JP5191682B2 - Phenol derivative having anthracene residue in side chain and method for producing the same - Google Patents

Description

  The present invention relates to a phenol derivative having an anthracene residue in the side chain and a method for producing the same.

With the advent of an advanced information society, information communication devices such as mobile phones and personal computers are spreading. Information processing capability and information transmission speed are listed as characteristics required for information communication equipment.
Conventional information communication systems are performed by mutually converting electrical signals or optical signals and electrical signals. However, it is expected that this system will be limited to handle larger amounts of information. Therefore, a system that communicates with an optical signal without converting the optical signal and the electrical signal has been studied.

  As one of the considerations, attention is focused on an optical switching system in which an optical signal is switched as it is. Light can switch not only wide-band signals that are electrically difficult to switch, but also high-speed signals of several gigahertz or more that cannot be handled electrically. Among them, a refractive index conversion type system using photoisomerization and photodimerization has attracted attention. As a refractive index conversion material, a material having large molecular refraction and density change before and after the photoreaction is required from the Lorentz-Lorentz equation.

  By the way, it is known that a star polymer is positioned as a branched polymer together with a hyperbranched polymer and a dendrimer, and its characteristics are also different from the corresponding linear polymer. In addition, it is reported that the star polymer has a higher segment density as it is closer to the core part, and a star polymer having a short arm length has a higher molecular density than a linear polymer, and therefore has a higher refractive index. (Non-Patent Document 1). Therefore, when a star polymer is applied to a refractive index conversion material, a larger refractive index change can be expected than a linear polymer.

The present inventors have proposed calix derivatives excellent in thermal stability by introducing norbornadiene or anthracene as a photoreactive group into a calixarene compound. It has been reported that these calix derivatives have a characteristic that the refractive index changes greatly by light irradiation (Patent Documents 1 and 2).
Moreover, it has been reported that the above calix derivatives show a large change in refractive index as compared with conventional linear polymers.
Furthermore, it is also clear that the refractive index change accompanying photodimerization is larger than that of norbornadiene or azobenzene (see Non-Patent Document 2).
H. Kudo, H .; Inoue, T .; Nishikubo, and T. Anada, Polymer Journal, Vol. 38, no. 3 (2006) H. Kudo, W.H. Ueda, K .; Seijio, K .; Mitani, T .; Nishikubo, and T. Anada, Bull. Chem. Soc. Jpn. , 77, 1415 (2004) JP 2003-306470 A JP 2004-262822 A

  An object of the present invention is to provide a material that can be suitably used as an optical material in the field of optical communication or the like based on the above findings.

The present inventors have found that a phenol derivative having an anthracene residue in the side chain has a high refractive index and can be used as an optical material.
According to the present invention, the following phenol derivatives and methods for producing the same are provided.
1. A phenol derivative represented by the following formula (1) or (2).
[Wherein, m is an integer of 4 to 10, and n is an integer of 1 to 1000. R ₁ is hydrogen, a hydroxyl group or an alkyl group having 1 to 10 carbon atoms, R ₂ is a divalent organic group having 1 to 20 carbon atoms, X is chlorine, bromine or iodine, and R ₃ is represented by the following formula: It is a group represented by (3a) or formula (3b).
(In the formula, R ₄ is a divalent organic group having 1 to 20 carbon atoms.)]
2. 2. The method for producing a phenol derivative according to 1, wherein a compound represented by the following formula (4) or formula (5) is reacted with a compound represented by the following formula (6a) or formula (6b).
(In the formula, m is an integer of 4 to 10, n is an integer of 1 to 1000, R ₁ is hydrogen, a hydroxyl group or an alkyl group having 1 to 10 carbon atoms, and R ₂ is an alkyl group having 1 to 20 carbon atoms. X is chlorine, bromine or iodine, and R ₄ is a divalent organic group having 1 to 20 carbon atoms.)
3. An optical material containing the phenol derivative of 1 above and having a refractive index in the range of 1.500 to 1.900.
4). 4. An optical waveguide made of the optical material as described in 3 above.
5. 4. An optical film comprising the optical material as described in 3 above.
6). 4. A refractive index conversion material comprising the optical material described in 3 above.

