JP2009030022A - Naphthalene polymer for high refractive index material and method for producing the same - Google Patents

Abstract

To provide a naphthalene polymer for low refractive index materials having a low molecular weight having dihydroxynaphthalene as a repeating unit and having a hydroxynaphthalene unit and an oxynaphthalene unit, and a method for producing the same.
A polymer having a low molecular weight and an excellent performance as a high refractive index material by conducting a polymerization reaction under specific conditions using a dihydroxynaphthalene derivative as a raw material and taking out the obtained polymerization reaction product by solvent extraction or the like. A method for producing a naphthalene polymer having
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Description

The present invention relates to a low molecular weight naphthalene polymer for high refractive index materials having a structure derived from dihydroxynaphthalene as a repeating unit, and a method for producing the same.

  Naphthalene polymers obtained by polymerizing naphthalenes are useful as engineering plastics, etc., and by mixing with other polymers, additives, etc., mechanical strength, heat resistance, electrical characteristics and chemical characteristics It is possible to make the resin excellent in. The resin thus obtained has excellent processability and can be used for a wide range of applications such as electronic component materials, electrical component materials, and mechanical component materials.

  However, high refractive index materials obtained by polymerizing such naphthalenes have been known so far. However, they do not have a sufficient refractive index, or have a high molecular weight and thus have poor solubility. Many had drawbacks.

  On the other hand, since the polymerization of a compound using an enzyme is a reaction utilizing the high substrate specificity of the enzyme, the target product can be efficiently produced, which is advantageous for cost reduction. Further, since the reaction is performed under mild conditions, it consumes less energy and is an excellent method that can reduce the environmental load.

  Thus, as a method for producing a naphthalene polymer using an enzyme, for example, a method in which 1-naphthol or 2-naphthol is polymerized in a mixed solvent of methanol and a phosphate buffer has been proposed (Non-Patent Document). 1).

Such a naphthol polymer is usually a naphthol unit (hereinafter abbreviated as a hydroxy naphthalene unit) in which naphthols as monomers are bonded between carbon atoms on the aromatic ring and the resulting molecule has a phenolic hydroxyl group. ) And the oxynaphthalene unit (hereinafter abbreviated as oxynaphthalene unit) obtained by bonding between the carbon atom on the aromatic ring of one naphthol monomer and the phenolic hydroxyl group of the other naphthol Both are structural units.
A naphthol polymer in which a hydroxynaphthalene unit and an oxynaphthalene unit are present in the molecule is specifically produced only by an enzymatic method, and has flexibility because aromatic rings are bonded through oxygen atoms. It becomes a polymer.
As described above, it has not been known so far that the naphthalene polymer according to the present invention has excellent characteristics of low molecular weight and high refractive index.

Technology development for rationalization of energy use biocatalyst, etc. Research and development of elemental technology Research and development of enzyme-catalyzed polymerization technology of deformalin resin 2001 results report, New Energy and Industrial Technology Development Organization

The polymerization reaction product of 1-naphthol obtained by the method described in Non-Patent Document 1 has a large weight average molecular weight of 15000 to 20000, and the polymerization reaction product of 2-naphthol also has a weight average molecular weight of 4500 to 5000. And it was relatively big. As a result, the solvent solubility and fluidity were low.

  The present invention has been made in view of the above problems, has a structure derived from dihydroxynaphthalene as a repeating unit, and has a hydroxynaphthalene unit and an oxynaphthalene unit, a low molecular weight naphthalene polymer for a high refractive index material, It is another object of the present invention to provide a manufacturing method thereof.

  As a result of intensive studies, the inventors conducted a polymerization reaction under specific conditions using a dihydroxynaphthalene derivative as a raw material, and by taking out the obtained polymerization reaction product by solvent extraction or the like, a low molecular weight naphthalene polymer was obtained. It has been found that it can be produced, and that the obtained naphthalene polymer has excellent performance as a high refractive index material, and the present invention has been completed.

That is, the present invention
General formula (1), (2), (3) or (4)

A naphthalene polymer for a high refractive index material having a structure represented by the above formula as a repeating unit is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the low molecular weight high refractive index material naphthalene polymer for materials and its manufacturing method can be provided. Since the obtained polymer has a low molecular weight, it has high solubility in an organic solvent and the like, and since it contains a large amount of hydroxyl groups, it has a feature that it can be easily crosslinked with other polymers.

The naphthalene polymer of the present invention has a repeating unit represented by the general formula (1), (2), (3) or (4), and has a weight average molecular weight of 3000 or less. In the naphthalene polymer of the present invention, the ratio between the number of repeating units represented by the general formula (1) or (2) and the number of repeating units represented by the general formula (3) or (4) is particularly limited. Not.

  Moreover, although a weight average molecular weight is not specifically limited, When solvent solubility and fluidity | liquidity are considered, it is preferable that it is 300-3000. The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is not particularly limited because the ratio required according to the application is different. For example, those having an appropriate molecular weight include those in the range of 3.0 or less, more preferably those in the range of 1.05 to 3.0, and particularly preferably 1. The thing of 05 or more and less than 2.0 is mentioned.

