.V.Gemert，A.Chopra，A.Kumar，PCT?WO?15629，2000.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of photochromic cross-linked polymer containing naphthyl hydroxide pyran group.
The present invention mainly synthesizes following two party monomers (structural formula is as follows) that contain a plurality of polymerized units, and then obtains polymkeric substance with the polymerization of free radical party method.
Agents useful for same is in the reaction: aluminum chloride, 1-bromine hexanol, triethylamine, methacrylic acid, 1,5-dihydroxy naphthlene, tosic acid pyridinium salt, thionyl chloride, acetylene lithium, vinylbenzene and Diisopropyl azodicarboxylate etc.
The present invention relates generally to following several reaction:
1) esterification of phenol: in reaction flask, add 8～10g phenolic compound and 50mL diacetyl oxide, reflux 6 hours, steam diacetyl oxide, residuum adds 100mL water, uses chloroform extraction then three times, combined chloroform solution, washing chloroformic solution, anhydrous sodium sulfate drying.Column chromatography separate the phenol acetic ester compounds, productive rate is between 80～90%.
2) prepare Benzoyl chloride by phenylformic acid: 8.0～10.0g is dissolved in the 50mL thionyl chloride the carboxylic phenol acetic ester, and reflux 5 hours steams excessive thionyl chloride then, and decompression steams the chloride compounds of prepared in reaction again, and productive rate is between 70～90%.
3) preparation of benzophenone cpd: the chloride compounds of equimolar amount and phenol acetic ester compound and 50mL methylene dichloride are joined in the reaction flask, stir, add aluminum chloride 0.3～0.5g, place ice-water bath to react 18h, reaction finishes.Use dichloromethane extraction then three times, combined dichloromethane solution, washing dichloromethane solution, anhydrous sodium sulfate drying.Column chromatography separate benzophenone compound, productive rate is between 70～93%.
4) 1,1-phenylbenzene-2-ethynyl-1-hydroxy kind compound synthetic: in reaction flask, the 0.3mmol benzophenone compound is joined among the 50mL DMF, stir, add 0.3～0.45mmol acetylene lithium then, at room temperature react about 20h, reaction finishes and pours in the 250mL water.Use the chloroform extraction aqueous solution then three times, combined chloroform solution, washing chloroformic solution, anhydrous sodium sulfate drying.The column chromatography separation obtains acetylene compound, productive rate 60～75%.
5) the naphthols pyrylium compound is synthetic: in reaction flask, add the compound that contains alkynyl and 1 of equimolar amount, the 5-dihydroxy naphthlene stirs in the 50mL methylene dichloride, adds tosic acid hydrochloride (PPTS) 0.3～0.5g, at room temperature reacts about 2 days.After finishing, reaction uses dichloromethane extraction three times, combined dichloromethane solution, washing dichloromethane solution, anhydrous sodium sulfate drying.Column chromatography separate the naphthols pyrylium compound, productive rate is between 50～68%.
6) decomposition reaction of acetic ester: in reaction flask, the about 5.0g of naphthols pyrylium compound of acetoxyphenyl is joined in the 50mL ethanol, stir, add 1.0g sodium hydroxide then, be heated to 70～80 ℃ of about 12h of reaction, steam ethanol after reaction finishes, add 100mL water, the pH value of transferring solution is to slightly acidic.Use chloroform extraction then three times, combined chloroform solution, washing chloroformic solution, anhydrous sodium sulfate drying.Column chromatography separate hydroxy-containing compounds, productive rate is between 80～95%.
7) with third rare acyl chlorides and phenol or the synthetic ester of alcohol: reaction flask places ice-water bath, add 25mL methylene dichloride, tetrahydrofuran (THF) 10mL and contain phenolic group or the compound 0.3mmol of alcohol radical, mix and stir, add triethylamine 1.0～1.8mmol then, slowly drip the dichloromethane solution of 1.0～1.4mmol methacrylic chloride then, naturally rise to room temperature, react about 16h.In reaction mixture, add 100mL water then, use dichloromethane extraction three times, combined dichloromethane solution, washing dichloromethane solution, anhydrous sodium sulfate drying.Column chromatography separate monomeric compound, productive rate is between 65～85%.
8) polyreaction: under the nitrogen protection, in 25mL single port reaction flask, 1.0g monomer 5 and 0.1～0.3g Diisopropyl azodicarboxylate are dissolved in 8～10mL tetrahydrofuran (THF) (THF), reacted 4～6 hours down at 80～95 ℃.Sedimentation in methyl alcohol behind the concentration of reaction solution, centrifugation.Precipitation is dissolved in the tetrahydrofuran (THF) again, and sedimentation again repeats twice, gets faint yellow polymer solids, and productive rate is between 80～90%.