  ADVANTAGE OF THE INVENTION According to this invention, the phenol derivative useful as an optical material and its manufacturing method can be provided.

The phenol derivative of the present invention is represented by the following formula (1) or (2).

In the formula, m is an integer of 4 to 10, and n is an integer of 1 to 1000. R ₁ is hydrogen, a hydroxyl group (—OH) or an alkyl group having 1 to 10 carbon atoms, R ₂ is a divalent organic group having 1 to 20 carbon atoms, and R ₃ is a group having an anthracene structure, X is chlorine, bromine or iodine.

  Since the phenol derivative of the present invention has a photoreactive group in its structural unit, it has a photoreactive characteristic that changes its characteristics when it receives specific light, for example, ultraviolet rays. Moreover, since the phenol derivative of the formula (2) has a calixarene skeleton, the characteristics that the molecular density is higher and the refractive index is higher than the linear compound that is the phenol derivative of the formula (1) are obtained.

In the above formulas (1) and (2), examples of the alkyl group having 1 to 10 carbon atoms represented by R ₁ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, There are sec-butyl group, t-butyl group and the like.
R ₁ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.

Examples of the divalent organic group having 1 to 20 carbon atoms represented by R ₂ include an methylene group, an ethylene group, a propylene group, an isopropylidene group, an ethylidene group, an acetylene group, and an aromatic group such as a phenylene group. It is done. In addition, a group in which a substituent such as a halogen atom, a nitro group, a carboxyl group, or an amino group is bonded to these organic groups may be used. R ₂ is preferably an isopropylidene group, a propylene group, or an ethylidene group.

R ₃ is a group represented by the following formula (3a) or (3b).

In the formula, R ₄ is a divalent organic group having 1 to 20 carbon atoms.
Examples of the divalent organic group represented by R ₄ include an methylene group, an ethylene group, an acetylene group; an aromatic group such as a phenylene group; an ester group, a ketone group, an acetyl group, a thioketone group, —CH ₂ —OCO— (CH _{2) 2 -CO -, - CH} 2 -CO- , and the like.
R ₄ is preferably a ketone group, —CH ₂ —OCO— (CH ₂ ) ₂ —CO—, —CH ₂ —CO—.

n is a polymerization degree and is an integer of 1-1000. Although it depends on the application, n can be used as a resin, and is preferably in the range of 10 to 500.
m is an integer of 4 to 10, preferably 4 to 6.

Then, the manufacturing method of the phenol derivative of this invention is demonstrated.
In the method for producing a phenol derivative of the present invention, a compound represented by the following formula (4) or formula (5) is reacted with a compound represented by formula (6a) or formula (6b).

In the formula, m, n, R ₁ , R ₂ and R ₄ represent the same groups as those in the above formulas (1) to (3b), respectively.
In the case of producing the phenol derivative of the above formula (1), the compound of the formula (4) and the formula (6a) or the formula (6b) is used. In the case of producing the phenol derivative of the above formula (2), the formula (5) And a compound of formula (6a) or formula (6b) are reacted.

In addition, the compound of Formula (4) or (5) can be obtained by making glycidyl methacrylate react with the initiator shown by following formula (7), (8).
(In the formula, m, X, R _{1 and} R ₂ are the same as those in the formulas (1) and (2).)

The reaction between the initiator represented by the above formulas (7) and (8) and glycidyl methacrylate is preferably carried out in the presence of a transition metal and a ligand. This method is illustrated in WO 97/18247.
The compound containing a transition metal that can participate in the reduction step has the formula: M ^{n +} X ′ _n (where M is Cu, Au, Ag, Hg, Ni, Pd, Pt, Rh, Co, Ir, Fe, Ru, Os, Re, Mn, Cr, Mo, W, V, Nb, Ta and Zn can be selected, and -X 'is halogen (especially bromine or chlorine), OH, (O) _1/2 , 1-6 Alkoxy groups having the following carbon atoms: (SO ₄ ) _1/2 , (PO ₄ ) _1/3 , (HPO ₄ ) _1/2 , (H ₂ PO ₄ ), triflate, hexafluorophosphate, methanesulfonate , Aryl sulfonate, SeR, CN, NC, SCN, CNS, OCN, CNO, N ₃ and R′CO ₂ groups, wherein R ′ is H, or linear or branched and contains 1 to 6 carbon atoms An alkyl group having one or more halogen atoms, in particular An aryl group optionally substituted with a nitrogen and / or chlorine atom can be shown, and n can be selected from those corresponding to a metal charge.
Preferably, one is selected wherein M represents copper or ruthenium and X ′ represents bromine or chlorine. Mention may be made especially of copper chloride.

