CN103172878A - Synthesis method of silicon-based photochromic elastomer containing naphthol pyran and having cross-linked structure - Google Patents
Synthesis method of silicon-based photochromic elastomer containing naphthol pyran and having cross-linked structure Download PDFInfo
- Publication number
- CN103172878A CN103172878A CN2012103291758A CN201210329175A CN103172878A CN 103172878 A CN103172878 A CN 103172878A CN 2012103291758 A CN2012103291758 A CN 2012103291758A CN 201210329175 A CN201210329175 A CN 201210329175A CN 103172878 A CN103172878 A CN 103172878A
- Authority
- CN
- China
- Prior art keywords
- photochromic
- elastomer
- pyran
- monomer
- silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention belongs to a synthesis method of an organic/polymer material, and specifically relates to a synthesis method of a silicon-based photochromic elastomer containing naphthol pyran and having a cross-linked structure. Hydrogen-containing silicon oil is used as a soft chain segment, a naphthol pyran polymer monomer containing a polymerization unit is a photochromic functional group, and a naphthol pyran polymer monomer containing two polymerization units is a cross linking agent; and at certain temperature, a silicon-based photochromic elastomer having a cross-linked structure is prepared by taking chloroplatinic acid as a catalyst. In the preparation process, the conditional reaction materials are proportioned, and the content of the photochromic elastomer is 20-50% so as to ensure that the obtained block polymer has the properties of an elastomer. At present, a report about the silicon-based photochromic elastomer containing naphthol pyran and having a cross-linked structure is unavailable. The elastomer with the structure has the characteristics of an elastomer and has photochromic property, and can be used for preparing a flexible optical device.
Description
Technical field
[0001] the invention belongs to the synthetic method of organic/polymer materials, be specifically related to a kind of silica-based photochromic elastomeric synthetic method that crosslinking structure contains naphthyl hydroxide pyran group that has.
Background technology
[0002] photochromism (Photochromism) refers to that a compound molecule can carry out reversible variation having between two kinds of molecularities of different spectral qualities being subject under the different wave length radiation molecule, and the molecule of these two kinds of different structures has different spectral qualities, and is as different in colour-change or absorption spectrum.This under the effect of light or heat, reversible change phenomenon can occur and be called photochromism in the molecular structure of compound
[1]Photochromic compound and polymkeric substance thereof are a kind of new function materials, can be widely used in the Disciplinary Frontiers such as optical switch, optical storage and nonlinear optics
[2-3], wherein photochromic material also has a well-known application to be applied to exactly chameleon glass block, and the naphthols pyrans is to be applied to color-changing lens the earliest and the photochromic material of moulding
[4]Because photochromic material has huge potential using value, scientific workers are in this field, comprise that the performance characterization of design, preparation and material of novel material and the aspects such as preparation of device all done a large amount of work
[5]The photochromic material of report mainly contains the Luo oxazine at present
[6], nitrogen benzide
[7], the phenoxy group naphtho naphthoquinone
[8], diarylethene
[9], naphthols pyrans and spiro-pyrans
[10]Deng group.
Elastomerics (or being called rubber) is the elastomeric network structure that contains the low cross-linking degree of chemistry or physical nodes.Since nineteen forty-four pure natural and the elastomerics of synthetic by reported first since
[11], the researchist conducts extensive research all kinds of elastomeric properities and application, makes elastomerics all have practical application aspect a lot.Elastomerics can be used for cable jacket, casting films, fiber, automotive upholstery, exterior trimming parts, sealing articles for use, non-woven fabrics, packing, personal hygiene article, coating etc., in addition, elastomerics also can be applicable to curable product, as implanted medical material and artificial muscle etc.
[12]
Although common amorphous polymer has good application aspect a lot, the deficiency on self using is arranged also.These materials are all crisp and easily broken usually, and need in very high temperature, namely could realize on the second-order transition temperature of polymkeric substance on some is used.For example, polystyrene can not at room temperature carry out when the application aspect actuator, can only just can more than the second-order transition temperature of polymkeric substance
[13]In addition organizational project and useful for drug delivery aspect have the multipolymer of the biodegradable material of potential application such as polylactide, caprolactone and rac-Lactide and glycollide also must be more than the physiology stability when using
[14]Because elastomerics has good flexibility at normal temperatures, can prepare difform devices such as having bending, and have at normal temperatures good processibility, just in time made up these deficiencies of amorphous polymer.
