JP6258078B2 - Dinaphthothiophene compound, polymer containing dinaphthothiophene skeleton and method for producing the same - Google Patents

Description

  The present invention relates to a dinaphthothiophene compound, a polymer containing a dinaphthothiophene skeleton, and a method for producing the same. More specifically, the present invention relates to a refractive index improver, a dinaphthothiophene compound useful as a high refractive index material, and a polymer containing a dinaphthothiophene skeleton.

Plastic optical materials are lighter than inorganic materials such as glass and have features such as being hard to break and easy to process. Application to spectacle lenses, camera lenses, industrial lenses, retardation compensators for liquid crystal displays, optical fibers, etc. Is expected. However, current plastic optical materials have many problems to be solved. For example, in lens applications, characteristics such as high refractive index and high heat resistance are required, but the refractive index of plastic lenses currently in practical use does not reach the refractive index of high refractive index glass materials, and is also heat resistant. Therefore, further performance improvement is required.
Under such circumstances, the inventors of the present invention have studied an organic compound having a high refractive index. As a result, dinaphtho [2,1-b: 1 ′, 2′-d] thiophene represented by the following formula ( Hereinafter, for the sake of convenience, the present inventors have found that (hereinafter simply referred to as dinaphthothiophene) has a high refractive index that is rare as an organic compound. The numbers in the formula are substitution position numbers.

  Based on the above findings, the present inventors have synthesized various dinaphthothiophene compounds and found compounds having a high refractive index. Furthermore, if a polymer containing a dinaphthothiophene skeleton having a high refractive index is obtained, it can be expected as a refractive index improver for new optical materials or existing optical materials, so a polymer containing a dinaphthothiophene skeleton is synthesized. doing. Patent applications have already been filed for such dinaphthothiophene compounds and polymers containing a dinaphthothiophene skeleton (Patent Documents 1 and 2).

JP 2011-178985 A JP 2012-136576 A

The polymer containing a dinaphthothiophene derivative and a dinaphthothiophene skeleton described in Patent Documents 1 and 2 above can achieve the intended purpose of having a high refractive index and excellent heat resistance. However, it is desirable to further improve characteristics such as refractive index, heat resistance and solubility in a solvent. That is, the dinaphthothiophene compound specifically described in the patent document is on a benzene ring condensed with a thiophene ring (more specifically, a position close to a sulfur atom at the 6-position of the dinaphthothiophene ring). Therefore, the polymer derived from the dinaphthothiophene compound has a structure in which the thiophene ring is close to the main chain of the polymer. By the way, dinaphthothiophene differs from benzothiophene in which the benzene ring and the thiophene ring have the same planar structure, and the thiophene ring and naphthalene ring do not have the same planar structure, but have a structure in which the two naltalene rings are slightly inclined. ing. This structural specificity increases the electron density of the sulfur moiety, which is considered to contribute to the improvement of the refractive index of dinaphthothiophene. Therefore, a compound having a high refractive index can be obtained by introducing a substituent or a polymerizable functional group on a benzene ring not condensed with a thiophene ring instead of a benzene ring condensed with a thiophene ring in dinaphthothiophene. In addition, by deriving a polymer from the compound having the polymerizable functional group introduced therein, a polymer having a high refractive index and a high heat resistance can be obtained, and an improvement in solubility in a solvent can be expected.
The present invention has been made based on such consideration, and from dinaphthothiophene, a compound in which a substituent or a polymerizable functional group is introduced on a benzene ring that is not condensed with a thiophene ring, and a compound in which the polymerizable functional group is introduced. The obtained polymer is provided.

  This invention made | formed in order to solve said subject is a dinaphtho thiophene compound represented by following General formula (1).

In the above formula, R is a substituent on the benzene ring that is not condensed with the thiophene ring, and is a hydroxyl group, 2-allyloxy group, vinyloxy group, 2,3-epoxypropoxy group (that is, glycidyloxy group), 2- ( meth) acryloyloxy group, 2- (meth) acryloyloxy ethoxy, R 1 ^O-group (wherein, R ¹ is oxygen or sulfur represents an alkyl group which may contain a hetero atom) or HO-X —O— group (wherein X represents an alkylene chain or an aralkylene chain which may contain oxygen or sulfur as a hetero atom).

The compound represented by the general formula (1) is a novel compound not described in any literature. The compound is useful as a refractive index improver, and is useful as a monomer for a polymer containing a dinaphthothiophene skeleton described later and as a raw material for synthesizing the monomer.
Moreover, as a substituted position of the substituent R, it is preferable that it is 2,12 position or 3,11 position of a dinaphtho thiophene ring.

The polymer containing a dinaphthothiophene skeleton according to the present invention is a polymer containing a dinaphthothiophene skeleton having a structure represented by the following formula (2) or (3) as a repeating unit. However, in the polymer, the main chain of the polymer is bonded to a benzene ring not condensed with the thiophene ring.
In the following formulas (2) and (3), X represents the same as above, Y represents an alkylene chain, aralkylene chain or arylene chain which may contain oxygen or sulfur as a hetero atom, and Z represents an oxygen atom or a sulfur atom.
Hereinafter, for convenience, “a polymer containing a dinaphthothiophene skeleton having a structure represented by formula (2) as a repeating unit” is referred to as “a polymer containing a dinaphthothiophene skeleton represented by formula (2)”. Called. The same applies to a polymer including a dinaphthothiophene skeleton having a structure represented by the formula (3) as a repeating unit.

Furthermore, the manufacturing method of the polymer containing the dinaphthothiophene skeleton of the present invention is represented by the above formula (2) or (3) from a dinaphthothiophene compound represented by the following formula (1-E). This is a method for producing a polymer containing a dinaphthothiophene skeleton.
Further, the present invention is a refractive index improver comprising a dinaphthothiophene compound represented by the general formula (1) or a polymer containing a dinaphthothiophene skeleton represented by the formula (2) or (3).

  According to the present invention, a substituent or a polymerizable functional group is introduced on a benzene ring that is not condensed with a thiophene ring in dinaphthothiophene, and a compound having a high refractive index can be obtained. Polymers containing a dinaphthothiophene skeleton derived from a group-introduced compound can be made into a material having a high refractive index and heat resistance because the thiophene ring is separated from the main chain, and further improved solubility in solvents. Can be planned.

As described above, the dinaphthothiophene compound according to the present invention is a dinaphthothiophene compound represented by the general formula (1).
In the compound, R ¹ is an alkyl group which may contain oxygen or sulfur as a hetero atom.

  Examples of the alkyl group that may contain a hetero atom include a linear or branched alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, dodecyl group, cetyl group, methoxymethyl group, 2-methoxyethyl group, ethoxymethyl group, 2- (ethoxy) ethyl group, Examples thereof include a 2- (methyl mercapto) ethyl group.

