KR20000014038A - Process for preparing diarylethene substituted styrene copolymer and photorecordig thin film - Google Patents

Abstract

PURPOSE: A diarylethene copolymer is prepared which has a good mechanical property, rapid photochromism and processability. CONSTITUTION: The diarylethene copolymer(formula 1: R1 is hydrogen atom, C1-22 alkyl, fluorine, substituted or unsubstituted phenyl or phenylalkyl; R2 is C1-22 alkylene substituted or unsubstituted fluorine; R3 is oxygen atom or C1-3 alkylene substituted or unsubstituted fluorine; R4 is same to R1 or C1-22 alkylene or alkyleneoxyalkyl ester substituted or unsubstituted fluorine; R5 is same to R2 or C1-22 alkyleneoxy group substituted or unsubstituted fluorine; X and Y are independently oxygen, nitrogen, or sulfur atom; Z is fluorine substituted or not substituted methylene or carbonyl; o, p, q, and r are mole ratios; o+p+q+r=1) is prepared.

Description

Method for preparing styrenic copolymer composition substituted with diarylethene and method for manufacturing optical recording thin film

The present invention relates to a method for producing a styrenic copolymer composition substituted with diarylethene having excellent adhesiveness, fast photochromic speed, excellent adhesiveness, and excellent processability, and a method for manufacturing an optical recording thin film.

Since diarylethene-based photochromic compounds have been synthesized in 1985, they have been known as stable photochromic compounds without heat discoloration after irradiation (Japan Kokai Tokkyo Koho; JP 86263935 A2, J. Org. Chem., 1991 , 49, 373). Accordingly, the synthesis method of various derivatives has been studied, and many studies have been published to use them in reversible optical disks, erasable optical disks, optical switches for photo-integrated devices, organophotoreceptors, photoelectrodes, etc. (Japan Kokai Tokkyo Koho; JP 91261782 A2, ; JP 91261781 A2, JP 91261762 A2, JP 92178383 A2, JP 92178382 A2, JP 94199846 A2 ,, JP 91135977 A2, JP 9359025 A2, JP 93169820 A2, JP 9311406 A2, JP 93301873 A2, JP 942670725 A2 JP 9669083 A2, JP 96245579 A2, JP 9761647 A2, JP 9780681 A2; Takeshita, M; Uchida, K .; Irie, M. Chem. Commun, 1996, 1807-1808, etc.).

The diarylethene-based compound changes color when exposed to ultraviolet light, and then returns to the original color of the compound when irradiated with light of a different wavelength, and is used in applications where color change or colorization caused by light is caused. Various types of photochromic compounds have been proposed (Japan Kokai Tokkyo Koho; JP 9589954 A2, JP 9771585 A2, JP 9777743 A2, JP 9777767 A2, JP 05-301873 A2, etc.).

Among them, fluorine-substituted diaryl ethene and diaryl ethene substituted with maleic anhydride have high dark stability and fast photochromic properties, and are compatible with polymer resins. Has been published (J. Org. Chem., 1991, 49, 373).

However, when the low molecular weight diarylethene compound is introduced into the polymer resin, the compatibility is not sufficient, and the diarylethene photochromic compound is eluted from the polymer medium during long-term storage and phase separation occurs. Accordingly, there is a problem in that the reliability and storage stability of the optical record is poor when used for a long time. In particular, when applied optically, photochromic reversibly occurs, accompanied by a change in refractive index. The problem of phase separation of low molecular weight diaryethene is different every time the photochromicity or refractive index changes are repeated. It will lead to an error.

To solve this problem, polymers in which diarylethene is substituted with a side chain in the polymethacryl backbone have been developed (Japan Kokai Tokkyo Koho; JP 06/240242 A2). However, the synthesis of the diaryethene methacrylate monomer is difficult by using a low temperature reaction, the prepared polymer has poor mechanical properties, and the adhesive strength on the plastic plate such as glass plate, PC, PMMA, PE has a disadvantage.