Photochromic group is incorporated in elastomerics, can makes elastomerics have novel character.Such as azobenzene group is incorporated in elastomerics SBS, make elastomerics can be used for preparing grating and optical storage
[15], under the effect of light, shape and the internal pressure of introducing the elastomer sample of liquid crystal azobenzene group all can change.In addition, the photochromic group with liquid crystal property is incorporated into makes elastomerics in elastomerics bending phenomenon occurs under the effect of optical radiation, make material namely have liquid crystal property and have again elastomeric characteristic
[16]By free radical polymerisation process, Luo oxazine and spiro-pyrans are incorporated in elastomerics SBS, elastomeric stretching can cause the dynamic (dynamical) considerable change of photochromic colour killing
[17]
In patent ZL201010290640.2, we utilize the atom transferred free radical method to prepare the photochromic elastomerics of Han Luo oxazine and spiro-pyrans, connect by ester group between polybutadiene block and photochromic polymer block.In this application, we adopt containing hydrogen silicone oil as soft chain segment, take the naphthols pyrans polymerization single polymerization monomer that contains a polymerized unit as the photochromic function group, take the naphthols pyrans polymerization single polymerization monomer that contains two polymerized units as linking agent, the silica-based photochromic elastomerics that utilizes Platinic chloride to have crosslinking structure for the catalyzer preparation.At present, yet there are no the relevant this silica-based photochromic elastomeric report that crosslinking structure contains naphthyl hydroxide pyran group that has.Like this material make the kind of not only having enriched the photochromic polymer material, also may provide the material of the light functional polymer with distinguishing feature and excellent property for the polymers function material.
Reference:
[?1?]?R.?S.?Becker,?J.?Michl,
?J.?Am.?Chem.?Soc,?1966,88,5931-5933.
[?2?]?G.?Berkovic,?V.?Krongauz,?V.?Weiss,
?Chem.?Rev.?2000,100,1741-1754.
[?3?]?J.?A.?Delaire,?K.?Nakatani,?
Chem.?Rev.?2000,100,1817-1846.
[4?]?S.?Higgins,?Chasing?a?Rainbow,?
Chem.?Bar.?2003,6,26-29
[5?]?M.Irie,?
Chem.?Rew.?2000,100,1685-1716.
[6?]?Y.?Fu,?H.?Chen,?D.?Qiu,?et?al.,?
Langmuir,?2002,18,4989-4995.
[7]?J.?A.?Delaire,?K.?Nakatani,?
Chem.?Rev.,?2000,100,?1817-1845.
[8]?J.?Malkin,?A.?Zelichenok,?V.?Krongauz,?et?al.,?
J.?Am.?Chem.?Soc.,?1994,116,1101-1105.
[9]?M.?Tomasulo,?E.?Deniz,?R.?J.?Alvarado,?F.?M.?Raymo,
?J.?Phys.?Chem.?C?2008,?112,?8038-8045.
[10]?K.?Nakatani,?P.?Yu,?
Adv.?Mater.,?2001,13(18),1411-1413.
[11]?C.?E.?Hall,?E.?A.?Hauser,?D.?S.?le?Beau,?F.?O.?Schmitt?and?P.?TalaIay,?
Ind.?Eng.?Chem,?1944,?36,?634.
[12]?H.?B.?LEE,?H.?QUACH,?D.?B.?BERRY,?and?W.?J.?STITH,?
Polymeric?Materials?and?Artificial?Organs,?Chapter?7,?1984,?pp?99-109,?ACS?Symposium?Series,?Volume?256.
[13]?J.?He,?Y.?Zhao,?Y.?Zhao,?
Soft?matter,?2009,5,308.
[14]?B.?G.?Amsden,?G.?Misra,?F.?Gu,?H.?M.?Younes,?
Biomacromolecules,?2004
,?5,?
2479.
[15]?Y.?Zhao,?S.?Y.?Bai,?D.?Dumont,?T.?V.?Galstian,?