X is an alkylene chain or an aralkylene chain which may contain oxygen or sulfur as a hetero atom. Examples of the alkylene chain include linear or branched alkylene chains having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a decamethylene group, Examples include a propylene group and a cyclohexylene group. Examples of the alkylene chain that may contain oxygen or sulfur heteroatoms include polyoxyalkylene chains having oxyethylene or oxypropylene as a repeating unit.
Examples of the alkylene part of the aralkylene chain which may contain an oxygen or sulfur hetero atom include the above-described alkylene chains.
Y is an alkylene chain, aralkylene chain or arylene chain which may contain oxygen or sulfur as a hetero atom. Examples of the alkylene chain and the aralkylene chain include the above-described chains. Examples of the arylene chain include a phenylene group, a naphthylene group, a phenanthrenylene group, a pyrenylene group, a biphenylene group, a benzophenanthrenylene group, and a dibenzophenanthrenylene group.

  The dinaphthothiophene compound represented by the general formula (1) can be synthesized by various synthesis methods, and can be produced by, for example, the following reaction steps. In addition, in the said reaction process type | formula, reaction itself of each process is all well-known reaction.

The compound represented by the formula (1-a), which is a kind of the compound represented by the general formula (1) of the present invention, is a 1,1′-binaphthol derivative represented by the formula (5) in the presence of a base. It is reacted with N, N-dimethylthiocarbamoyl chloride to form a dimethylthiocarbamate compound represented by the formula (6), and this dimethylthiocarbamate compound is then heated in a high boiling solvent such as sulfolane (boiling point 285 ° C.). Can be obtained.
The reaction for producing the dimethylthiocarbamate represented by the above formula (6) is performed in an organic solvent such as DMF in the presence of a base such as sodium hydride, and the reaction temperature is 60 to 100 ° C. The reaction is usually completed in 1 to 4 hours. After completion of the reaction, the dimethylthiocarbamate body (6) is precipitated by cooling and can be obtained by filtration. The amount of N, N-dimethylthiocarbamoyl chloride used with respect to the 1,1′-binaphthol derivative is about 2 to 3 moles.
Next, the compound represented by the formula (1-a) can be obtained by heating the produced dimethylthiocarbamate (6) in a high boiling point solvent such as sulfolane. The reaction temperature at this time is about 200 to 270 ° C., and the heating time is about 5 to 10 hours. After completion of the reaction, the compound represented by the formula (1-a) can be obtained by cooling and collecting the precipitated crystals by filtration.

  The compound represented by the formula (1-b) can be obtained by subjecting the compound represented by the formula (1-a) to a dealkylation reaction. This reaction can be performed by heating in an organic solvent such as toluene in the presence of a Lewis acid such as aluminum chloride and N, N-dimethylaniline. The reaction temperature at this time is about 90 to 120 ° C., and the heating time is about 10 to 15 hours. After completion of the reaction, the compound represented by the formula (1-b) can be obtained by diluting with aqueous hydrochloric acid and collecting the precipitate by filtration.

  The compound represented by the formula (1-c) can be obtained by reacting epichlorohydrin with the compound represented by the formula (1-b). This reaction is carried out in the presence of a base or a quaternary ammonium salt using epichlorohydrin in excess of the solvent. The reaction temperature at this time is about 100 to 120 ° C., and the heating time is about 1 to 3 hours. After completion of the reaction, excess epichloro is distilled off, diluted with a poor solvent such as isopropyl alcohol, and the precipitate is collected by filtration to obtain the compound represented by the formula (1-c).

  The compound represented by the formula (1-d) can be obtained by reacting an allyl halide such as allyl bromide with the compound represented by the formula (1-b). This reaction is carried out in an organic solvent such as DMF in the presence of a base such as sodium hydride. The reaction temperature at this time is 15 ° C. or less, preferably 10 ° C. or less, and the reaction time is about 3 to 7 hours. After completion of the reaction, the compound represented by the formula (1-d) can be obtained by diluting with water and collecting the precipitate by filtration.

The compound represented by the formula (1-e) can be obtained by reacting the compound represented by the formula (1-b) with ethylene carbonate. This reaction is carried out under heating in an organic solvent such as DMF in the presence of a base such as sodium hydride or potassium carbonate. The reaction temperature at this time is about 90 to 110 ° C., and the reaction time is about 3 to 7 hours. After completion of the reaction, the compound represented by the formula (1-e) can be obtained by diluting with aqueous hydrochloric acid and collecting the precipitate by filtration.
Here, instead of ethylene carbonate, Q—X—Z—H (wherein X is the same as above, Q is a halogen atom such as a chlorine atom, bromine atom or iodine atom, and Z is an oxygen atom or a sulfur atom) by reacting a compound represented by), the compounds -CH ₂ -CH ₂ -OH group in the compound represented by the formula (1-e) was converted to the group represented by -X-Z-H Can be obtained. In this specification, this compound and the compound represented by the formula (1-e) are collectively referred to as a compound represented by the following formula (1-E).
In the compound represented by the formula (1-E), the group —X—Z—H includes — [CH (R ² ) —CH ₂ —Z—] _p —H (wherein Z represents The same, R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and p is a positive integer, preferably 1 to 10, more preferably 1 to 6). A polyoxyethylene group and a polyoxypropylene group.

  In the formula, X and Z are the same as described above, and the group —O—X—ZH is bonded to a benzene ring not condensed with the thiophene ring.

  The compound represented by the formula (1-f) can be obtained by reacting methacrylic anhydride or methacrylic acid chloride with the compound represented by the formula (1-b). This reaction is performed in the presence of a base such as N, N-dimethylaniline in an organic solvent that does not adversely influence the reaction. The reaction temperature at this time is 50 ° C. or less, preferably about 40 ° C. or less, and the reaction time is about 1 to 25 hours. After completion of the reaction, the compound represented by the formula (1-f) can be obtained by diluting with water and collecting the precipitate by filtration.

The present invention also provides a polymer containing a dinaphthothiophene skeleton represented by formulas (2) to (3).
The polymer containing the dinaphthothiophene skeleton represented by the formula (2) can be produced by reacting the dinaphthothiophene compound represented by the formula (1-E) with diphenyl carbonate.
In this reaction, the dinaphthothiophene compound represented by the formula (1-E) and diphenyl carbonate are used in approximately equimolar amounts, and the reaction is carried out in the presence of a base such as N, N-dimethylaniline under heating. In this case, the reaction temperature is about 180 to 250 ° C., preferably after heating in the presence of an inert gas and under reduced pressure degassing, and the reaction time is about 1 to 2 hours. After completion of the reaction, the polymer is cooled and the precipitated solid is washed with a solvent such as methanol, whereby a polymer containing a dinaphthothiophene skeleton represented by the formula (2) can be obtained.