Main innovate point of the present invention is: the consistent cross-linked polymer that contains naphthols pyrans photochromic group is provided, compare with adulterated photochromic material, photochromic group not can with polymer body generation phenomenon of phase separation, material is more stable, can obtain the different cross-linked polymer of performance with the monomer polymerization of different other function.This polymkeric substance has actual application value.
Embodiment
Embodiment 1: the preparation of monomer a, and reaction formula is as follows:
The preparation of compound 1:
In reaction flask, add the 10g P-hydroxybenzoic acid, the 50mL diacetyl oxide, reflux 6 hours steams diacetyl oxide, and residuum adds 100mL water, uses chloroform extraction then three times, combined chloroform solution, washing chloroformic solution, anhydrous sodium sulfate drying.Column chromatography separate white solid, 8.8g is to the carboxylic phenol acetic ester.
8.5g is dissolved in the 50mL thionyl chloride the carboxylic phenol acetic ester, and reflux 5 hours steams excessive thionyl chloride then, and decompression steams the chloride compounds 1 of prepared in reaction, 7.3g again.
The preparation of compound 2:
10g phenol joins in the 50mL diacetyl oxide, and reflux 8 hours steams the excessive acetic acid acid anhydride then.Add 100mL water in the residuum, use chloroform extraction three times, washing chloroformic solution, anhydrous sodium sulfate drying.Column chromatography separate colourless liquid, 9.2g.
The preparation of compound 3:
In reaction flask, 7.0g compound 1 is joined in the 50mL methylene dichloride, stir, add 9.0g compound 2 then, the 0.5g aluminum chloride places ice-water bath to react 18h.After finishing, reaction uses dichloromethane extraction three times, combined dichloromethane solution, washing dichloromethane solution, anhydrous sodium sulfate drying.Column chromatography separate compound 3,9.76g, productive rate 89%.
The preparation of compound 4:
In reaction flask, 9.5g compound 3 is joined in the 50mL dry DMF, stir, add 1.0g acetylene lithium then, at room temperature react about 20h, after finishing, reaction adds 200mL water.Use chloroform extraction then three times, combined chloroform solution, washing chloroformic solution, anhydrous sodium sulfate drying.Column chromatography separate compound 4,6.5g, productive rate 65%.
The preparation of compound 5:
In reaction flask, 6.5g compound 4 is joined in the 50mL methylene dichloride, stir, add 3g 1 then, the 5-dihydroxy naphthlene adds 0.5g tosic acid hydrochloride (PPTS), at room temperature reacts about 2d.After finishing, reaction adds dichloromethane extraction three times of 100mL water, combined dichloromethane solution, washing dichloromethane solution, anhydrous sodium sulfate drying.Column chromatography separate compound 5-a, 5.4g, productive rate 60%.
In reaction flask, 5.0g compound 5-a is joined in the 50mL ethanol, stir, add 1g sodium hydroxide then, be heated to 80 ℃ of about 12h of reaction, reaction finishes, and steams ethanol, adds 100mL water.The pH value of transferring mixture with diluted hydrochloric acid aqueous solution is to acid.Use chloroform extraction then three times, combined chloroform solution, washing chloroformic solution, anhydrous sodium sulfate drying.Column chromatography separate compound 5-b, 3.3g, productive rate 85%.
The preparation of monomer a:
Place ice-water bath at reaction flask, add 25mL methylene dichloride, tetrahydrofuran (THF) 10mL and compound 5-b 3.3g, mix and stir, add triethylamine 15mL then, slowly drip the dichloromethane solution of 8mL methacrylic chloride (3.5g) then, at room temperature react about 16h, reaction finishes.Use dichloromethane extraction then three times, combined dichloromethane solution, washing dichloromethane solution, anhydrous sodium sulfate drying.Column chromatography separate compound 5,4.0g, productive rate 80%.
Embodiment 2: the preparation of monomer b, and reaction formula is as follows:
The concrete reaction example of implementing:
Compound 6 and 7 preparation:
In reaction flask, 10.0g phenol, 20.0g salt of wormwood and a small amount of KI are joined among the 50mL DMF, stir, be heated to 85 ℃ and reacted 0.5 hour down.Add 20.0g 1-bromine hexanol then, continue reaction 12 hours, add 250mL water after reducing to room temperature.Use dichloromethane extraction then three times, combined dichloromethane solution, washing dichloromethane solution, anhydrous sodium sulfate drying.Column chromatography separate compound 6,17.5g, productive rate 85%.