In addition, since it is substituted with alkylene substituted with hydrogen or fluorine between diarylethene and methacryl group, it cannot stabilize the polarized excited state structure generated when the diarylethene group is irradiated by light and excited within an extremely short time. There is a limit to the application to the photochromic thin film using the polarity of the excited state, such as the application of a fast refractive index change.

In order to solve the above problems, the present inventors are connected to a polar group such as a carboxyl group, and are easily synthesized and separated, and have excellent photochromic properties, excellent mechanical properties, and a diaryl that can solve the problem of phase separation or compound formation. A study was made on how to synthesize tenpolymers. As a result, the formula to the benzene ring of ten XR ₂ OC (= O) in the diaryl as 2 - (where X is a methacrylate group) the dia to the X monomer to the reel to and styrenic monomer of the general formula (3) is substituted by the formula Polymerization of the composition comprising the compound of 4 in the presence of the initiator to produce a photochromic polymer of the general formula (1) excellent in mechanical properties, fast photochromic speed, excellent processability, from a composition in which the polymer is dissolved in an organic solvent It was found that the photochromic thin film was formed and the present invention was completed.

1 is a TGA showing the weight loss with respect to the heat of the copolymer of diarylethene-styrene prepared in Example 5;

FIG. 2 is a graph showing changes in the spectrum absorption spectrum (dotted line: before light irradiation and solid line: 1 minute after light irradiation) that appear when irradiating a short wavelength of 310 nm to the thin film prepared in Example 11. FIG.

Accordingly, it is a first object of the present invention to provide a diarylethene-based polymer having excellent photochromic properties. Diaryl ethene-based polymer according to the invention corresponds to the formula (1).

[In the above formula,

R ₁ represents a hydrogen atom or a C _1-22 alkyl group, or a fluorine group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted pentylalkyl group;

R ₂ represents a C _1-22 alkylene group unsubstituted or substituted with fluorine;

R ₃ represents a C _1-3 alkylene group unsubstituted or substituted with a bond line, an oxygen atom, or fluorine;

X and Y each independently represent an oxygen, nitrogen or sulfur atom;

Z represents a methylene group or a carbonyl group unsubstituted or substituted with fluorine.]

R ₄ is the same as R ₁ or represents a C _1-22 alkylene or alkyleneoxy alkylester group unsubstituted or substituted with fluorine, and the aforementioned alkylene group or alkyleneoxy alkylester group is a methacryl group, an acryl group, a di It may be substituted with one or more selected from fluoroacryl groups and the like;

R ₅ is the same as R ₂ or represents a C _1-22 alkyleneoxy group unsubstituted or substituted with fluorine;

o, p, q and r are numbers representing mole fractions, satisfying o + p + q + r = 1 and each representing a number of 0 or more and 1 or less.]

The diarylethene-based polymer of the formula (1) according to the present invention has excellent photochromic properties, such as fast photochromic speed.

The diarylethene-based polymer represented by Formula 1 may be prepared from a diarylethene compound of Formula 2, a styrene monomer of Formula 3, and a compound of Formula 4.

Accordingly, a second object of the present invention is to provide a method for preparing a diaryethene-based polymer of Formula 1 from a diarylethene compound of Formula 2, a styrene monomer of Formula 3, and a compound of Formula 4.

[Formula 1]

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X, Y, Z, o, p, q and r are as defined in claim 1]

According to one preferred embodiment of the present invention, the diarylethene-based polymer of Formula 1 may be selected from the group consisting of tetrahydrofuran, toluene, C _1-10 alcohol, acetonitrile, acetone, DMSO, DMF, α-methylnaphthalene, 30 ° C. to 400 hours for 0.5 to 10 hours in the presence of at least one solvent selected from the group consisting of methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylenecarbonate, sulfolane and xylene It is manufactured by reacting at the temperature of ° C.

A third object of the present invention is to provide a composition consisting of a diarylethene compound of formula (2), a styrene monomer of the formula (3) and a compound of the formula (4) for the preparation of the diarylethene-based polymer of formula (1) according to the present invention will be.

The composition according to the present invention is tetrahydrofuran, toluene, C _1-10 alcohol, acetonitrile, acetone, DMSO, DMF, α-methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichloro It may include one or more solvents selected from the group consisting of benzene, dichlorotoluene, propylene carbonate, sulfolane and xylene.