Further, as a ligand, carbon monoxide; optionally substituted porphyrins and porphycenes; optionally substituted ethylenediamine and propylenediamine; tertiary amine-containing polyamines such as pentamethyldiethylenetriamine; optionally substituted Good amino alcohols such as aminopropanol and aminoethanol; glycols such as optionally substituted ethylene glycol or propylene glycol; arenes such as optionally substituted benzene; optionally substituted cyclopentadiene; substituted Mention may be made of pyridines and bipyridines which may have been prepared; acetonitrile; 1,10-phenanthroline; cryptands and crown ethers; or sparteine.
Preferred ligands, C ₂ -C ₁₅ alkyl group, in particular C ₆ -C ₁₂ group, among them good pyridines substituted with nonyl and bipyridines; or polyamines having a tertiary amine, e.g. pentamethyldiethylenetriamine Especially selected from.

  Polymerization of the monomer glycidyl methacrylate in the presence of an initiator of formulas (7), (8), a compound containing a transition metal and a ligand acting as an activator results in formulas (4), (5 A phenol derivative having a structure that can be represented by:

  Solvents used in the reaction are ethers such as diethyl ether and tetrahydrofuran, halogen solvents such as dichloromethane and chloroform, hydrocarbon solvents such as hexane and toluene, N, N-dimethylformamide, N-methylpyrrolidone and N-dimethylacetamide. An aprotic polar solvent such as acetone, ketone solvents such as acetone and cyclohexanone, and esters such as ethyl acetate can be used. Moreover, it can be made to react even without solvent.

  The reaction temperature is usually between −50 to 100 ° C., preferably 0 to 70 ° C., more preferably 0 to 40 ° C. If the reaction temperature is less than −50 ° C., the reaction time may be prolonged, and if the reaction temperature exceeds 100 ° C., side reactions may occur.

  The step of reacting the compound of the formula (4) or (5) with the compound of the formula (6a) or the formula (6b) can be performed in a solvent using a catalyst as necessary.

  As the catalyst, quaternary ammonium salts such as tetrabutylammonium bromide and tetraethylammonium chloride, and metal salts such as lithium chloride and lithium bromide can be used.

  The amount of the catalyst is preferably 0.1 to 10 mol%, more preferably 3 to 7 mol%, based on the epoxy group of the compound of formula (4) or formula (5).

  Solvents include ethers such as diethyl ether and tetrahydrofuran, halogen solvents such as dichloromethane and chloroform, hydrocarbon solvents such as hexane and toluene, N, N-dimethylformamide, 1-methyl-2-pyrrolidone and N-dimethyl. Aprotic polar solvents such as acetamide, ketone solvents such as acetone and cyclohexanone, and esters such as ethyl acetate can be used, and 1-methyl-2-pyrrolidone is preferred.

The reaction temperature is usually 30 to 100 ° C., preferably 50 to 80 ° C. If the reaction temperature is less than 30 ° C, the reaction time may be longer, and if the reaction temperature exceeds 100 ° C, side reactions may occur. The reaction time is preferably 24 to 48 hours.
The reaction is desirably performed in a state where moisture can be removed, such as an ampoule sealed tube.

The phenol derivative of the present invention can be suitably used as an optical material alone or in a state in which various additives, resins and the like are mixed.
The refractive index of the optical material of the present invention is preferably 1.500 to 1.900. In the present invention, a material having such a high refractive index can be obtained.

The optical material of the present invention can be formed into a film by dissolving in a solvent to form a solution, applying the solution on an arbitrary support, and drying.
As a solvent for dissolving the phenol derivative of the present invention, methyl cellosolve acetate, tetrahydrofuran, 1-methyl-2-pyrrolidone, dimethylformaldehyde, chloroform, methylene chloride and the like can be used.
By using the solution, for example, an optical waveguide can be formed on a substrate or the like.