In addition, the polymer containing the dinaphthothiophene skeleton represented by the formula (3) is added to the dinaphthothiophene compound represented by the above formula (1-E): HOOC-Y-COOH (wherein Y represents It can be obtained by reacting a reactive derivative in the carboxy group of the compound represented by Examples of the reactive derivative include acid halides, mixed acid anhydrides, etc. Specific examples of such compounds include adipic acid dichloride (also referred to as adipic acid chloride, the same applies to other dichlorides), and succinic acid dichloride. And glutaric acid dichloride and 1,4-cyclohexanedicarboxylic acid dichloride.
In this reaction, the dinaphthothiophene compound represented by the formula (1-E) and the reactive derivative at the carboxy group of the dicarboxylic acid are used in approximately equimolar amounts, and the reaction is carried out in an organic solvent such as diphenyl ether with heating. At this time, under an inert gas stream, the reaction temperature is about 160 to 200 ° C., and the reaction time is about 1.5 to 3 hours. After completion of the reaction, the reaction mixture is cooled, and the precipitated solid is washed with a solvent such as methanol, and then dissolved in chloroform and reprecipitated in diethyl ether to obtain a polymer containing a dinaphthothiophene skeleton represented by the formula (3). Can be obtained.

  In the polymer containing the dinaphthothiophene skeleton represented by the above formula (2) or (3), the mass average molecular weight is preferably 700 to 200,000, more preferably 1000 to 50000, still more preferably 1000 to 20000. is there. If the mass average molecular weight is 700 or more, the film-forming property, volatilization resistance, compatibility and solvent resistance are good. If the mass average molecular weight is 200,000 or less, particularly 20000 or less, the solubility in a solvent is reduced. Increase in viscosity is suppressed.

The polymer containing the dinaphthothiophene compound represented by the general formula (1) and the dinaphthothiophene skeleton represented by (2) or (3) of the present invention is useful as a refractive index improver and is a conventional plastic optical material. The refractive index can be improved by adding to the material.
The conventional plastic optical material is not particularly limited. For example, poly (meth) acrylic acid resin, polystyrene resin, polyvinyl ether resin, polyolefin resin, polycarbonate resin, polyester resin, polyimide resin, polyamide resin, for example. Resins, polysulfide resins, polyurethane resins, polysiloxane resins and the like are exemplified, and may be blend resins and copolymer resins.
The addition amount to the plastic optical material of the polymer containing the dinaphthothiophene compound represented by the general formula (1) and the dinaphthothiophene skeleton represented by (2) or (3) is appropriately determined according to the desired characteristics. Although it can be adjusted, it is usually adjusted to about 10 to 90% by weight, preferably about 30 to 70% by weight.
Further, the polymer itself containing the dinaphthothiophene skeleton represented by (2) or (3) can be used as an optical material.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

Example 1
In a 3 L flask of 7,7′-dimethoxy-1,1′-bi-2-naphthol, 348.4 g (2.0 mol) of 2-hydroxy-7-methoxynaphthalene, 1285 mL of methanol, 118 mL of water, 104 g of sodium hydroxide ( 2.6 mol), and the temperature is raised to 50 ° C. After the temperature rise, 1431 g (3.0 mol) of a 34% aqueous ferric chloride solution is added dropwise over 2 hours and reacted at the same temperature for 3 hours. After the reaction, 720 mL of methanol, 312.9 g (3.0 mol) of 35% hydrochloric acid, and 468 mL of water were injected, and after cooling to 10 ° C. or lower, the crystals were filtered, washed with 870 mL of water, and dried to give 318.1 g. (0.9 mol) of 7,7′-dimethoxy-1,1′-bi-2-naphthol was obtained as gray crystals. (Purity: 98%, theoretical yield 90%)
¹ H NMR (400 MHz, CDCl ₃ ) δ: 3.50 (s, 6H), 5.24 (s, 6H), 6.43 (d, J = 2.6, 2H), 6.97 (dd, J = 8.8, 2.6, 2H), 7.12 (d, J = 8.8, 2H), 7.68 (d, J = 8.8, 2H) and 7.75 (d, J = 8.8, 2H) ppm.
¹³ C NMR (100 MHz, CDCl ₃ ) δ: 55.0, 103.1, 110.3, 115.1, 115.9, 124.6, 129.8, 130.9, 134.7, 153.2 and 158.9 ppm.
mp: 151.8 ° C

Example 2
7,7′-dimethoxy-1,1′-binaphthalene-2,2′-diyl O, O′-bis (N, N-dimethylthiocarbamate)
A 1 L flask is charged with 189.0 g of N, N-dimethylformaldehyde and 31.2 g (0.78 mol) of 60% sodium hydride under a nitrogen stream and cooled to 15 ° C. or lower. Separately, in another 1 L flask under nitrogen flow, 405.0 g of N, N-dimethylformaldehyde, 106.0 g of 7,7′-dimethoxy-1,1′-bi-2-naphthol (purity 98%, 0.3 Mol) is stirred and dissolved, transferred to a dropping funnel, and dropped into the above solution at 15 ° C. or lower over 1 hour. After dropping, the mixture was aged at 15 ° C. or lower for 1 hour, charged with 100.1 g (0.81 mol) of N, N-dimethylthiocarbamoyl chloride, heated to 80 ° C., and reacted for 2 hours. After the reaction, 378.0 g of water was added dropwise at the same temperature over 30 minutes, cooled to 10 ° C. or lower, filtered at the same temperature, washed with 150.0 g of water, and dried to obtain 139.9 g of 7, 7′-Dimethoxy-1,1′-binaphthalene-2,2′-diyl O, O′-bis (N, N-dimethylthiocarbamate) was obtained as brown crystals. (Purity: 96%, yield 86%)
¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ: 2.52 (s, 6H), 3.07 (s, 6H), 3.61 (s, 6H), 6.78 (d, J = 2. 4, 2H), 7.10 (dd, J = 9.0, 2.5, 2H), 7.43 (d, J = 8.8, 2H), 7.79 (d, J = 9.0) , 2H) and 7.88 (d, J = 8.8, 2H) ppm.
¹³ C NMR (100 MHz, CDCl ₃ ) δ: 38.0, 42.7, 55.4, 105.0, 118.5, 123.1, 126.9, 128.0, 129.2, 134.7 , 150.1, 157.9 and 186.1 ppm.
mp: 186.7 ° C