A fifth object of the present invention is to provide a diarylethene compound of formula (2) for preparing a diarylethene polymer of formula (1) according to the present invention. The diarylethene compound of the formula (2) is substituted with XR ₂ OC (═O) —, where X is a methacryl group, in the benzene ring of diarylethene.

A sixth object of the present invention is to provide a photochromic thin film of the diarylethene-based polymer of formula (1). The photochromic thin film may be prepared by heat treating or photocrosslinking a composition composed of a diarylethene compound of Formula 2, a styrene monomer of Formula 3, and a compound of Formula 4 in the presence or absence of a solvent and in the presence of an initiator. . The photochromic thin film thus prepared has a fast photochromic speed and excellent mechanical properties.

The diarylethene compound of formula (2) of the present invention reacts diarylethene, which is commercially available or prepared by a known method, with acetyl chloride to prepare monoacetyl-substituted diarylethene, followed by hydration, and then methacryl It is prepared by reacting with a substituted alkylene alcohol and can generally be obtained in a yield of at least 90%.

For example, 1- [6 '-(methacryloyloxyethyloxycarbonyl) -2'-methylbenzo [b] thiophen-3'-yl] -2- (2' '-methylbenzo [b ] Thiophene-3 ''-yl) hexafluorocyclopentene is prepared from 1,2-bis (2-methylbenzo [b] thiophen-3-yl) hexafluorocyclopentene.

Specifically, aluminum trichloride (AlCl ₃ ) is slowly added to a solution of 1,2-bis (2-methylbenzo [b] thiophen-3-yl) hexafluorocyclopentene and acetyl chloride in nitrobenzene at room temperature. After the addition, the mixture was reacted at room temperature for 5 hours, and then water was added to stop the reaction. When extracted with chloroform, 1- [6'-acetyl-2'-methylbenzo [b] thiophen-3'-yl]- 2- (2 ''-methylbenzo [b] thiophen-3 ''-yl) hexafluorocyclopentene is obtained in 84% yield. The resulting product is dissolved in dioxane, the resulting solution is slowly added dropwise to the sodium hypochlorite / dioxane solution at 30-80 ^o C and the resulting reaction mixture is continued at 50-110 ^o C for 0.5-10 hours. After reaction and purification, 1- (6'-carboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2 ''-methylbenzo [b] thiophen-3 ''- 1) hexafluorocyclopentene is obtained in a yield of 99%.

1- (6'-carboxy-2'-methylbenzo [b] thiophen-3'-yl] -2- (2 ''-methylbenzo [b] thiophen-3 ''-yl) hexavalent Fluorocyclopentene is dissolved in 2-hydroxyethyl methacrylate, DCC, DMAP and dichloromethane and stirred at room temperature to give a yield of 92% The formulas (2) and (3) of the present invention utilize commercially available compounds Can be.

As described above, the photochromic polymer of the present invention dissolves at least one compound selected from the diarylethene compound of Formula 1 and the compounds of Formulas 2 and 3 in an organic solvent, and after adding a thermosetting agent, 30 ° C. to 150 ° C. Preferably, the resulting mixture is heated by reaction at a temperature of 40 ° C. to 120 ° C. for 0.5 to 150 hours, preferably 2 to 100 hours. For example, the styrene copolymer of photochromic diaryl ethene

38% by weight of 1- [6 '-(methacryloinoxyethyloxycarbonyl) -2'-methylbenzo [b] thiophen-3'-yl] -2- (2''-methylbenzo [ b] thiophen-3 ''-yl) hexafluorocyclopentene, 40% styrene, 22% butylmethacrylate is dissolved in THF, followed by addition of a thermosetting agent and heating under reflux under a nitrogen atmosphere. The weight average molecular weight of the prepared polymer is 10500 based on polystyrene, and the dispersity (M _w / M _n ) is 1.49, so that a photochromic polymer can be prepared by dissolving in a solution.