In the 150mL round-bottomed flask, 16.0g compound 6 is joined in the 50mL diacetyl oxide, reflux 8 hours steams the excessive acetic acid acid anhydride then.Add 100mL water in the residuum, use chloroform extraction three times, washing chloroformic solution, anhydrous sodium sulfate drying.Column chromatography separate compound 7,17.3g, productive rate 89%.
Compound 8,9 and 10 preparation:
In reaction flask, 10g P-hydroxybenzoic acid, 15.0g salt of wormwood and a small amount of KI are joined among the 65mL DMF, stir, be heated to 85 ℃ and reacted 0.5 hour down.Add 13.5g 1-bromine hexanol then, continue reaction 12 hours, add 300mL water after being reduced to room temperature.Use dichloromethane extraction then three times, combined dichloromethane solution, washing dichloromethane solution, anhydrous sodium sulfate drying.Column chromatography separate compound 8,14.6g, productive rate 85%.
In the reaction flask of water trap is housed, 12.0g compound 8 and 3.5g glacial acetic acid are joined in the 50mL benzene, the back that stirs adds the 6mL vitriol oil.Heating reflux reaction 10 hours is reduced to room temperature, steams solvent benzol, and residuum is poured in the 150mL water, uses chloroform extraction then three times, combined chloroform solution, washing chloroformic solution, anhydrous sodium sulfate drying.Column chromatography separate compound 9,11.3g, productive rate 80%.
10.0g compound 9 is dissolved in the 50mL thionyl chloride, and reflux 5 hours steams excessive thionyl chloride then, and decompression steams the chloride compounds 10 of prepared in reaction, 9.4g, productive rate 88% again.
The preparation of compound 11:
In reaction flask, under the ice-water bath condition 7.0g compound 7 is joined in the 50mL anhydrous methylene chloride, stir, add 9.0g compound 10 then, the 0.8g aluminum chloride, stirring reaction 18h after reaction finishes, adds 100mL water.Use the dichloromethane extraction secondary then, combined dichloromethane solution, washing dichloromethane solution, anhydrous sodium sulfate drying.Column chromatography separate compound 11,11.4g, productive rate 76%.
The preparation of compound 12:
In reaction flask, 11.0g compound 11 is joined among the 50mL DMF, stir, add 1g acetylene lithium then, at room temperature react about 20h, after reaction finished, reaction solution was to going in the 300mL water.Use chloroform extraction then three times, combined chloroform solution, washing chloroformic solution, anhydrous sodium sulfate drying.Column chromatography separate compound 12,7.5g, productive rate 65%.
The preparation of compound 13:
In reaction flask, with 10.0g 1,5-dihydroxy naphthlene, 12.0g salt of wormwood and a small amount of KI join among the 45mLDMF, stir, and are heated to 90 ℃ and react 0.5 hour down.Add 12.0g 1-bromine hexanol then, continue reaction 12 hours, add 250mL water after being reduced to room temperature.Use dichloromethane extraction then three times, combined dichloromethane solution, washing dichloromethane solution, anhydrous sodium sulfate drying.Column chromatography separate compound 13,7.2g, productive rate 66%.
The preparation of compound 14:
In reaction flask, 8.0g compound 12 and 6.5g compound 13 are joined in the 50mL methylene dichloride, stir, add 0.7g tosic acid hydrochloride (PPTS) then, at room temperature react about 3d.Reacted the back and added 100mL water, used dichloromethane extraction three times, combined dichloromethane solution, washing dichloromethane solution, anhydrous sodium sulfate drying.Column chromatography separate compound 14,7.4g, productive rate 63.4%.
The preparation of compound 15:
In reaction flask, with 7.0g compound 14, join in the 60mL ethanol, stir, add 1.2g sodium hydroxide then, be heated to 80 ℃ of about 10h of reaction, reaction finishes, and steams ethanol, adds 100mL water.Transfer the pH value of solution to slightly acidic, to use chloroform extraction three times with aqueous hydrochloric acid, combined chloroform solution, washing chloroformic solution, anhydrous sodium sulfate drying.Column chromatography separate compound 15,4.9g, productive rate 80%.
The preparation of monomer b:
Place ice-water bath at reaction flask, add 35mL methylene dichloride, tetrahydrofuran (THF) 15mL and 4.5g compound 15, mix and stir, behind the adding 5mL triethylamine, slowly drip the dichloromethane solution of 2mL methacrylic chloride (0.86g) then, rise to the about 20h of room temperature afterreaction.Add 150mL water after reaction finishes, use dichloromethane extraction three times, combined dichloromethane solution, washing dichloromethane solution, anhydrous sodium sulfate drying.Column chromatography separate monomer b, 4.6g, productive rate 80%.