Adv.?Mater.?2002,?14,?512.
[16]?M.?Warner,?E.?M.?Terentjev?Liquid?Crystal?Elastomers.?Oxford:?Clarendon?Press,?2003.
[17]?X.?C.?Zhao,?Guang?Wang,?Kuo?Zhang,?J?Appl?Poly?Sci,?Published?on?line.?http://onlinelibrary.wiley.com/advanced/search/results.
Summary of the invention
The purpose of this invention is to provide a kind of silica-based photochromic elastomeric synthetic method that crosslinking structure contains naphthyl hydroxide pyran group that has.
Monomer 1,2 and synthesized reference document (the Xiancai Zhao of monomer 3, Guang Wang and Kuo Zhang, Journal of Applied Polymer Science, 2012,124 (5), 4157 – 4164 and Xiancai Zhao, Guang Wang and Kuo Zhang, Journal of Applied Polymer Science, published on line, http://onlinelibrary.wiley.com/advanced/search/results) prepare.The structural formula of the naphthols pyrans polymerization single polymerization monomer 1,2,3,4 that the application selects is as follows:
In reaction, agents useful for same is: n-butyllithium solution, benzophenone, trimethylsilyl acetylene, 2,6-dihydroxy naphthlene, ethylene bromohyrin, 6-bromoethanol, 4-hydroxy phenyl benzophenone, third rare acyl chlorides, hydrochloric acid, triethylamine, Platinic chloride, containing hydrogen silicone oil, divinyl.
The synthetic route of monomer 4 and step be as shown in Figure 2:
Synthesizing of compound a:With 9.9g(50 mmol) 4-dihydroxy benaophenonel, 10.3g (75 mmol) Anhydrous potassium carbonate, a fritter potassiumiodide and 100ml N, the mixture of dinethylformamide (DMF) was heated to 70 reactions after 1 hour in the 250ml there-necked flask of return line is housed, splash into the 15ml solution of 6.8g (55mmol) ethylene bromohyrin.Then be down to room temperature after being warming up to 85 ℃ of reaction 24h, mixture is poured in 400ml distilled water, regulate pH=6 with hydrochloric acid, static 1 hour, suction filtration.With ethyl acetate (50ml * 3) extraction, anhydrous sodium sulfate drying.Product chromatographic column purifying (ethyl acetate: sherwood oil=1:4), get white solid, 6.0g, productive rate 60%.
Compound b's is synthetic:Under the anhydrous and oxygen-free condition, 3ml (20mmol) trimethylsilyl acetylene and 5ml tetrahydrofuran (THF) are joined in 100ml single port flask, after making reaction system be down to-10 ℃ with the electronics low-temperature cooling system, add 8ml(20mmol) n-Butyl Lithium, stirring reaction one hour.The tetrahydrofuran solution of 6ml compound a (2.8g, 20mmol) joins in reaction system, continues reaction and is warming up to 0 ℃ after 3 hours, adds the methanol solution of 20ml potassium hydroxide (1.36g).React and rise to normal temperature after 15 minutes, transfer pH=7 with Glacial acetic acid, with ethyl acetate extraction three times.Product is through silica gel column chromatography separating purification (ethyl acetate: sherwood oil=1:5), get yellow solid 2.0g, productive rate 71%.
Compound c's is synthetic:
With 20g(124.9mmol) 2, the mixture of 6-dihydroxy naphthlene, 24.3g (17.48mmol), a fritter potassiumiodide and 110mlDMF was heated to 80 reactions after 1 hour in the 250ml there-necked flask of return line is housed, splash into the 20ml solution of 15.6g (124.9mmol) ethylene bromohyrin.Then be down to room temperature after being warming up to 85 ℃ of reaction 24h, mixture is poured in 450ml distilled water, regulate pH=6 with hydrochloric acid, static 1 hour, suction filtration.With ethyl acetate (50ml * 3) extraction, anhydrous sodium sulfate drying.Product chromatographic column purifying (ethyl acetate: sherwood oil=5:8), get white solid, 4.5g, productive rate 22%.