And 22% by weight of 1- [6 '-(methacryloinoxyethyloxycarbonyl) -2'-methylbenzo [b] thiophen-3'-yl] -2- (2' '-methylbenzo [b] thiophen-3 ''-yl) 10% weight loss from TGA showing heat loss of the copolymer prepared from hexafluorocyclopentene, the temperature of which is 350 degrees or more, very good thermal stability. Indicates. The diarylethene polymers provided according to the present invention can be dissolved in conventional solvents such as toluene, xylene, chloroform, lower alcohols, or mixtures thereof.

Another object of the present invention is to provide a composition based on a diarylethene polymer having excellent thermal stability, and according to the present invention, the following composition is provided: toluene, chloroform, hexane, acetone, lower alcohol, At least one solvent selected from the group consisting of conventional organic solvents such as 1,2-dichloroethane, methyl ethyl ketone, sulfolane, xylene, 3-nitro-α, α, α-tripulolonitro, and mixtures thereof, and The composition comprising the diaryl ethene polymer prepared by the above method, at least one compound selected from the group consisting of tetraalkoxy silane, trialcohol glycidyl silane, tetraalkoxytitanium, hydrochloric acid, organic acid Containing composition; A composition comprising at least one resin selected from the group consisting of polyolefins, polystyrenes, polyvinyl butyral, polycarbonates, polyesters, polyacrylates, polyurethanes, and diarylethene polymers of the formula (4).

The polymer composition of the present invention described above is at least one selected from the group consisting of α-methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, sulfolane, quinoline, dichlorobenzene, dichlorotoluene, propylenecarbonate, and xylene It may further contain a high boiling point solvent.

The component ratio of each component of the composition of the present invention may be different depending on the use of the composition, but when the composition is used to produce a photochromic thin film as described below, the arylethene-based polymer of the formula (4) Preference is given to using in a proportion of 0.01 to 100% by weight of the total weight and using other components in a proportion of 0 to 99% by weight. When each component of the composition of the present invention is out of the component ratio, it is not preferable because the mechanical properties of the resulting thin film is not good. In addition, when the diarylethene polymer of the present invention is used in cosmetics, fibers, clays, and other compositions for light stabilizers or other purposes, the ratio of weight% may be used from 0.01 to several FPM units.

The above-described polymer composition of the present invention may be added various additives, lubricants, thickeners and the like that are obvious to those skilled in the art in order to improve heat resistance, mechanical properties, processing properties and the like.

Still another object of the present invention is to provide a photosensitive thin film having photosensitivity to ultraviolet light, visible light and near infrared light in the region of 200 to 800 nm using the above-described composition.

When the composition containing the diaryl ethene polymer prepared as described above is coated on a general support such as a plastic resin, a glass plate, an aluminum plate, a mylar film, or a conductive glass, it shows excellent absorption in a wavelength range of 200 to 500 nm. Diaryl ethene polymer thin film is provided. In addition, irradiating light such as sunlight or ultraviolet rays to the thin film thus prepared provides a diaryethene polymer thin film exhibiting good absorption in the wavelength region of 300 to 800 nm, wherein the coating is a roll coating or spin coating or bar coating. Spray coating, dip coating and the like can be used.

In addition, the diaryl ethene polymer of the formula (1) of the present invention is processed by dissolving in one or more solvents selected from the group consisting of ether, alcohol, aromatic hydrocarbon, monoterpene hydrocarbon and liquid paraffin or polyvinyl butyral (PVB), A photochromic thin film is also provided by mixing with a general purpose polymer such as polycarbonate (PC) and milling and then applying it onto the support.

The diaryl ethene polymer provided in the present invention is capable of solution processing but exhibits an absorption peak in the region of 200 to 800 nm and has a thermal stability of 350 ° C. or higher, so that the display device, the optical switch device, the optical integrated device, the solar cell, the sensor, etc. The possibility of application to other recording elements and optical elements is very high and these also belong to the scope of the present invention.

Features and other advantages of the present invention as described above will be more clearly described with reference to the following examples, but the scope of the present invention is not limited only to the following examples.