Example 3
To a 1 L flask connected to a 2,12-dimethoxydinaphthothiophene distillation apparatus, 7,7′-dimethoxy-1,1′-binaphthalene-2,2′-diyl O, O′-bis (N, N-dimethylthiocarbamate) 162.7 g (purity 96%, 0.3 mol) and sulfolane 300 g are charged at room temperature, heated to 255 ° C., and reacted at 255 to 265 ° C. for 6 hours. In addition, in temperature rising and reaction, it carries out, distilling off the low boiling-point component byproduced. After the reaction, it is cooled to 50 ° C., 170 mL of methanol is added dropwise at the same temperature, cooled to 10 ° C. or less, the crystal is filtered, washed with 300 mL of methanol, and dried to obtain 70.3 g of 2,12-dimethoxydioxide. Naphthothiophene was obtained as light brown crystals. (Purity: 97%, 66% yield)
¹ H NMR (400 MHz, CDCl ₃ ) δ: 3.78 (s, 6H), 7.17-7.20 (m, 2H), 7.74-7.79 (m, 4H), 7.86 ( d, J = 8.8, 2H) and 8.09 (br, 2H) ppm.
¹³ C NMR (100 MHz, CDCl ₃ ) δ: 55.3, 107.2, 116.5, 118.4, 126.8, 127.1, 130.1, 130.4, 130.6, 138.9 and 156.6 ppm.
mp: 168.0 ° C, refractive index (n _632.8 ): 1.757

Example 4
Under a nitrogen stream, 106.5 g of 2,12-dimethoxydinaphthothiophene (purity 97%, 0.3 mol), 1380 mL of toluene, 145.4 g of N, N-dimethylaniline, into a 3 L flask of 2,12-dihydroxydinaphthothiophene. (1.2 mol) and 160.0 g (1.2 mol) of aluminum chloride are charged at room temperature, and the temperature is raised to 105 ° C. It reacts at 105-115 degreeC for 15 hours, and cools to 30 degrees C or less. Add 1050 mL of water and 250.3 g (2.4 mol) of 35% hydrochloric acid, raise the temperature to 50 ° C., filter, wash with 900 mL of water, and dry to give 101.0 g of 2,12-didihydroxydinaphtho. Thiophene was obtained as blue crystals (purity 94%, yield 94%).
The crystals were recrystallized from 750 mL of methanol to obtain 84.9 g (yield 89.4%) of 100% pure 2,12-dihydroxydinaphthothiophene.
¹ H NMR (400 MHz, DMSO-d ₆ ) δ: 7.22 (d, J = 8.7, 2.2, 2H), 7.82-7.88 (m, 4H), 7.95 (d , J = 8.7, 2H), 8.15 (d, J = 2.2, 2H) and 10.06 (brs, 2H) ppm.
¹³ C NMR (100 MHz, DMSO-d ₆ ) δ: 109.4, 117.3, 117.7, 126.2, 127.3, 129.6, 130.5, 131.0, 138.2 and 155 .2 ppm.
mp: 317.8 ° C

Example 5
Under a nitrogen stream, 63.3 g of 2,12-dihydroxydinaphthothiophene (purity 100%, 0.2 mol), N, N-dimethylformamide into a 1 L flask of 2,12-bis (2-hydroxyethoxy) dinaphthothiophene 413 mL, caustic soda 8.0 g (0.2 mol) and ethylene carbonate 116.2 g (1.32 mol) are charged at room temperature, and the temperature is raised to 90 ° C. It reacts at 90-110 degreeC for 5 hours, and cools to 30 degrees C or less. Add 600 g of 17% hydrochloric acid, raise the temperature to 50 ° C., filter, wash with 300 mL of hot water, and dry to give 77.2 g of 2,12-bis (2-hydroxyethoxy) dinaphthothiophene as pale yellow crystals (Purity 99%, yield 94.5%).
¹ H NMR (400 MHz, DMSO-d ₆ ) δ: 3.84 (m, 4H), 4.12 (m, 4H), 5.06 (s, 2H), 7.38-7.40 (m, 2H), 8.00-8.08 (m, 4H) and 8.10-8.15 (m, 4H) ppm.
mp: 177.5 ° C

Reference Example 6
To a flask of 2,12-diallyloxydinaphthothiophene under a nitrogen stream, 63.3 g of 2,12-dihydroxydinaphthothiophene (purity 100%, 0.2 mol), N, N-dimethylformamide 1963 mL, 60% hydrogen Sodium chloride 20.8 g (0.52 mol) is charged at room temperature, stirred for 1 hour or longer, and then cooled to 10 ° C. or lower. 62.9 g (0.52 mol) of allyl bromide is added dropwise at 10 ° C. or lower and reacted at the same temperature for 5 hours. After the reaction, 600 mL of water was added and stirred at 10 ° C. or lower for 1 hour or longer, followed by filtration, washing with 200 mL of water and methanol in order, and drying to obtain 71.3 g of 2,12-diallyloxydinaphthothiophene. Obtained as pale yellow crystals (purity 99%, yield 89%).
¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ: 4.44 (d, J = 4.2, 4H), 5.15 (d, J = 10.4, 2H), 5.27 (d, J = 17.2, 2H), 5.89-5.98 (m, 2H), 7.11 (d, J = 8.2, 2H), 7.61 (br, 4H), 7.72 (d , J = 8.8, 2H), and 8.10 (br, 2H) ppm.
¹³ C NMR (100 MHz, CD ₂ Cl ₂ ) δ: 68.8, 108.5, 116.2, 117.7, 118.3, 126.6, 127.1, 130.0, 130.3, 130 .5, 132.9, 138.8 and 155.5 ppm.
mp: 89.7 ° C., refractive index (n _632.8 ): 1.729

Example 7
To a flask with a reflux apparatus of 2,12-diglycidyloxydinaphthothiophene 3L, 63.3 g of 2,12-dihydroxydinaphthothiophene (purity 100%, 0.2 mol), 1900 g of epichlorohydrin, benzyltri-n-butylammonium chloride 37.4 g (0.12 mol) is charged at room temperature, stirred for 30 minutes or more, and then heated to reflux (100 to 120 ° C.). After reacting under reflux for 1 hour, cool to 50 ° C. or lower. After switching from the reflux device to the distillation device, the solution was concentrated under reduced pressure at 50 ° C. or lower to recover excess epichlorohydrin, and then 2000 mL of isopropyl alcohol was added at 50 ° C. or lower and stirred at the same temperature for 1 hour or longer. By sequentially washing with water and methanol, and drying, 62.7 g of 2,12-diglycidyloxydinaphthothiophene was obtained as a white solid (purity 97%, yield 71%).
1H NMR (400 MHz, CD ₂ Cl ₂ ) δ: 2.74-2.76 (m, 2H), 2.88-2.91 (m, 2H), 3.37-3.42 (m, 2H) 3.93-4.02 (m, 2H), 4.26-4.30 (m, 2H), 7.26-7.30 (m, 2H), 7.82-7.87 (m, 4H), 7.94-7.96 (m, 2H) and 8.15-8.17 (m, 2H) ppm.
mp: 133.1 ° C., the refractive index _{(n 632.8):} 1.723