The order in which the repeating units represented by the general formulas (1) to (4) of the naphthalene polymer of the present invention are bonded in the polymer is not particularly limited. Moreover, even if it is a copolymer with another polymer, it can use preferably.

  In the naphthalene polymer of the present invention, the position at which dihydroxynaphthalene bonds is not particularly limited, and when the repeating unit is represented by the general formula (1) or (3), Any one carbon atom at the 1st to 8th positions where the oxygen atom and the phenolic hydroxyl group are not bonded participates in the bonding between the monomers. In addition, when the repeating unit is represented by the general formula (2) or (4), any two carbon atoms at the 1st to 8th positions to which no phenolic hydroxyl group is bonded are the monomers. Involved in binding.

Hereinafter, the manufacturing method of the naphthalene polymer of this invention is demonstrated.
◎ Manufacturing method 1
The method for producing a naphthalene polymer of the present invention includes a step of oxidative polymerization of dihydroxynaphthalene in water or an aqueous solution or in a mixed solvent of water or an aqueous solution and an organic solvent in the presence of an oxidoreductase. The obtained naphthalene polymer has repeating units represented by the general formulas (1) and (2) or the general formulas (3) and (4), and has a weight average molecular weight of 3000 or less. And
(Polymerization reaction)
In this production method, water or an aqueous solution, or a mixed solvent of water or an aqueous solution and an organic solvent is used as a reaction solvent, and a buffer solution can be cited as a preferable aqueous solution.

  Examples of the buffer solution include citrate buffer solution, phosphate buffer solution, malonate buffer solution, oxalate buffer solution, tartaric acid buffer solution, acetate buffer solution and succinate buffer solution. A buffer solution and a phosphate buffer solution are preferable.

The reaction may include one or more organic solvents. Such an organic solvent can be used without particular limitation as long as it does not reduce the activity of the oxidoreductase. Examples of such organic solvents include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohol solvents such as methanol and ethanol, ethers such as diethyl ether and tetrahydrofuran, N, N-dimethylformamide (DMF), and the like. Amide solvents such as N, N-dimethylacetamide (DMA), and organic solvents such as dimethyl sulfoxide (DMSO). These solvents can be used alone or in admixture of two or more organic solvents.
Further, as the water-soluble organic solvent contained in the organic solvent, water-soluble alcohols such as methanol, ethanol, isopropyl alcohol, and ethylene glycol are particularly preferable. These solvents can be used alone or in admixture of two or more organic solvents.

  When water or a mixed solvent of an aqueous solution and an organic solvent is used as the reaction solvent, the monomer polymerization reaction can be carried out even with a very small amount of the organic solvent in the mixed solvent. The amount of the organic solvent in the mixed solvent is preferably 1% by volume to 75% by volume.

  In this production method, a low molecular weight naphthalene polymer having a weight average molecular weight of 3000 or less can be efficiently obtained by oxidative polymerization of a monomer in the presence of an oxidoreductase.

  The oxidoreductase used in this production method is an enzyme having oxidative polymerization ability, and oxidase or peroxidase is preferable. These oxidases and peroxidases may be used alone or in combination of two or more.

  Examples of the oxidase include laccase, catechol oxidase, ascorbate oxidase, bilirubin oxidase, tyrosinase, and polyphenol oxidase. Among these, laccase is preferable. In the present invention, the oxidase used may be used alone or in combination of two or more.

  Laccases are known to exist widely in plants, animals and microorganisms, and those of various origins can be used, but plant-derived and microorganism-derived laccases are preferred.

  As plant-derived laccase, laccase derived from lacquer wood is preferred. Moreover, as microorganism-derived laccase, what is derived from bacteria and fungi (including filamentous fungi and yeast) is preferable, but among fungi, it originates from basidiomycetes such as white rot fungi, and fungi. Laccase is particularly preferred.

Such particularly preferred laccases include the genus Aspergillus; the genus Neurospora; the genus Pyricularia such as P. oryzae; the T. villosa, Genus Trametes such as T. versicolor; genus Rhizotonia such as R. solani; genus Coprinus hill such as C. cinereus; C. hirstus), Corius versicolor and other Coriols genera Include those to come.
Examples of the commercially available laccase include “Laccase Daiwa EC-Y120” (trade name; manufactured by Daiwa Kasei Co., Ltd.).

In the present invention, these laccases may be used alone or in combination of two or more.
As the peroxidase, those of various origins as described above can be used, but those derived from plants, bacteria or basidiomycetes are preferable, and those derived from horseradish or basidiomycetes are particularly preferable. As such peroxidase, manganese peroxidase, horseradish peroxidase, soybean peroxidase, and lignin peroxidase are preferable, and manganese peroxidase and horseradish peroxidase are particularly preferable.