Examples 1-4 Preparation of Substituted Diarylethene Monomers

Example 1: 1- (6'-acetyl-2'-methylbenzo [b] thiophen-3'-yl) -2- (2 ''-methylbenzo [b] thiophen-3 ''-yl) Synthesis of hexafulluorcyclopentene

2.67 g of 1,2-Bis (2-methylbenzo [b] thiophen-3-yl) hexafluorocyclopentene and 0.8 ml of acetyl chloride synthesized by a known method were dissolved in 40 ml of nitrobenzene, and then 2.28 g at room temperature. AlCl ₃ is slowly added. After reacting the reaction mixture at room temperature for 5 hours, the reaction was stopped with H ₂ O and extracted with chloroform. The organic layer was dried with MgSO ₄ , removed with solvent under reduced pressure and separated by column chromatography (20% ethyl acetate-hexane) to give 2.44 g of 1- (6'-acetyl-2'-methylbenzo [b] thiophene. -3'-yl) -2- (2 ''-methylbenzo [b] thiophen-3 ''-yl) hexafluorocyclopentene is prepared. Yield 84%.

mp = 62 ^o C

IR (KBr, Cm ⁻¹ ); 1684 (-CO group)

¹ H-NMR (300 MHz, CDCl ₃ ) δ 8.29-7.54 (4H), 7.39-7.17 (3H), 2.63 (3H), 2.56-2.46 (3H), 2.24,2.20 (3H)

¹³ C-NMR δ15.6, 15.9, 27.1, 119.3, 119.7, 122.3, 122.4, 122.6, 123.2, 123.5, 124.7, 124.9, 125.1, 133.7, 138.5, 138.6, 142.0, 143.1, 147.9, 197.6

MS (m / z); 510 (M ⁺ , 100), 495 (67), 452 (10), 419 (13), 84 (71)

high-resolution MS; Theoretical value C ₂₅ H ₁₆ OF ₆ S ₂ : 510.0547 Experimental value: 510.0529

Example 2: 1- (6'-carboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2 ''-methylbenzo [b] thiophen-3 ''-yl) Synthesis of Hexafluorocyclopentene

1- (6'-acetyl-2'-methylbenzo [b] thiophen-3'-yl) -2- (2 ''-methylbenzo [b] thiophen-3 '' prepared by Example 1 -D) A solution of 0.11 g of hexafluorocyclopentene in 0.7 ml of dioxane is added dropwise to 2.8 ml (10% solution) of sodium hypochlorite and 0.4 ml of dioxane with agitation slowly at 50 ^° C. The reaction mixture is stirred for 2 more hours at 80 ^o C. The reaction is stopped with saturated sodium carbonate and extracted with chloroform. The organic layer was dried with MgSO ₄ , the solvent was removed under reduced pressure, and dried in a vacuum oven (60 ^o C) for 24 hours. The colorless 1- (6'-carboxy-2'-methylbenzo [b] thiophene-3 ' -Yl) -2- (2 ''-methylbenzo [b] thiophen-3 ''-yl) hexafluorocyclopentene is prepared in a yield of 99%. The melting point of the prepared compound is 98 ^° C., and the -COOH group is characteristic of 1692 Cm ⁻¹ (KBr pellet) in the infrared spectral absorption spectrum.

¹ H-NMR (300 MHz, CDCl ₃ ) δ 8.46-7.53 (4H), 7.34-7.19 (3H), 2.52,2.48 (3H), 2.27,2.22 (3H)

¹³ C-NMR δ15.6, 15.9, 119.3, 119.8, 122.3, 122.6, 124.9, 125.1, 125.4, 125.7, 126.3, 126.4, 138.3, 138.5, 138.7, 142.7, 143.2, 148.2, 172.5

MS (m / z); 512 (M ⁺ , 100), 482 (11), 464 (5), 445 (11), 419 (24)

high-resolution MS; Theoretical value: C ₂₄ H ₁₄ O ₂ F ₆ S ₂ : 512.0339 Experimental value: 512.0352

Example 3: 1- (6'-Methacryloyloxyethyloxycarboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2 ''-methylbenzo [b] thiophene Synthesis of -3 ''-yl) hexafluorocyclopentene