Example 8
To a flask of 2,12- bis (2-methacryloyloxyethoxy) dinaphthothiophene 3 L, 40.9 g of 2,12-dihydroxydiethoxy-dinaphthothiophene (purity 99%, 0.1 mol), tetrahydrofuran 1800 mL, 2,2 , 6,6-tetramethylpiperidine-1-oxyl 0.1 g and N, N-dimethyl-4-aminopyridine 3.7 g (0.03 mol) were charged at room temperature, respectively, and 18.5 g (0. 12 mol) is added dropwise at 40 ° C. or lower and reacted at the same temperature for 20 hours. After the reaction, 600 mL of water was added, cooled to 10 ° C. or lower, stirred for 1 hour or longer at the same temperature, filtered, washed with 200 mL of water and methanol in order, and dried to obtain 36.6 g of 2,12- Bis (2-methacryloyloxyethoxy) dinaphthothiophene was obtained as a white solid (purity 99%, yield 67.0%).
¹ H NMR (400 MHz, CDCl ₃ ) δ: 1.89-1.90 (m, 6H), 4.27-4.30 (m, 4H), 4.48-4.50 (m, 4H), 5.52-5.53 (m, 2H), 6.07-6.07 (m, 2H), 7.28 (dd, J = 8.92, 2.5, 2H), 7.82-7 .88 (m, 4H), 7.96 (d, J = 8.9, 2H) and 8.20 (d, J = 2.5, 2H) ppm.
mp: 110.1 ° C., the refractive index _{(n 632.8):} 1.647

Example 9
2,12-bis [2- (2-hydroxyethoxy) ethoxy] dinaphthothiophene (hereinafter referred to as DDEGODNT)
To a 500 mL flask, 2,12-dihydroxydinaphthothiophene 12.0 g (100% purity, 37.93 mmol), N, N-dimethylformamide 240 mL, potassium carbonate 42.0 g (303.44 mmol), 2- (2-chloro Ethoxy) -ethanol 36.2 g (purity 98%, 284.5 mmol) is charged at room temperature, heated to 80-85 ° C., and reacted at the same temperature for 20 hours. After the reaction, the mixture was cooled to room temperature, 190 mL of water and 190 mL of ethyl acetate were added, stirred for 30 minutes or more, then separated and dried to obtain 13.4 g of DDEGDNT as a white solid (purity 99%, yield) 71.0%).
¹ H NMR (400 MHz, CDCl ₃ ) δ: 3.20 (brs, 2H), 3.65-3.68 (m, 4H), 3.74-3.76 (m, 4H), 3.82- 3.85 (m, 4H), 4.12-4.14 (m, 4H), 7.24 (dd, J = 2.4, 7.4, 2H), 7.78-7.83 (m , 4H), 7.91 (d, J = 8.9, 2H) and 8.11 (d, J = 2.4, 2H) ppm.
mp: 104.8 ° C., the refractive index _(n 632.8): 1.677

Example 10
2,12-bis [2- [2- (2-hydroxyethoxy) ethoxy] ethoxy] dinaphthothiophene (hereinafter referred to as DTEGODNT)
To a 100 mL flask, 3.0 g (purity 100%, 9.48 mmol) of 2,12-dihydroxydinaphthothiophene, 60 mL of N, N-dimethylformamide, 10.4 g (75.2 mmol) of potassium carbonate, 2- [2- ( 2-Chloroethoxy) ethoxy] -ethanol 12.0 g (purity 98%, 69.7 mmol) is charged at room temperature, heated to 80-85 ° C., and reacted at the same temperature for 20 hours. After the reaction, the reaction mixture was cooled to room temperature, added with 50 mL of water and 50 mL of toluene, stirred for 30 minutes or more, separated, and dried to obtain 2.9 g of DTEGODNT as a brown viscous liquid (purity 99%, yield) 71.0%).
¹ H NMR (400 MHz, CDCl ₃ ) δ: 3.15 (brs, 2H), 3.57-3.59 (m, 4H), 3.65-3.67 (m, 4H), 3.70- 3.72 (m, 8H), 3.86-3.89 (m, 4H), 4.17-4.20 (m, 4H), 7.28 (dd, J = 2.4, 8.9) , 2H), 7.80-7.87 (m, 4H), 7.93 (d, J = 8.9, 2H) and 8.16 (d, J = 2.4, 2H) ppm,
Refractive index _(n 632.8): 1.653.

Example 11
In a 3 L flask of 6,6′-dimethoxy-1,1′-bi-2-naphthol, 348.4 g (2.0 mol) of 2-hydroxy-6-methoxynaphthalene, 1285 mL of methanol, 118 mL of water, 104 g of sodium hydroxide ( 2.6 mol), and the temperature is raised to 50 ° C. After the temperature rise, 1431 g (3.0 mol) of a 34% aqueous ferric chloride solution is added dropwise over 2 hours and reacted at the same temperature for 3 hours. After the reaction, 720 mL of methanol and 312.9 g (3.0 mol) of 35% hydrochloric acid were injected and cooled to 10 ° C. or lower, and then the crystals were filtered, washed with 870 g of water, and dried to obtain 328.7 g (0. 93 mol) of 6,6′-dimethoxy-1,1′-bi-2-naphthol was obtained as gray crystals. (Purity: 98%, theoretical yield 93%)
¹ H NMR (400 MHz, CDCl ₃ ) δ: 3.90 (s, 6H), 6.97-6.97 (m, 2H), 7.06 (d, J = 9.0, 2H), 7. 21-7.21 (m, 2H), 7.35 (d, J = 9.0, 2H) and 7.85 (d, J = 9.0, 2H) ppm.
¹³ C NMR (100 MHz, CDCl ₃ ) δ: 55.4, 106.8, 111.3, 118.1, 119.8, 125.8, 128.5, 130.0, 130.4, 150.9 and 156.4 ppm.
mp: 198.7 ° C

Example 12
6,6′-dimethoxy-1,1′-binaphthalene-2,2′-diyl O, O′-bis (N, N-dimethylthiocarbamate)
A 1 L flask is charged with 310 mL of N, N-dimethylformaldehyde and 52.0 g (1.3 mol) of 60% sodium hydride under a nitrogen stream and cooled to 15 ° C. or lower. Separately, in another 1 L flask under a nitrogen stream, 700 mL of N, N-dimethylformaldehyde, 176.7 g of 6,6′-dimethoxy-1,1′-bi-2-naphthol (purity 98%, 0.5 mol) Is stirred and dissolved, transferred to a dropping funnel, and added dropwise to the previous solution at 15 ° C. or lower over 1 hour. After dropping, the mixture was aged at 15 ° C. or lower for 1 hour, charged with 160.0 g (1.3 mol) of N, N-dimethylthiocarbamoyl chloride, heated to 80 ° C., and reacted for 2 hours. After the reaction, 600 mL of water was added dropwise at the same temperature over 30 minutes, cooled to 10 ° C. or lower, filtered at the same temperature, washed with 250 mL of water, and dried to yield 268.5 g of 6,6′-dimethoxy. -1,1'-Binaphthalene-2,2'-diyl O, O'-bis (N, N-dimethylthiocarbamate) was obtained as light brown crystals. (Purity: 96%, yield 99%)
¹ H NMR (400 MHz, CDCl ₃ ) δ: 2.58 (s, 6H), 3.10 (s, 6H), 3.90 (s, 6H), 6.95 (d, J = 8.2) 2H), 7.19 (br, 2H), 7.32 (d, J = 8.4, 2H), 7.55 (d, J = 8.4, 2H) and (m, 2H), 7. 35 (d, J = 9.0, 2H) and 7.83 (d, J = 8.2, 2H) ppm.
mp: 217.8 ° C