Synthesizing of monomer 4:
Under nitrogen protection in the round-bottomed flask of 50ml with 2.08g (10mmol)
bAnd 2.04g (10mmol)
cBe dissolved in 10ml CH
2Cl
2, stirred 10 minutes under room temperature, add the 0.2g p-methyl benzenesulfonic acid.At reaction 48h, decompression steams CH
2Cl
2, with this mixture of acetic acid ethyl dissolution, (4 * 30ml) extractions, anhydrous sodium sulfate drying is with silica gel column chromatography (ethyl acetate: sherwood oil=1:2) get orange/yellow solid 1.05g, productive rate 48%. after separation to add afterwards water
Containing the naphthols pyrans has the silica-based photochromic elastomeric synthetic method of crosslinking structure: in the three-necked flask of the 100ml that reflux condensing tube and dropping funnel are housed, add the containing hydrogen silicone oil, 25～55ml toluene of 1.5～2.0g and with respect to the solution of 0.5～2.5% Platinic chloride of naphthols pyrans polymerization single polymerization monomer quality, pass into 15 minutes post-heating of argon gas, when temperature rises to 50～100
oDuring C, drip the mixing solutions that 0.2～0.5g has 10～30ml toluene of the naphthols pyrans monomer of a polymerized unit and the monomer 4 that 0.2～0.4g has the linking agent effect, dripped off in 1～3 hour, then continue to be heated to reflux, stopped reaction after 1～4 hour.Remaining toluene is removed in underpressure distillation, residuum is dissolved in a small amount of tetrahydrofuran solvent, sedimentation obtains photochromic elastomerics 2～4 times in cold methyl alcohol after the aluminium sesquioxide post is gone out catalyzer, and product is the very low solid matter of hardness, productive rate 70～90%.
Major advantage of the present invention is: a kind of photochromic elastomeric synthetic method that crosslinking structure contains the naphthols pyrans that has take Platinic chloride as catalyzer prepares is provided, operation is simple for present method, and prepared product namely has photochromic property and has again elastomeric character.At present, yet there are no the relevant this silica-based photochromic elastomeric report that crosslinking structure contains naphthyl hydroxide pyran group that has.Like this material make the kind of not only having enriched the photochromic polymer material, also may provide the material of the light functional polymer with distinguishing feature and excellent property for the polymers function material.
Description of drawings
Accompanying drawing 1 is the abosrption spectrogram of film before and after UV-irradiation that product of the present invention is pressed into;
Accompanying drawing 2 is synthetic route and steps of monomer 4.
Embodiment
Embodiment 1:In the three-necked flask of the 100ml that reflux condensing tube and dropping funnel are housed, add the aqueous solution of containing hydrogen silicone oil, 25ml toluene and the 0.004g Platinic chloride of 1.5g, pass into 15 minutes post-heating of argon gas, when temperature rises to 65
oDuring C, drip the 0.3g monomer
1With the 0.1g monomer
4The toluene mixing solutions of 15ml, dripped off in 2 hours, then continue to be heated to reflux, stopped reaction after 2 hours.Remaining toluene is removed in underpressure distillation, residuum is dissolved in a small amount of tetrahydrofuran solvent, and sedimentation obtains photochromic elastomerics 3 times in cold methyl alcohol after the aluminium sesquioxide post is gone out catalyzer, and product is the very low solid matter of hardness, 1.64g, productive rate 86.3%.The structural formula of product is as follows:
After using vulcanizing press that product is pressed into film, film can extend under stretching action within the specific limits, the state before can automatically recovering again to stretch after the cancellation stretching action.This proves absolutely that product has elastomeric character.Made film can change by diffraction under UV-irradiation, illustrates that it has photochromism.Accompanying drawing is the abosrption spectrogram of film before and after UV-irradiation, further illustrates product and has photochromic property.