  When the phenol derivative is a resin, a molded product such as an optical film can be produced by a known molding method such as injection molding or extrusion molding.

  The phenol derivative of the present invention is extremely useful as a refractive index conversion material used in an optical storage element, an optical switch system, and the like because a photodimerization product is obtained by light irradiation.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

Example 1
A compound represented by the following formula (1a) (hereinafter abbreviated as (1a)) was synthesized.

In an eggplant flask, 0.057 g (0.02 mmol) of a compound of the following formula (4a), 0.120 g (0.54 mmol) of 9-anthracenecarboxylic acid (hereinafter abbreviated as 9-ATC), tetrabutylammonium bromide (hereinafter, 0.006 g (0.018 mmol) was added, and dissolved in 1.8 mL of 1-methyl-2-pyrrolidone. Then, it was made to react at 70 degreeC for 48 hours.

The synthesis of (4a) will be described in Synthesis Example 1 described later.
After completion of the reaction, the reaction mother liquor was diluted with chloroform, washed twice with NaHCO ₃ solution and twice with water, and the organic layer was dried using anhydrous magnesium sulfate.
After the desiccant was filtered off, the solution was concentrated, and reprecipitation purification was performed twice using chloroform as both solvents and diethyl ether as a poor solvent. The precipitated solid was collected and dried under reduced pressure to obtain 0.11 g (yield: 85.0%) of (1a) as a pale yellow solid.
The results of infrared spectroscopic analysis (IR) and ¹ H-NMR measurement of the obtained compound are shown below.
IR (KRS, cm ⁻¹ ):
3485 (νO—H), 1727 (νC═O ester), 1447 (νC = C aromatic), 1201, 1151 (νC—O—C ester), 892 (νC—O—C epoxy).
¹ H NMR (600 MHz, DMSO-d ₆ , TMS) δ (ppm):
0.85-1.40 (m, H ^a ), 1.76-1.91 (m, H ^b ), 4.00-4.17 (m, H ^{c, d} ), 4.55-4. 65 (m, H ^e ), 5.53 (br, H ^f ), 7.44 (br, H ^g ), 8.02 (br, H ^h ), 8.55 (br, H ⁱ )
The identification result of the hydrogen atom by ¹ H-NMR measurement is shown below.

Moreover, it reacted similarly using (4a) from which polymerization degree (n) differs. The introduction rate of 9-anthracenecarboxylic acid into (4a) was calculated from ¹ H-NMR. The results are shown in Table 1.

Example 2
A compound represented by the following formula (1b) (hereinafter abbreviated as (1b)) was synthesized.

In an eggplant flask, 0.057 g (0.02 mmol) of the compound of (4a) and 0.12 g (0.54 mmol of 2-anthracenecarboxylic acid (hereinafter abbreviated as 2-ATC)) are added to the epoxy group. Double), tetrabutylammonium bromide (0.006 g, 5 mol%, 0.018 mmol) was added, dissolved in 1.8 mL of 1-methyl-2-pyrrolidone, and reacted at 70 ° C. for 48 hours.
Reprecipitation purification was performed twice using tetrahydrofuran as a good solvent and a mixed solvent of methanol and diethyl ether (1: 4) as a poor solvent. The precipitated solid was collected and dried under reduced pressure to obtain a pale yellow solid in a yield of 0.10 g (82%). The structure was confirmed by IR and ¹ H NMR.
IR (KRS, cm ⁻¹ ):
3429 (νO—H), 1719 (νC═O ester), 1582 (νC = C aromatic), 1234, 1151 (νC—O—C ester), 890 (νC—O—C epoxy)
¹ H NMR (600 MHz, DMSO-d ₆ , TMS) δ (ppm):
0.82-1.37 (m, H ^a ), 1.86-2.17 (m, H ^b ), 4.01-4.28 (m, H ^{c, d, e} ), 5.44 ( ^{br, H f), 7.32 (} br, H g), 7.73 (br, H h), 8.19-8.43 (m, H i)
The identification result of the hydrogen atom by ¹ H-NMR measurement is shown below.