Example 13
To a 1 L flask connected to a 3,11-dimethoxydinaphthothiophene distillation apparatus, under a nitrogen stream, 6,6′-dimethoxy-1,1′-binaphthalene-2,2′-diyl O, O′-bis (N, N-dimethylthiocarbamate) 162.7 g (purity 96%, 0.3 mol) and sulfolane 300 g are charged at room temperature, heated to 255 ° C., and reacted at 255 to 265 ° C. for 6 hours. In addition, in temperature rising and reaction, it carries out, distilling off the low boiling-point component byproduced. After the reaction, it is cooled to 50 ° C., 170 mL of methanol is added dropwise at the same temperature, cooled to 10 ° C. or lower, the crystal is filtered, washed with 300 mL of methanol, and dried to give 69.2 g of 3,11-dimethoxydioxide. Naphthothiophene was obtained as light brown crystals. (Purity: 97%, yield 65%)
¹ H NMR (400 MHz, CDCl ₃ ) δ: 3.96 (s, 6H), 7.26 (dd, J = 9.2, 2.7, 2H), 7.31 (d, J = 2.7) , 2H), 7.78 (d, J = 8.6, 2H), 7.87 (d, J = 8.6, 2H) and 8.72 (d, J = 9.2, 2H) ppm.
¹³ C NMR (100 MHz, CDCl ₃ ) δ: 55.3, 107.5, 116.2, 121.4, 125.0, 126.5, 127.4, 131.4, 133.5, 136.4 and 156.8 ppm.
mp: 183.9 ° C

Example 14
Under a nitrogen stream, 106.5 g of 3,11-dimethoxydinaphthothiophene (purity 97%, 0.3 mol), 1380 mL of toluene, 145.4 g of N, N-dimethylaniline under a nitrogen stream into a 2 L flask of 3,11-dihydroxydinaphthothiophene. (1.2 mol) and 160.0 g (1.2 mol) of aluminum chloride are charged at room temperature, and the temperature is raised to 105 ° C. It reacts at 105-115 degreeC for 15 hours, and cools to 30 degrees C or less. Add 1050 mL of water and 250.3 g (2.4 mol) of 35% hydrochloric acid, raise the temperature to 50 ° C., filter, wash with 900 mL of water, and dry to obtain 92.0 g of 3,11-didihydroxydinaphtho. Thiophene was obtained as blue crystals (purity 98%, yield 95%).
The crystals were recrystallized from 750 mL of methanol to obtain 84.5 g (yield 89%) of 3,11-dihydroxydinaphthothiophene having a purity of 100%.
¹ H NMR (400 MHz, DMF-d7) δ: 7.31 (dd, J = 9.1, 2.6, 2H), 7.51 (d, J = 2.6, 2H), 7.90 ( d, J = 8.7, 2H), 8.05 (d, J = 8.7, 2H), 8.73 (d, J = 9.1, 2H) and 10.10 (s, 2H) ppm .
¹³ C NMR (100 MHz, DMF-d7) δ: 111.3, 117.2, 121.9, 124.5, 127.1, 127.7, 131.8, 134.9, 136.2 and 156. 0 ppm.
mp: 303.0 ° C

Example 15
Under a nitrogen stream, 63.3 g of 3,11-dihydroxydinaphthothiophene (purity 100%, 0.2 mol), N, N-dimethylformamide into a 1 L flask of 3,11-bis (2-hydroxyethoxy) dinaphthothiophene 413 mL, caustic soda 8.0 g (0.2 mol) and ethylene carbonate 116.2 g (1.32 mol) are charged at room temperature, and the temperature is raised to 90 ° C. It reacts at 90-110 degreeC for 5 hours, and cools to 30 degrees C or less. Add 600 g of 17% hydrochloric acid, raise the temperature to 50 ° C., filter, wash with 300 mL of hot water, and dry to obtain 76.6 g of 3,11-dihydroxydiethoxydinaphthothiophene as pale yellow crystals ( Purity 94%, yield 89.0%).
¹ H NMR (400 MHz, DMSO-d6) δ: 3.81-3.85 (m, 4H), 4.19-4.21 (m, 4H), 4.96 (br, 2H), 7.30 (Dd, J = 9.2, 2.7, 2H), 7.61 (d, J = 2.7, 2H), 7.98 (d, J = 8.7, 2H), 8.13 ( d, J = 8.7, 2H) and 8.61 (d, J = 9.2, 2H) ppm.
mp: 220.3 ° C

Reference Example 16
To a flask of 3,11-diallyloxydinaphthothiophene under a nitrogen stream, 63.3 g (purity 100%, 0.2 mol) of 3,11-dihydroxydinaphthothiophene, 1963 mL of N, N-dimethylformamide, 60% hydrogen Sodium chloride 20.8 g (0.52 mol) is charged at room temperature, stirred for 1 hour or longer, and then cooled to 10 ° C. or lower. 62.9 g (0.52 mol) of allyl bromide is added dropwise at 10 ° C. or lower and reacted at the same temperature for 5 hours. After the reaction, 600 mL of water was added and stirred at 10 ° C. or lower for 1 hour or longer, followed by filtration, washing with 200 mL of water and methanol in order, and drying to obtain 72.8 g of 3,11-diallyloxydinaphthothiophene. Obtained as pale yellow crystals (purity 98%, yield 90.0%).
¹ H NMR (400 MHz, CDCl ₃ ) δ: 4.69-4.71 (m, 4H), 5.34 (dd, J = 10.5, 1.4, 2H), 5.50 (dd, J = 17.2, 1.6, 2H), 6.10-6.20 (m, 2H), 7.22 (dd, J = 9.2, 2.7, 2H), 7.32 (d, J = 2.7, 2H), 7.76 (d, J = 8.6, 2H), 7.86 (d, J = 8.6, 2H) and 8.72 (d, J = 9.2) , 2H) ppm.
¹³ C NMR (100 MHz, CDCl ₃ ) δ: 68.9, 108.6, 116.6, 117.8, 121.4, 125.1, 126.5, 127.4, 131.4, 133.2 , 133.5, 136.4 and 155.8 ppm. mp: 174.2 ° C., refractive index (n ₆₃₃ ): 1.730