Embodiment 2:
In the three-necked flask of the 100ml that reflux condensing tube and dropping funnel are housed, add the aqueous solution of containing hydrogen silicone oil, 18ml toluene and the 0.003g Platinic chloride of 1.0g, pass into 15 minutes post-heating of argon gas, when temperature rises to 80
oDuring C, drip the 0.2g monomer
2With the 0.08g monomer
4The toluene mixing solutions of 10ml, dripped off in 1.5 hours, then continue to be heated to reflux, stopped reaction after 3 hours.Remaining toluene is removed in underpressure distillation, residuum is dissolved in a small amount of tetrahydrofuran solvent, and sedimentation obtains photochromic elastomerics 3 times in cold methyl alcohol after the aluminium sesquioxide post is gone out catalyzer, and product is the very low solid matter of hardness, 0.98g, productive rate 76.5%.The structural formula of product is as follows:
Embodiment 3:
In the three-necked flask of the 100ml that reflux condensing tube and dropping funnel are housed, add the aqueous solution of containing hydrogen silicone oil, 25ml toluene and the 0.003g Platinic chloride of 1.2g, pass into 15 minutes post-heating of argon gas, when temperature rises to 45
oDuring C, drip the 0.25g monomer
3With the 0.1g monomer
4The toluene mixing solutions of 15ml, dripped off in 2.5 hours, then continue to be heated to reflux, stopped reaction after 3 hours.Remaining toluene is removed in underpressure distillation, residuum is dissolved in a small amount of tetrahydrofuran solvent, and sedimentation obtains photochromic elastomerics 3 times in cold methyl alcohol after the aluminium sesquioxide post is gone out catalyzer, and product is the very low solid matter of hardness, 1.28g, productive rate 82.6%.The structural formula of product is as follows:
Claims (2)
1. containing the naphthols pyrans has the silica-based photochromic elastomeric synthetic method of crosslinking structure, it is characterized in that: in the three-necked flask of the 100ml that reflux condensing tube and dropping funnel are housed, add the containing hydrogen silicone oil, 25～55ml toluene of 1.5～2.0g and with respect to the solution of 0.5～2.5% Platinic chloride of naphthols pyrans polymerization single polymerization monomer quality, pass into 15 minutes post-heating of argon gas, when temperature rises to 50～100
oDuring C, drip the mixing solutions that 0.2～0.5g has 10～30ml toluene of the naphthols pyrans monomer of a polymerized unit and the monomer 4 that 0.2～0.4g has the linking agent effect, dripped off in 1～3 hour, continue again to be heated to reflux, stopped reaction after 1～4 hour, remaining toluene is removed in underpressure distillation, residuum is dissolved in a small amount of tetrahydrofuran solvent, sedimentation obtains photochromic elastomerics 2～4 times in cold methyl alcohol after the aluminium sesquioxide post is gone out catalyzer, product is the very low solid matter of hardness, productive rate 70～90%, wherein the monomer structure formula is respectively:
。
2. have by what method claimed in claim 1 made a silica-based photochromic elastomerics that crosslinking structure contains naphthyl hydroxide pyran group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210329175.8A CN103172878B (en) | 2012-09-07 | 2012-09-07 | Synthesis method of silicon-based photochromic elastomer containing naphthol pyran and having cross-linked structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210329175.8A CN103172878B (en) | 2012-09-07 | 2012-09-07 | Synthesis method of silicon-based photochromic elastomer containing naphthol pyran and having cross-linked structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103172878A true CN103172878A (en) | 2013-06-26 |
| CN103172878B CN103172878B (en) | 2014-10-01 |
Family
ID=48633102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210329175.8A Expired - Fee Related CN103172878B (en) | 2012-09-07 | 2012-09-07 | Synthesis method of silicon-based photochromic elastomer containing naphthol pyran and having cross-linked structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103172878B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356282A (en) * | 2014-10-19 | 2015-02-18 | 吉林大学 | Photochromic fluorescent switchable nanoparticle containing naphthopyran as well as preparation method |