1- (6'-carboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2 ''-methylbenzo [b] thiophen-3 ''-as prepared in Example 2 I) 2.3 g of hexafluorocyclopentene, 0.69 ml of methacrylic acid 2-hydroxyester, 1.2 g of DCC, and 60 mg of DMAP are added to 50 ml of dichloromethane and stirred at room temperature for 5 hours. 50 ml of dichloromethane was added thereto, diluted with water, washed with water, and the dichloromethane layer was separated. Purification by flash chromatography (10% ethyl acetate-hexane) after removal of moisture with MgSO ₄ was carried out to yield colorless 1- (6'-methacryloyloxyethyloxycarboxy-2'-methylbenzo [b] thiophene-3. '-Yl) -2- (2''-methylbenzo [b] thiophen-3''-yl) hexafluorocyclopentene is prepared in a yield of 92%.

mp = 52 ^o C

IR (KBr, Cm ⁻¹ ); 1723 (-COO- group)

¹ H-NMR (300 MHz, CDCl ₃ ) δ 8.41-7.54 (4H), 7.37-7.17 (3H), 6.15 (s, 1H), 5.59 (s, 1H), 4.63-4.49 (m, 4H), 2.51 , 2.47 (3H), 2.24, 2.20 (3H), 1.95 (s, 1H)

¹³ C-NMR δ15.6, 15.9, 18.7, 62.8, 63.3, 119.3, 119.7, 122.3, 122.6, 124.8, 124.9, 125.1, 126.0, 126.3, 126.6, 136.3, 138.2, 138.3, 138.6, 142.1, 143.1, 166.4, 167.6

MS (m / z); 624 (M ⁺ , 100), 593 (3), 495 (43), 479 (7), 419 (4), 248 (9), 113 (55), 69 (24)

high-resolution MS; Theoretical value C ₃₀ H ₂₂ O ₄ F ₆ S ₂ : 624.0864 Experimental value: 624.0862

Example 4: 1- (6'-methacryloyloxypolyethyleneoxycarboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2 ''-methylbenzo [b] thiophene Synthesis of -3 ''-yl) hexafluorocyclopentene

1- (6'-carboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2 ''-methylbenzo [b] thiophen-3 ''-as prepared in Example 2 I) 2.3 g of hexafluorocyclopentene, 1 g of methacrylic acid polyethylene polyethyleneoxycarboxylic acid (weight average molecular weight 350), 1.5 g of DCC, and 79 mg of DMAP were added to 60 ml of dichloromethane and stirred at room temperature for 5 hours. 60 ml of dichloromethane was added thereto, diluted with water, washed with water, and the dichloromethane layer was separated. Removal of the solvent and purification afforded colorless 1- (6'-methacryloyloxypolyethyleneoxycarboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2 ''-methylbenzo [ b] thiophen-3 ''-yl) hexafluorocyclopentene is prepared in a yield of 90%.

Example 5-7 Preparation of Copolymers of Substituted Spirobenzopyran Compounds

Example 5

0.4 g of the diarylethene derivative prepared in Example 3, 0.89 g of styrene, and 0.52 g of butylmethacrylate are dissolved in THF, followed by addition of 1 Wt% of AIBN of the total single molecule. The reaction is refluxed for 72 hours in a nitrogen atmosphere, then cooled to room temperature and the solvent is removed under reduced pressure to give a solid polymer. Reprecipitation with ethyl ether and hexane and drying under reduced pressure at 60 ^° C. for 24 hours yielded a diarylethene styrene copolymer in a yield of 40%. The glass transition temperature of the prepared polymer is 66 degrees, the weight average molecular weight is 11500, the dispersity (M _w / M _n ) is 1.60 to dissolve in the solution to prepare a photochromic polymer easy to process. A thermogravimetric analysis showing the pyrolysis temperature is shown in FIG. 1.