Example 17
To a flask equipped with a reflux apparatus of 3,11-diglycidyloxydinaphthothiophene 3L, 34.6 g of 3,11-dihydroxydinaphthothiophene (purity 98%, 0.2 mol), epichlorohydrin 1900 g, benzyltri-n-butylammonium chloride 37.4 g (0.12 mol) is charged at room temperature, stirred for 30 minutes or more, and then heated to reflux (100 to 120 ° C.). After reacting under reflux for 1 hour, cool to 50 ° C. or lower. After switching from the reflux device to the distillation device, the solution was concentrated under reduced pressure at 50 ° C. or lower to recover excess epichlorohydrin, and then 2000 mL of isopropyl alcohol was added at 50 ° C. or lower and stirred at the same temperature for 1 hour or longer. By sequentially washing with water and methanol and drying, 80.3 g of 3,11-diglycidyloxydinaphthothiophene was obtained as a white solid (purity 95%, yield 89.0%).
¹ H NMR (300 MHz, CDCl ₃ ) δ: 2.85-2.87 (m, 2H), 2.97-3.00 (m, 2H), 3.46-3.50 (m, 2H), 4.14-4.20 (m, 2H), 7.23-7.37 (m, 2H), 7.80-7.93 (m, 4H) and 8.73-8.76 (m, 2H) ) Ppm.
mp: 210.1 ° C., refractive index (n ₆₃₃ ): 1.7208

Example 18
To a flask of 3,11- bis (2-methacryloyloxyethoxy) dinaphthothiophene 3 L, 33.0 g of 3,11-dihydroxydiethoxy-dinaphthothiophene (purity 94%, 0.1 mol), tetrahydrofuran 1800 mL, 2,2 , 6,6-tetramethylpiperidine-1-oxyl 0.1 g and N, N-dimethyl-4-aminopyridine 3.7 g (0.03 mol) were charged at room temperature, respectively, and 18.5 g (0. 12 mol) is added dropwise at 40 ° C. or lower and reacted at the same temperature for 20 hours. After the reaction, the mixture was cooled to 30 ° C. or lower, stirred at the same temperature for 1 hour or longer, filtered, washed with 200 mL of water and methanol in order, and dried to give 47.5 g of 3,11-bis (2-methacryloyl). Oxyethoxy) dinaphthothiophene was obtained as a white solid (purity 99%, yield 87.0%).
¹ H NMR (400 MHz, CDCl ₃ ) δ: 1.98-1.99 (m, 6H), 4.44 (dd, J = 5.12, 4.48, 4H), 4.62 (dd, J = 5.12, 4.48, 4H), 5.61-5.62 (m, 2H), 6.19-6.20 (m, 2H), 7.23-7.25 (m, 2H) , 7.38-7.38 (m, 2H), 7.81 (d, J = 8.6, 2H), 8.92 (d, J = 8.6, 2H) and 8.74 (d, J = 9.3, 2H) ppm
mp: 196.2 ° C

Example 19
Synthesis of polycarbonate DNTPC

In a three-necked flask, 2.02 g (5.0 mmol) of 2,12-dihydroxyethoxydinaphthothiophene (DHEODNT), 1.07 g (5.0 mmol) of diphenyl carbonate and 6.0 mg of N, N-dimethylaminopyridine (0 .05 mmol) was weighed and heated at 180 ° C. for 30 minutes in a nitrogen atmosphere, and then heated at 250 ° C. for 30 minutes while degassing under reduced pressure. After cooling to room temperature, the precipitated solid was washed with methanol and acetone to obtain 0.84 g of a pale yellow solid.
The physical property values of DNTPC are as follows.
IR (KBr): 1744, 1260 cm ⁻¹
Glass transition temperature 104 ° C (DSC, in nitrogen stream, 10 ° C / min)
5wt% weight loss temperature 379 ° C (TGA, in nitrogen stream, 10 ° C / min)

Example 20
Synthesis of polycarbonate DNTPCDE

In a three-necked flask, DDEGODNT 5.00 g (12.4 mmol), diphenyl carbonate 2.70 g (12.6 mmol) and zinc acetate 45 mg (0.25 mmol) were weighed and heated at 160 ° C. for 30 minutes in a nitrogen atmosphere. Thereafter, the temperature was gradually raised while degassing under reduced pressure, followed by heating at 250 ° C. and 2 mmHg for 30 minutes. After cooling to room temperature, the precipitated solid was dissolved in chloroform and purified by reprecipitation from methanol to obtain 6.2 g of a white solid.
The physical property values of DNTPDE are as follows.
IR (KBr): 1745 cm ⁻¹
Melting temperature 68 ° C (DSC, in a nitrogen stream, 10 ° C / min)
5wt% weight loss temperature 325 ° C (TGA, in nitrogen stream, 10 ° C / min)
¹ HNMR (400 MHz, CDCl ₃ ) δ: 8.2 to 7.1 (br, 10H), 4.5 to 4.0 (br, 8H), 3.6 to 3.9 (br, 8H)
IR (film): 1744 cm ⁻¹
GPC (CHCl ₃ ) polystyrene conversion: number average molecular weight 4,300, mass average molecular weight 5,200

Example 21
Synthesis of polycarbonate DNTPCTE

DTEGODNT 2.9 g (5.0 mmol), diphenyl carbonate 1.07 g (5.0 mmol) and N, N-dimethylaminopyridine 6.0 mg (0.05 mmol) were weighed in a three-necked flask, and the mixture was 30 ° C. at 180 ° C. in a nitrogen atmosphere. After heating for 30 minutes, the temperature was gradually raised while degassing under reduced pressure, followed by heating at 250 ° C. and 2 mmHg for 30 minutes. After cooling to room temperature, the precipitated solid solution was dissolved in chloroform and precipitated from methanol to obtain 3.3 g of a pale yellow solid solution.
The physical property values of DNTPCTE are as follows.
IR (KBr): 1744 cm ^−1
1 HNMR (400 MHz, CDCl ₃ ) δ: 8.2 to 7.2 (br, 10H), 4.3 to 4.1 (br, 8H), 3.9 to 3.7 (br, 4H), 3 .7 to 3.4 (br, 12H) ppm
IR (film): 1744 cm ⁻¹
GPC (CHCl ₃ ) polystyrene conversion: number average molecular weight 10,200, mass average molecular weight 27,000

Example 22
Synthesis of polyester DNTPE-1

To a three-necked flask was added 2.02 g (5.0 mmol) of 2,12-dihydroxyethoxydinaphththiophene (DHEODNT), 0.91 g (5.0 mmol) of adipic acid chloride and 23 ml of diphenyl ether (Ph ₂ O). In a nitrogen atmosphere, the mixture was heated at 185 ° C. for 2 hours with good stirring. The reaction solution was cooled to room temperature, and the precipitated solid was washed with methanol. The obtained solid was dissolved in chloroform, reprecipitated from ether, and then dried under reduced pressure to obtain 2.16 g (yield, 78.4%) of DNTPE-1 as a white solid.
The physical property values of DNTPE-1 are as follows.
Glass transition temperature 103 ° C (DSC, in nitrogen stream, 10 ° C / min)
5 wt% weight loss temperature 379 ° C (TGA in nitrogen stream, 10 ° C / min)
¹ HNMR (400 MHz, CDCl ₃ ) δ: 8.5 to 7.1 (br, 10H), 4.5 to 4.0 (br, 8H), 2.5 to 2.1 (br, 4H), 1 .9 to 1.4 (br, 4H) ppm
IR (film): 1744 cm ⁻¹
GPC (CHCl ₃ ) polystyrene conversion: number average molecular weight 4,740, mass average molecular weight 11,300