| WO2020261961A1 (en) * | 2019-06-27 | 2020-12-30 | 株式会社トクヤマ | Chromene compound and photochromic optical article |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1242009A (en) * | 1996-12-23 | 2000-01-19 | 康宁股份有限公司 | (Benzofuran) naphthopyrans, the compositions and (CO) polymer matrices containing them |
| CN1250438A (en) * | 1997-03-21 | 2000-04-12 | 康宁股份有限公司 | Naphthopyran derivatives, compositions and (CO) polymers matrices containing same |
| CN1608216A (en) * | 2001-12-27 | 2005-04-20 | 光学转变公司 | Photochromic optical article |
| WO2005095541A1 (en) * | 2004-03-04 | 2005-10-13 | Transitions Optical, Inc. | Photochromic optical article |
-
2012
- 2012-09-07 CN CN201210329175.8A patent/CN103172878B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1242009A (en) * | 1996-12-23 | 2000-01-19 | 康宁股份有限公司 | (Benzofuran) naphthopyrans, the compositions and (CO) polymer matrices containing them |
| CN1250438A (en) * | 1997-03-21 | 2000-04-12 | 康宁股份有限公司 | Naphthopyran derivatives, compositions and (CO) polymers matrices containing same |
| CN1608216A (en) * | 2001-12-27 | 2005-04-20 | 光学转变公司 | Photochromic optical article |
| WO2005095541A1 (en) * | 2004-03-04 | 2005-10-13 | Transitions Optical, Inc. | Photochromic optical article |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356282A (en) * | 2014-10-19 | 2015-02-18 | 吉林大学 | Photochromic fluorescent switchable nanoparticle containing naphthopyran as well as preparation method |
| WO2020261961A1 (en) * | 2019-06-27 | 2020-12-30 | 株式会社トクヤマ | Chromene compound and photochromic optical article |
| EP3995493A4 (en) * | 2019-06-27 | 2023-10-04 | Tokuyama Corporation | Chromene compound and photochromic optical article |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103172878B (en) | 2014-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102643432B (en) | Preparation method for cholesteric siloxane side-chain liquid crystal polymer | |
| KR101614824B1 (en) | Polydialkylsiloxane-bridged bi-photochromic molecules | |
| AU2011227188B2 (en) | Silicone (meth)acrylamide monomer, polymer, ophthalmic lens, and contact lens | |
| JP5568643B2 (en) | Photochromic material | |
| CN109608564B (en) | Azo-phenyl-containing side chain type liquid crystal polymer with microphase separation structure and preparation method thereof | |
| CN103145994A (en) | Trapezoidal polysiloxane and preparation method thereof | |
| CN103172878B (en) | Synthesis method of silicon-based photochromic elastomer containing naphthol pyran and having cross-linked structure | |
| AU710875B2 (en) | Chromene compounds and photochromic materials | |
| CN108484905A (en) | A kind of side chain has the cluster peptide and preparation method thereof of UCST behaviors containing carboxyl | |
| CN109456435A (en) | A kind of synthetic method of the perfluorocyclobutanearyl polyarylether containing Phthalazinone | |
| KR20110090830A (en) | Novel fluorinated compounds, composition comprising the same and method for preparing of film using the same | |
| US20110198546A1 (en) | Photochromic material | |
| WO2011116206A1 (en) | Silicone (meth)acrylamide monomer, polymer, ophthalmic lens, and contact lens | |
| CN112552897A (en) | Triaryl ethylene photochromic material, method and application as 3D printing ink | |
| CN115991709B (en) | Alkenyl-terminated tetraaryl metalloporphyrin compound containing ethylene glycol unit, and preparation method and application thereof | |
| CN106279247B (en) | A kind of furans functionalization cage modle polyhedral oligomeric silsesquioxane and preparation method thereof | |
| JP2006282990A (en) | Thermoplastic resin composition, method for producing the same, and optical actuator material | |
| CN106496557A (en) | A kind of preparation method of high transparency high temperature resistant fluorinated polyimide resin | |
| CN110698676A (en) | Photochromic material, preparation method and contact lens | |
| JP5835723B2 (en) | Divinyl ether homopolymer, production method thereof and use thereof | |
| CN1687300A (en) | Nano composite materials and products of photochromism of heterocyclic ring substituted spirooxazine compounds | |
| CN114051497A (en) | Chromene compound and photochromic optical article | |
| CN104629056A (en) | Preparation method of phenyl vinyl silicon resin | |
| CN104788677A (en) | Phenyl hydrogen silicone resin with H group in T chain link and preparation method thereof | |
| CA2582605A1 (en) | Photochromic compound and optical functional material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141001 Termination date: 20150907 |
|
| EXPY | Termination of patent right or utility model |