Example 6

In Example 3 0.93 g of a diarylethene derivative, 0.91 g of styrene, and 0.57 g of butylmethacrylate are dissolved in THF, followed by addition of 1 Wt% of AIBN of the total monomolecule. The reaction is refluxed for 72 hours in a nitrogen atmosphere, then cooled to room temperature and the solvent is removed under reduced pressure to give a solid polymer. Reprecipitation with ethyl ether and hexane and drying under reduced pressure at 60 ^° C. for 24 hours yields a diarylethene styrene copolymer in a yield of 60%. The glass transition temperature of the produced polymer is 77 degrees, the weight average molecular weight is 10500, the dispersity (M _w / M _n ) is 1.49 to dissolve in the solution to prepare a photochromic polymer easy to process.

Example 7

The copolymer was prepared by stirring for 90 hours using the diarylethene derivative prepared in Example 4 instead of the diarylethene derivative prepared in Example 5 in Example 5. The yield of the copolymer produced is 56%.

Example 8

0.35 g of biaryallylcarbonate (CR-39, containing 3% IPP) and 0.12 g of styrene prepared in Example 3 were dissolved in THF 2 mL, and then stirred at 40 ° C. for 4 hours. After cooling to room temperature and precipitation by addition of hexane, 0.5 g of diarylethene-based polymer is prepared. The polymer produced shows high solubility in DMF.

Example 9

In Example 5, 0.6 g of polyethylene glycol monomethacrylate (molecular weight 350) was added and the copolymer was prepared in the same manner to prepare a polymer in a yield of 60%.

Examples 10 to 13 Preparation of Photochromic Thin Films

Example 10

0.5 g of the diaryl ethene copolymer prepared in Example 5 was dissolved in 5 ml of xylene and 2 ml of toluene, stirred at room temperature for 1 hour, and then concentrated until the weight change was reduced by 30%. The prepared solution was filtered using a 0.45 micron syringe filter, and the solution was applied onto a glass plate using a spin coater, and dried for 12 hours under reduced pressure in an oven at 50 degrees. A transparent photochromic thin film having excellent adhesiveness and high strength was prepared on the glass plate. do. When light of 300 nm or more is irradiated on the manufactured thin film, the color turns red. Phase separation did not occur even after 6 months of storage in the dark, and no association was found. In addition, no phase separation was observed when repeatedly irradiated with light. FIG. 2 shows a change in absorption spectrum of a thin film when irradiated with a short wavelength of 310 nm.

Example 11

0.1 g of the diarylethene copolymer prepared in Example 6 was dissolved in 0.8 ml of xylene and 0.2 ml of toluene, stirred at room temperature for 1 hour, and then filtered using a 0.45 micron syringe filter. When applied on a plate and dried for 12 hours under reduced pressure in an oven at 50 degrees, a transparent photochromic thin film having excellent adhesiveness and high strength is prepared on a PC plate. Irradiation of short wavelength of 340 nm to the prepared thin film turns red and blocks the light and keeps red when stored in dark room. Phase separation did not occur even after 6 months of storage in the dark, and no association was found.

Example 12 [Comparative Example]

1- (6'-methacryloyloxyethyl-2'-methylbenzo [b] thiophen-3'-yl) -2- (2 by known method (Japan Kokai Tokkyo Koho; JP 06/240242 A2) `` -Methylbenzo [b] thiophen-3 ''-yl) hexafluorocyclopentene (40% by weight) and methyl methacrylate (60% by weight) were activated to prepare a polyketylmethacrylic acid polymer It was. After dissolving the prepared copolymer in chloroform and coating it on the glass plate, the mechanical properties were poor, and there was a problem of poor adhesion.

Example 13

0.2 g of the diarylethene copolymer prepared in Example 8 was dissolved in a mixed solvent of 0.8 ml of DMF, 0.2 ml of THF, and ethylene glycol, stirred at room temperature for 1 hour, and then filtered using a 0.45 micron syringe filter. When applied to a polyester film using a bar coater and dried for 12 hours under reduced pressure in an oven at 50 degrees, a transparent photochromic thin film having excellent adhesiveness and excellent strength is prepared on the polyester film. Irradiation of short wavelength of 340 nm to the prepared thin film turns red and blocks the light and keeps red when stored in dark room. Phase separation did not occur even after 6 months of storage in the dark, and no association was found.