The preparation of polymkeric substance:
The preparation of polymkeric substance 1: under the nitrogen protection, in 25mL single port reaction flask, with 1.0g monomer a, the 0.1g Diisopropyl azodicarboxylate is dissolved in the 7mL tetrahydrofuran (THF) (THF), reacts 6 hours down at 80 ℃.Sedimentation in methyl alcohol behind the concentration of reaction solution, centrifugation.Precipitation is dissolved in the tetrahydrofuran (THF) again, and sedimentation again repeats twice, gets faint yellow polymer solids 0.85g, molecular weight 107500, molecular weight dispersity 1.82.
The preparation of polymkeric substance 2: under the nitrogen protection, in 25mL single port reaction flask, with 0.9g monomer b, 0.07g Diisopropyl azodicarboxylate (AIBN) is dissolved in the 7mL tetrahydrofuran (THF) (THF), reacts 7 hours down at 95 ℃.Sedimentation in methyl alcohol behind the concentration of reaction solution, centrifugation.Precipitation is dissolved in the tetrahydrofuran (THF) again, and sedimentation again repeats twice, gets faint yellow polymer solids 0.73g, molecular weight 96300, molecular weight dispersity 1.95.
The preparation of polymkeric substance 3: under the nitrogen protection, in 25mL single port reaction flask, with 0.9g monomer a, 0.3g butyl acrylate and 0.08g Diisopropyl azodicarboxylate (AIBN) are dissolved in the 7mL tetrahydrofuran (THF) (THF), react 6 hours down at 85 ℃.Sedimentation in methyl alcohol behind the concentration of reaction solution, centrifugation.Precipitation is dissolved in the tetrahydrofuran (THF) again, and sedimentation again repeats twice, gets faint yellow polymer solids 0.65g, molecular weight 87500, molecular weight dispersity 1.85.
The preparation of polymkeric substance 4: under the nitrogen protection, in 25mL single port reaction flask, with 0.8g monomer b, 0.2g vinylbenzene and 0.1g Diisopropyl azodicarboxylate (AIBN) are dissolved in the 10mL tetrahydrofuran (THF) (THF), react 7 hours down at 90 ℃.Sedimentation in methyl alcohol behind the concentration of reaction solution, centrifugation.Precipitation is dissolved in the tetrahydrofuran (THF) again, and sedimentation again repeats twice, gets faint yellow polymer solids 0.65g, molecular weight 116800, molecular weight dispersity 1.73.
Claims (2)
1. the synthetic method of photochromic cross-linked polymer containing naphthyl hydroxide pyran group is characterized in that: at first synthetic following two polymerization single polymerization monomers that contain a plurality of polymerized units, and its structural formula is as follows, and then obtains polymkeric substance with the free radical polymerisation process polymerization:
Agents useful for same is in the reaction: aluminum chloride, 1-bromine hexanol, triethylamine, methacrylic acid, 1,5-dihydroxy naphthlene, tosic acid pyridinium salt, thionyl chloride, acetylene lithium, vinylbenzene and Diisopropyl azodicarboxylate;
Concrete steps are as follows:
1) esterification of phenol: in flask, add 8～10g P-hydroxybenzoic acid and 50ml diacetyl oxide, reflux 6 hours steams diacetyl oxide, and residuum adds 100ml water, use chloroform extraction then three times, combined chloroform solution, washing chloroformic solution, anhydrous sodium sulfate drying, column chromatography separate the phenol acetic ester compound, productive rate is between 80～90%;
2) prepare Benzoyl chloride by phenylformic acid: 8.0～10.0g is dissolved in the 50ml thionyl chloride the carboxylic phenol acetic ester, and reflux 5 hours steams excessive thionyl chloride then, and decompression steams the chloride compounds of prepared in reaction again, and productive rate is between 70～90%;
3) preparation of benzophenone cpd: the chloride compounds of equimolar amount and phenol acetic ester compound and 50ml methylene dichloride are joined in the reaction flask, stir, add aluminum chloride 0.3～0.5g, place ice-water bath to react 18h, reaction finishes; Use dichloromethane extraction then three times, combined dichloromethane solution, the washing dichloromethane solution, anhydrous sodium sulfate drying, column chromatography separate benzophenone compound, productive rate is between 70～93%;