Moreover, it reacted similarly using (4a) from which polymerization degree (n) differs. The introduction rate of 2-anthracenecarboxylic acid into (4a) was calculated from ¹ H-NMR. The results are shown in Table 2.

Example 3
A phenol derivative represented by the following formula (2a) (hereinafter abbreviated as (2a)) was synthesized.

To the eggplant flask, 0.046 g (0.002 mmol) of the compound of the following formula (5a), 0.10 g (0.45 mmol) of 9-anthracenecarboxylic acid and 0.005 g (0.015 mmol) of TBAB were added, and 1-methyl Dissolved in 1.5 mL of -2-pyrrolidone. Then, it was made to react at 70 degreeC for 48 hours.

The synthesis of (5a) will be described in Synthesis Example 2 described later.
After completion of the reaction, the reaction mother liquor was diluted with chloroform, washed twice with NaHCO ₃ solution and twice with water, and the organic layer was dried using anhydrous magnesium sulfate. After the desiccant was filtered off, the solution was concentrated, and reprecipitation purification was performed twice using chloroform as both solvents and diethyl ether as a poor solvent. The precipitated solid was collected and dried under reduced pressure to obtain 0.081 g (yield: 76.0%) of (2a) as a pale yellow solid.
The results of IR analysis and ¹ H-NMR measurement of the obtained polymer compound are shown below.
IR (KRS, cm ⁻¹ ):
3484 (νO—H), 1726 (νC═O ester), 1450 (νC = C aromatic), 1200, 1149 (νC—O—C ester), 893 (νC—O—C epoxy)
¹ H NMR (600 MHz, DMSO-d ₆ , TMS) δ (ppm):
0.91-1.40 (m, H ^a ), 1.76-1.91 (m, H ^b ), 3.97-4.12 (m, H ^{c, d} ), 4.51-4. 61 (m, H ^e ), 5.48 (br, H ^f ), 7.39 (br, H ^g ), 7.97 (br, H ^h ), 8.51 (br, H ⁱ )
The identification result of the hydrogen atom by ¹ H-NMR measurement is shown below.

  Moreover, it reacted similarly using (5a) from which polymerization degree (n) differs. Table 3 shows the introduction ratio of 9-anthracenecarboxylic acid into (5a).

Example 4
A phenol derivative represented by the following formula (2b) (hereinafter abbreviated as (2b)) was synthesized.

In an eggplant flask, 0.046 g (0.002 mmol) of the compound (5a), 0.10 g (0.46 mmol, 1.5 times the epoxy) of 2-ATC, and 0.005 g (5 mol%, 0.015 mmol) and dissolved in 1.6 mL of NMP and reacted at 70 ° C. for 48 hours.
Reprecipitation purification was performed twice using THF as a good solvent and a mixed solvent of methanol and diethyl ether (1: 4) as a poor solvent. The precipitated solid was collected and dried under reduced pressure to obtain 0.086 g (yield: 83%) of a pale yellow solid. The structure was confirmed by IR and ¹ H NMR.
IR (KRS, cm ⁻¹ ):
3429 (νO—H), 1717 (νC═O ester), 1582 (νC = C aromatic), 1234, 1151 (νC—O—C ester), 890 (νC—O—C epoxy)
¹ H NMR (600 MHz, DMSO-d ₆ , TMS) δ (ppm):
0.90-1.37 (m, H ^a ), 1.74-2.16 (m, H ^b ), 4.08-4.29 (m, H ^{c, d, e} ), 5.43 ( ^{br, H f), 7.29 (} br, H g), 7.70 (br, H h), 8.17-8.41 (m, H i)
The identification result of the hydrogen atom by ¹ H-NMR measurement is shown below.

  Moreover, it reacted similarly using (5a) from which polymerization degree (n) differs. Table 4 shows the introduction rate of 2-anthracenecarboxylic acid into (2b).

Evaluation Example 1
The photoisomerization reaction of the polymer (1a) (n = 20, 30, 40) synthesized in Example 1 was evaluated by the following method.
(1a) was dissolved in THF, applied to a quartz cell to produce a film, and then dried under reduced pressure at room temperature. This film was irradiated with light [1.8-2.0 mW / cm ² (313 nm)] using a 500 W xenon lamp as a light source, and the decrease in absorption wavelength based on 9-ATC residues was traced using the UV spectrum. did. The light irradiation time was 0 to 3600 seconds.