As described above, according to the present invention, a copolymer of diaryethene-styrene having a fast photochromic speed, excellent adhesion, and excellent workability, a photochromic composition and a photochromic thin film using the same can be prepared.

Claims (10)

To the photochromic diaryl ethene-based polymer of the formula (4). [Formula 4] [In the above formula, R ₁ represents a hydrogen atom or a C _1-22 alkyl group, or a fluorine group, a substituted or unsubstituted pentyl group, a substituted or unsubstituted pentylalkyl group; R ₂ represents a C _1-22 alkylene group unsubstituted or substituted with fluorine; R ₃ represents a C _1-3 alkylene group unsubstituted or substituted with a bond line, an oxygen atom, or fluorine; X and Y each independently represent an oxygen, nitrogen or sulfur atom; Z represents a methylene group or a carbonyl group unsubstituted or substituted with fluorine.] R ₄ is the same as R ₁ or represents a C _1-22 alkylene or alkyleneoxy alkylester group unsubstituted or substituted with fluorine, and the aforementioned alkylene group or alkyleneoxy alkylester group is a methacryl group, an acryl group, a di It may be substituted with one or more selected from fluoroacryl groups and the like; R ₅ is the same as R ₂ or represents a C _1-22 alkyleneoxy group unsubstituted or substituted with fluorine; o, p, q and r are numbers representing mole fractions, satisfying o + p + q + r = 1 and each representing a number of 0 or more and 1 or less.] Method for preparing a photochromic diaryl ethene-based polymer represented by the following formula (4) prepared from a diaryl ethene compound of formula (1), a styrene-based monomer of formula (2) and a compound of formula (3), [Formula 1] [Formula 2] [Formula 3] [Formula 4] [Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X, Y, Z, o, p, q and r are as defined in claim 1] The compound of claim 2, wherein the tetrahydrofuran, toluene, C _1-10 alcohol, acetonitrile, acetone, DMSO, DMF, α-methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene And dichlorotoluene, propylene carbonate, sulfolane and xylene in the presence of one or more solvents for 0.5 to 10 hours at a temperature of 30 ℃ to 400 ℃. A thermosetting or photocurable polymerizable composition composed of a diarylethene compound of Formula 1, a styrene monomer of Formula 2, and a compound of Formula 3. [Formula 1] [Formula 2] [Formula 3] [Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X, Y and Z are as defined in claim 1.] The photochromic diarylethene-based polymer of formula 4 according to claim ₁ , and acetone, acetonitrile, C _1-10 alcohol, dimethylformamide (DMF), tetraalkoxysilane, trialkoxysilane, dialkoxysilane, sulfuric acid, Hydrochloric acid, organic acid, dimethyl sulfoxide, pyridine, N-methylpyrrolidone (NMP), sulfolane, α-methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, A photochromic diarylethene-based polymer composition composed of at least one solvent selected from the group consisting of propylene carbonate, xylene, methyl ethyl ketone and water. The composition of claim 5 comprising low molecular weight diarylethene. The composition according to claim 5, comprising at least one resin selected from the group consisting of polyvinyl butyral, polyolefin, polycarbonate, polyester, polymethyl methacrylate, polyurethane and the like. Diaryl ethene compound represented by the following formula (1). [Formula 1] [Wherein R ₁ , R ₂ , R ₃ , X, Y and Z are as defined in claim 1] A conductive electrode support selected from the group consisting of aluminum foil, aluminum drums, aluminum plates, platinum, mylar films, copper plates, conductive glasses and conductive plastics, or polypropylene, propylene carbonate, polymethylmethacrylate, polyurethane and conventional A photochromic diaryethene-based polymer comprising a support selected from the group consisting of plastics or glass and a diarylethene-based polymer according to claim 1 or a polymer composition according to any one of claims 5 to 7 coated on said support. pellicle. An optical recording medium, a photochromic window, a display element, a plastic mirror, a photochromic filter, an optical switch, a photosensitive drum, and a recording material comprising the diarylethene-based polymer according to claim 1 or the polymer composition according to any one of claims 5 to 7. Devices, solar cells, lenses, cosmetics, fibers, or optical devices.