4) 1,1-phenylbenzene-2-ethynyl-1-hydroxy kind compound synthetic: in reaction flask, the 0.3mmol benzophenone compound is joined among the 50ml DMF, stir, add 0.3～0.45mmol acetylene lithium then, at room temperature react 20h, reaction finishes and pours in the 250ml water; Use the chloroform extraction aqueous solution then three times, combined chloroform solution, the washing chloroformic solution, anhydrous sodium sulfate drying, the column chromatography separation obtains acetylene compound, productive rate 60～75%;
5) the naphthols pyrylium compound is synthetic: in reaction flask, add the compound that contains alkynyl and 1 of equimolar amount, the 5-dihydroxy naphthlene stirs in the 50ml methylene dichloride, adds tosic acid hydrochloride 0.3～0.5g, at room temperature reacts 2 days; Reaction finishes the back with dichloromethane extraction three times, combined dichloromethane solution, the washing dichloromethane solution, anhydrous sodium sulfate drying, column chromatography separate the naphthols pyrylium compound, productive rate is between 50～68%;
6) decomposition reaction of acetic ester: in reaction flask, the naphthols pyrylium compound 5.0g of acetoxyphenyl is joined in the 50ml ethanol, stir, add 1.0g sodium hydroxide then, be heated to 70～80 ℃ of reaction 12h, steam ethanol after reaction finishes, add 100ml water, the pH value of transferring solution is to slightly acidic; Use chloroform extraction then three times, combined chloroform solution, the washing chloroformic solution, anhydrous sodium sulfate drying, column chromatography separate hydroxy-containing compounds, productive rate is between 80～95%;
7) with acrylate chloride and phenol or the synthetic ester of alcohol: reaction flask places ice-water bath, add 25ml methylene dichloride, tetrahydrofuran (THF) 10ml and contain phenolic group or the compound 0.3mmol of alcohol radical, mix and stir, add triethylamine 1.0～1.8mmol then, slowly drip the dichloromethane solution of 1.0～1.4mmol methacrylic chloride then, naturally rise to room temperature, reaction 16h; In reaction mixture, add 100ml water then, with dichloromethane extraction three times, combined dichloromethane solution, washing dichloromethane solution, anhydrous sodium sulfate drying, column chromatography separate monomeric compound, productive rate is between 65～85%;
8) polyreaction: under the nitrogen protection, in 25ml single port reaction flask, 0.9～1.2g monomer 5 and 0.1～0.3g Diisopropyl azodicarboxylate are dissolved in 8～10ml tetrahydrofuran (THF), reacted 4～6 hours down at 80～95 ℃; Sedimentation in methyl alcohol behind the concentration of reaction solution, centrifugation; Precipitation is dissolved in the tetrahydrofuran (THF) again, and sedimentation again repeats twice, gets faint yellow polymer solids, and productive rate is between 80～90%.
2. the photochromic cross-linked polymer containing naphthyl hydroxide pyran group that makes according to the described preparation method of claim 1.
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| US6113814A (en) * | 1998-09-11 | 2000-09-05 | Transitions Optical, Inc. | Polymerizable polyalkoxylated naphthopyrans |
| CN1328108A (en) * | 2000-06-12 | 2001-12-26 | 中国科学院感光化学研究所 | Arylheterocycle substituted naphthopyran-type photochromic compound and its preparing process and usage |
| EP1214311B1 (en) * | 1999-09-17 | 2004-09-15 | Transitions Optical, Inc. | Novel indeno-fused photochromic naphthopyrans |
| CN1761660A (en) * | 2003-03-20 | 2006-04-19 | 光学转变公司 | Indeno-fused photochromic naphthopyrans, naphthols and photochromic articles |
| CN101215282A (en) * | 2007-12-27 | 2008-07-09 | 上海交通大学 | Photochromic naphtho-pyrans compounds and synthetic method thereof |
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Patent Citations (5)
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| US6113814A (en) * | 1998-09-11 | 2000-09-05 | Transitions Optical, Inc. | Polymerizable polyalkoxylated naphthopyrans |
| EP1214311B1 (en) * | 1999-09-17 | 2004-09-15 | Transitions Optical, Inc. | Novel indeno-fused photochromic naphthopyrans |
| CN1328108A (en) * | 2000-06-12 | 2001-12-26 | 中国科学院感光化学研究所 | Arylheterocycle substituted naphthopyran-type photochromic compound and its preparing process and usage |
| CN1761660A (en) * | 2003-03-20 | 2006-04-19 | 光学转变公司 | Indeno-fused photochromic naphthopyrans, naphthols and photochromic articles |
| CN101215282A (en) * | 2007-12-27 | 2008-07-09 | 上海交通大学 | Photochromic naphtho-pyrans compounds and synthetic method thereof |
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