The UV spectrum at each light irradiation time is shown in FIG. FIG. 1a is the UV spectrum of (1a) with a polymerization degree n of 20, FIG. 1b is the UV spectrum of (1a) with n = 30, and FIG. 1c is the UV spectrum of (1a) with n = 40.
In any of the figures, as the light irradiation time increased, the absorption due to the 9-ATC residue decreased, and it was confirmed that the light steady state was reached 60 minutes after the light irradiation.
The relationship between the light irradiation time of the 9-ATC residue calculated from the obtained UV spectrum and the isomerization rate and the results of plotting the isomerization rate at the initial stage of the reaction in the first-order rate equation are shown in FIGS. 1d and 1e, respectively.
Furthermore, Table 5 shows the isomerization rate calculated from the primary rate plot. As a result, all the isomerization rates were the same value.

Evaluation example 2
The photoisomerization reaction of the polymer (1b) (n = 20, 30, 40) synthesized in Example 2 was evaluated in the same manner as in Evaluation Example 1.
The UV spectrum at each light irradiation time is shown in FIG. 2a is the UV spectrum of (1b) with a polymerization degree n of 20, FIG. 2b is the UV spectrum of (1b) with n being 30, and FIG. 2c is the UV spectrum of (1b) with n being 40.
In any of the figures, as the light irradiation time became longer, the absorption due to the 2-ATC residue decreased, and it was confirmed that the light steady state was reached 60 minutes after the light irradiation.
The relationship between the light irradiation time and the isomerization rate of the 2-ATC residue calculated from the obtained UV spectrum and the results of plotting the isomerization rate at the initial stage of the reaction in the first-order rate equation are shown in FIGS. 2d and 2e, respectively.
The isomerization rate calculated from the primary rate plot is shown in Table 6. As a result, all the isomerization rates were the same value.

Evaluation Example 3
The photoisomerization reaction of the polymer (2a) (n = 20, 30, 40) synthesized in Example 3 was evaluated in the same manner as in Evaluation Example 1.
The UV spectrum at each light irradiation time is shown in FIG. 3a is the UV spectrum of (2a) with a polymerization degree n of 20, FIG. 3b is the UV spectrum of (2a) with n = 30, and FIG. 3c is the UV spectrum of (2a) with n = 40.
In any of the figures, as the light irradiation time increased, the absorption due to the 9-ATC residue decreased, and it was confirmed that the light steady state was reached 45 minutes after the light irradiation.
The relationship between the light irradiation time of the 9-ATC residue calculated from the obtained UV spectrum and the isomerization rate and the results of plotting the isomerization rate at the initial stage of the reaction in the first-order rate equation are shown in FIGS. 3d and 3e, respectively.
Furthermore, Table 7 shows the isomerization rate calculated from the primary rate plot. As a result, all the isomerization rates were the same value. In addition, the isomerization rate was faster for the polymer having 9-ATC residues.

Evaluation Example 4
The photoisomerization reaction of the polymer (2b) (n = 20, 30, 40) synthesized in Example 4 was evaluated in the same manner as in Evaluation Example 1.
The UV spectrum at each light irradiation time is shown in FIG. 4a is the UV spectrum of (2b) with a degree of polymerization n of 20, FIG. 4b is the UV spectrum of (2b) with n = 30, and FIG. 4c is the UV spectrum of (2b) with n = 40.
In any of the figures, as the light irradiation time increased, the absorption due to the 2-ATC residue decreased, and it was confirmed that the light steady state was reached 45 minutes after the light irradiation.
The relationship between the 2-ATC residue light irradiation time calculated from the obtained UV spectrum and the isomerization rate and the results of plotting the isomerization rate at the initial stage of the reaction in the first-order rate equation are shown in FIGS. 4d and 4e, respectively.
Furthermore, Table 8 shows the isomerization rate calculated from the primary rate plot. As a result, the shorter the arm length, the higher the isomerization rate and the higher isomerization rate.