Example 23
(1) Synthesis of 1,4-cyclohexanedicarboxylic acid chloride In a three-necked flask, 6.19 g (36 mmol) of 1,4-cyclohexanedicarboxylic acid (cis / trans = 7: 3) and 42.7 g (360 mmol) of thionyl chloride were added. In addition, 0.01 ml of N, N-dimethylformamide was added, and the mixture was heated to reflux for 3 hours. The reaction solution was cooled, 20 ml of toluene was added, the solvent was removed under reduced pressure, and the residue was purified by distillation to obtain 6.4 g of 1,4-cyclohexanedicarboxylic acid chloride (yield 85.0%, cis / trans = 6: 4).
Bp: 129-133 ° C / 5mmHg
¹ HNMR (400 MHz, CDCl ₃ ) δ: 3.0 to 2.9, 2.8 to 2.7 (m, 2H), 2.4 to 2.3, 2.1 to 2.0, 2.0 -1.8, 1.6-1.5 (m, 8H) ppm

(2) Synthesis of polyester DNTPE-2

In Example 22, 1.05 g (5.0 mmol) of 1,4-cyclohexanedicarboxylic acid chloride was added instead of adipic acid chloride, and 0.51 g of DNTPE-2 (yield: 64.5%) as a white solid.
The physical property values of DNTPE-2 are as follows.
Glass transition temperature 103 ° C (DSC, in nitrogen stream, 10 ° C / min)
5 wt% weight loss temperature 426 ° C. (TGA in nitrogen stream, 10 ° C./min)
¹ HNMR (400 MHz, CDCl ₃ ) δ: 8.5 to 7.1 (br, 10H), 4.5 to 4.0 (br, 8H), 2.4 to 1.1 (br, 10H) ppm
IR (film): 1732 cm ⁻¹
GPC (CHCl ₃ ) polystyrene conversion: number average molecular weight 6,940, mass average molecular weight 16,000

Example 24
Synthesis of polyester DNTPE-3

In Example 22, 1.02 g (5.0 mmol) of terephthalic acid chloride was added in place of adipic acid chloride, and the reaction was carried out in the same manner as in Example 22. Then, the reaction solution was poured into 200 mL of methanol and precipitated. The solid was filtered off and washed with ether to give 1.81 g (yield: 65.9%) of DNTPE-3 as a white solid.
The physical property values of DNTPE-3 are as follows.
Glass transition temperature 125 ° C (DSC, in nitrogen stream, 10 ° C / min)
5 wt% weight loss temperature 463 ° C. (TGA in nitrogen stream, 10 ° C./min)
¹ HNMR (400 MHz, CDCl ₃ / DMSO-d ₆ ) δ: 8.5 to 7.1 (br, 14H), 4.5 to 4.0 (br, 8H) ppm
IR (film): 1719 cm ⁻¹

Comparative Example The physical properties of polyethylene terephthalate (PET, Mylar, manufactured by DuPont) are as follows.
Glass transition temperature 80 ° C (Reference 1)
Decomposition temperature 340 ° C (Reference 2)
Reference 1: ZEUS INDUSTRIAL PRODUCTS, Inc. TECHNICAL NEWSLETTER “Focus on PET”, (2010)
Reference 2: GESTIS Substance Database, IFA
The polymers containing the dinaphthothiophene skeleton of Examples 19 to 23 in the main chain had a higher thermal decomposition temperature than that of the comparative example, and high thermal stability was shown.

Evaluation of refractive index Test examples 1 to 4
For each of the polymers obtained in Examples 20 to 21 and Examples 21 to 23, 20 mg of the polymer was dissolved in 1 mL of chloroform to form a solution, and this solution was then filtered through a membrane filter (0.50 μm). . One drop of the obtained filtrate was applied to the surface of a silicon wafer (15 mm square) using a Pasteur pipette, and chloroform contained in the applied filtrate was evaporated to form a film of refractive index improver ( A film thickness of 1 μm) was formed. All of the obtained polymer films were uniformly transparent, and the refractive index with respect to light of 632.8 nm was measured for each of the films by an Ellipson meter (DHA-OLX / S4, manufactured by Mizoji Optical Co., Ltd.). The results are shown in Table 1.
The polymers of Test Examples 1 to 4 gave an isotropic transparent film by spin coating, and showed a higher refractive index than the comparative example.

Claims (5)

A dinaphthothiophene compound represented by the following general formula (1).
(In the formula, R is a substituent on a benzene ring that is not condensed with a thiophene ring, and is a hydroxyl group, a 2,3-epoxypropoxy group, a 2- (meth) acryloyloxyethoxy group, an R ¹ O-group (formula In the formula, R ¹ represents an alkyl group which may contain oxygen or sulfur as a hetero atom, or a HO—X—O— group (wherein X is an alkylene which may contain oxygen or sulfur as a hetero atom) Represents a chain or an aralkylene chain))   The dinaphthothiophene compound according to claim 1, wherein the substitution position of R is the 2,12-position or the 3,11-position of the dinaphthothiophene ring. A polymer comprising a dinaphthothiophene skeleton having a structure represented by the following formula (2) or (3) as a repeating unit. However, in the polymer, the main chain of the polymer is bonded to a benzene ring not condensed with the thiophene ring. In the formula, X is an alkylene chain or aralkylene chain which may contain oxygen or sulfur as a hetero atom, Y is an alkylene chain, aralkylene chain or arylene chain which may contain oxygen or sulfur as a hetero atom, Z is An oxygen or sulfur atom.
  A refractive index improver comprising the dinaphthothiophene compound or polymer according to claim 1. In the dinaphthothiophene compound represented by the following formula (1-E), diphenyl carbonate or formula: HOOC-Y-COOH (wherein Y is an alkylene chain which may contain oxygen or sulfur as a hetero atom, an aralkylene chain) Or a dinaphthothiophene having the structure represented by the formula (2) or (3) as a repeating unit according to claim 3, which comprises reacting a reactive derivative at the carboxy group of the compound represented by A method for producing a polymer containing a skeleton.
(In the formula, X represents an alkylene chain or aralkylene chain which may contain oxygen or sulfur as a hetero atom, Z represents an oxygen or sulfur atom, and the group —O—X—ZH represents a benzene ring not condensed with a thiophene ring. Connected to)