Evaluation Example 5
The refractive index change before and after the light irradiation of the polymers (1a), (1b), (2a), and (2b) synthesized in Example 1-4 was measured. Specifically, a film of each polymer was prepared on a silicon wafer, and the refractive index of the film before light irradiation was measured using an ellipsometer (wavelength 632.8 nm).
Thereafter, light irradiation was performed using a 500 W xenon lamp ((1.8-2.0 mW / cm ² (313 nm)) as a light source. After the light irradiation, the refractive index of the film was measured. The glass transition point (Tg) was measured, and the measurement results are shown in Table 9.

  From the results in Table 9, the value of Δn is different between the star polymer (2a, 2b) and the linear polymer (1a, 1b), and as the arm length is shorter, the value of Δn of the star polymer is higher than that of the linear polymer. Was also found to show a large value. Therefore, it was clarified that the star polymer having a short arm length has a larger density change before and after the photoreaction than the linear polymer.

Synthesis Example 1 [Synthesis of Formula (4a)]
(1) Synthesis of monofunctional initiator [4-tert-butyl-2-bromoisobutyryloxybenzene] In a three-necked eggplant flask, 3.0 g (20 mmol) of 4-tert-butylphenol (4-tert-BuPhOH) ) Was dissolved in 80 mL of THF, and the system was placed in a nitrogen atmosphere. Subsequently, after adding 3.0 g (30 mmol) of triethylamine (NEt ₃ ), a solution obtained by diluting 6.9 g (30 mmol) of 2-bromoisobutyryl bromide (BIB) with 20 mL of THF was slowly added dropwise under ice cooling, The reaction was allowed to proceed for 24 hours at room temperature. The precipitated salt was filtered off, the solution was distilled off under reduced pressure, diluted with chloroform, washed once with 1N hydrochloric acid, three times with saturated aqueous sodium bicarbonate, and twice with water, and the organic layer was dried over anhydrous magnesium sulfate. And dried. After the desiccant was filtered off, the solution was distilled off under reduced pressure, and the precipitated solid was recrystallized using n-hexane to obtain white needle crystals.
The yield was 4.3 g (72%), and the melting point was 59.2-60.0 ° C.

(2) Synthesis of Formula (4a) 0.030 g (0.1 mmol) of the initiator synthesized in (1) above and 0.032 g (0.2 mmol) of 2,2′-bipyridine (bpy) in an ampule tube In addition, 0.315 g (2.22 mmol) of glycidyl methacrylate (GMA) and 0.010 g (0.1 mmol) of CuCl were weighed and dissolved in 2 mL of DMF. After that, a two-way cock was attached, frozen and degassed several times, and sealed. After thawing at room temperature, the reaction was allowed to proceed at room temperature for 48 hours. After completion of the reaction, reprecipitation purification was performed using THF as a good solvent and water as a poor solvent. The precipitated solid was recovered and then dissolved again in THF, and reprecipitation purification was performed using n-hexane as a poor solvent. The precipitated solid was collected and dried under reduced pressure to obtain a white powder solid.
The yield was 0.28 g (83%), the number average molecular weight (M _n ) = 3700, and the molecular weight distribution (M _w / M _n ) = 1.24.
Mn and Mw / Mn were measured under the following conditions.
Size exclusion chromatography (SEC): HLC-8020 manufactured by Tosoh Corporation (column: TSKgel G1000H, solvent: THF, standard: polystyrene)

Synthesis Example 2 [Synthesis of Formula (5a)]
(1) Synthesis of 8-functional initiator To a three-necked eggplant flask, 0.544 g (1 mmol) of calix [4] resorcinarene and 1.21 g (12 mmol) of NEt ₃ were added and dissolved in 25 mL of THF. Thereafter, 2.75 g (12 mmol) of BIB was diluted with 5 mL of THF, added dropwise gradually under ice cooling under a nitrogen atmosphere, stirred for 30 minutes, and reacted at 50 ° C. for 48 hours. After completion of the reaction, the precipitated salt is filtered off, the solution is diluted with chloroform, washed twice with aqueous sodium hydrogen carbonate solution, once with 1N hydrochloric acid and three times with water, and the organic layer is washed with anhydrous magnesium sulfate. Dried. After the desiccant was filtered off, the solution was concentrated and poured into a large amount of methanol to precipitate a solid. This was repeated twice, and the resulting white powder solid was recrystallized using chloroform to obtain white plate crystals.
The yield was 1.2 g (68%) and the melting point was 337.2-337.9 ° C.

(2) Synthesis of Formula (5a) Into an ampule tube, 0.022 g (0.0125 mmol) of the initiator synthesized in the above (1), 0.010 g (0.1 mmol) of CuCl, and 0.032 g (0 of bpy) 0.2 mmol) and 0.473 g (3.33 mmol) of GMA were weighed and dissolved in 5 mL of DMF. After that, a two-way cock was attached, frozen and degassed several times, and sealed. After thawing at room temperature, the reaction was allowed to proceed at room temperature for 24 hours. After completion of the reaction, reprecipitation purification was performed using THF as a good solvent and water as a poor solvent. The precipitated solid was recovered and then dissolved again in THF, and reprecipitation purification was performed using n-hexane as a poor solvent. The precipitated solid was collected and dried under reduced pressure to obtain a white powder solid.
Yield was 0.30 (61%), M _n = 17200, M _w / M _n = 1.21.

  The phenol derivative of the present invention is considered to be extremely useful as an optical material used for an optical storage element, an optical switching system, or the like.

It is a UV spectrum in each light irradiation time of (1a) whose polymerization degree n is 20. It is a UV spectrum in each light irradiation time of (1a) whose polymerization degree n is 30. It is a UV spectrum in each light irradiation time of (1a) whose polymerization degree n is 40. It is a figure showing the relationship between the light irradiation time of the 9-ATC residue computed from UV spectrum, and an isomerization rate. It is the figure which plotted the isomerization rate in the initial stage of the reaction in the first-order rate equation. It is a UV spectrum in each light irradiation time of (1b) whose polymerization degree n is 20. It is a UV spectrum in each light irradiation time of (1b) whose polymerization degree n is 30. It is a UV spectrum in each light irradiation time of (1b) whose polymerization degree n is 40. It is a figure showing the relationship between the light irradiation time of 2-ATC residue computed from UV spectrum, and an isomerization rate. It is the figure which plotted the isomerization rate in the initial stage of the reaction in the first-order rate equation. It is a UV spectrum in each light irradiation time of (2a) whose polymerization degree n is 20. It is a UV spectrum in each light irradiation time of (2a) whose polymerization degree n is 30. It is a UV spectrum in each light irradiation time of (2a) whose polymerization degree n is 40. It is a figure showing the relationship between the light irradiation time of the 9-ATC residue computed from UV spectrum, and an isomerization rate. It is the figure which plotted the isomerization rate in the initial stage of the reaction in the first-order rate equation. It is a UV spectrum in each light irradiation time of (2b) whose polymerization degree n is 20. It is a UV spectrum in each light irradiation time of (2b) whose polymerization degree n is 30. It is a UV spectrum in each light irradiation time of (2b) whose polymerization degree n is 40. It is a figure showing the relationship between the light irradiation time of 2-ATC residue computed from UV spectrum, and an isomerization rate. It is the figure which plotted the isomerization rate in the initial stage of the reaction in the first-order rate equation.

Claims (6)

A phenol derivative represented by the following formula (1) or (2).
[Wherein, m is 4 and n is an integer of 20 to 40 . R ₁ is a methyl group or a t-butyl group , R ₂ is an isopropylidene group , X is chlorine, bromine or iodine, and R ₃ is a group represented by the following formula (3a) or (3b) is there.
(In the formula, R ₄ is a divalent organic group having 1 to 20 carbon atoms.) The method for producing a phenol derivative according to claim 1, wherein a compound represented by the following formula (4) or (5) is reacted with a compound represented by the following formula (6a) or (6b).
(In the formula, m is 4 and n is an integer of 20 to 40. R ₁ is a methyl group or a t-butyl group , R ₂ is an isopropylidene group , and X is chlorine, bromine or iodine. And R ₄ is a divalent organic group having 1 to 20 carbon atoms.)   An optical material containing the phenol derivative of claim 1 and having a refractive index in the range of 1.500 to 1.900.   An optical waveguide made of the optical material according to claim 3.   An optical film comprising the optical material according to claim 3.   A refractive index conversion material comprising the optical material according to claim 3.