  Moreover, in this invention, these peroxidases may be used independently or may use 2 or more types together.

  Examples of manganese peroxidase include Phanerochaete chrysosporium, Phanerochaete sordida, Lentus bethulinus, and lentil (us). Mention may be made of degrading enzymes. These manganese peroxidases may be used alone or in combination of two or more.

  In this production method, when manganese peroxidase is used as the oxidoreductase, it is necessary to use divalent manganese during the polymerization reaction.

  The divalent manganese is not particularly limited as long as it is a manganese compound in which the oxidation number of manganese is +2. As such a thing, manganese sulfate can be mentioned, for example.

  Moreover, what is necessary is just to adjust the addition amount of bivalent manganese suitably according to the kind of substrate to be used.

  Examples of horseradish peroxidase include P6140, P9568, P2649, P2088 manufactured by SIGMA-ALDRICH, 77330, 77332 manufactured by Fluka, and 169-10791 manufactured by Wako Pure Chemical Industries, Ltd. These horseradish peroxidases may be used alone or in combination of two or more.

  Among these oxidoreductases, an oxidase and a laccase are preferable because a naphthalene polymer having a more uniform molecular weight can be obtained.

In the reaction using an oxidoreductase, an oxidant is used, but any oxidant that causes oxidative coupling may be used, and a peroxide is generally used. The peroxide may be either an organic peroxide or an inorganic peroxide. Particularly preferred is hydrogen peroxide. The concentration of peroxide is not particularly limited. In this case, the usage-amount of a peroxide is 0.3-10 times mole with respect to 1 mol of dihydroxy naphthalene, Preferably it is 0.5-5 times mole. The peroxide may be added to the reaction mixture all at once, but it is preferable to add it in portions in order to maintain the activity of the enzyme.
When an oxidase such as laccase is used as an oxidoreductase, molecular oxygen can be used as an oxidizing agent. As oxygen in this case, in addition to pure oxygen, it can be used in the form of air or a mixture of oxygen and an inert gas. These may be blown into the reaction mixture or simply present in the polymerization atmosphere.

The amount of these oxidoreductases used may be appropriately adjusted depending on the enzyme activity of the enzyme used. However, it is preferable to use an excessive amount with respect to the monomer as the raw material because the amount of extraction in Step 2 described later increases. . The concentration of oxidoreductase in the reaction solution is preferably 2 μmol / L or more, particularly preferably 20 μmol / L or more.

The reaction conditions may be appropriately adjusted according to the substrate concentration and the type and concentration of the oxidoreductase, but the reaction temperature can be set to a relatively low temperature, preferably 5 to 70 ° C., 20 It is especially preferable to set it as -60 degreeC. The pH may be appropriately adjusted according to the type of oxidoreductase, but is preferably pH 3.0 to 8.0, more preferably pH 3.5 to 7.0. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 hour to 20 hours. Moreover, the stirring method at the time of reaction is not specifically limited, Any of shaking, stirring using a rotor or a stirring blade may be sufficient.
This step may be performed either in a water bath or in an air stream as long as the stirring conditions satisfy the above conditions.

In this production method, the method of post-treatment of the reaction solution after the polymerization reaction is not particularly limited, and a conventionally known method may be applied. That is, for example, after removing insoluble matter, the solvent may be distilled off to remove the naphthalene polymer, or the solvent may be newly added to the reaction solution to precipitate out the naphthalene polymer.
◎ Production method 2
The method for producing a naphthalene polymer of the present invention includes a step of subjecting dihydroxynaphthalene to oxidative polymerization in the presence of an oxidoreductase in water or an aqueous solution, or in a mixed solvent of water or an aqueous solution and an organic solvent. And a step of extracting the polymerization reaction product with a solvent, and the obtained naphthalene polymer is a repeating unit represented by the general formulas (1) and (3) or the general formulas (2) and (4). And having a weight average molecular weight of 3000 or less.

  In this production method, a low molecular weight naphthalene polymer having a weight average molecular weight of 3000 or less can be obtained more efficiently by oxidative polymerization of a monomer in the presence of an oxidoreductase and performing solvent extraction after the reaction. .

The conditions described in the production method 1 may be applied as the polymerization process conditions, and the extraction process will be described below.
(Extraction process)
In this production method, following the polymerization step, a step of solvent extraction of the polymerization reaction product obtained in the step is performed. By performing solvent extraction, a low molecular weight naphthalene polymer having a weight average molecular weight of 3000 or less can be efficiently obtained.

  The reaction product obtained in the polymerization step is a mixture of the target naphthalene polymer and other impurities. In the extraction step, the naphthalene polymer is solvent extracted from the reaction solution containing this mixture.

  The extraction solvent used in the extraction step is preferably an organic solvent. Among them, an acetate solvent such as ethyl acetate and butyl acetate, a ketone solvent such as methyl isobutyl ketone and cyclohexanone, and an alcohol solvent such as n-butanol are preferable. In particular, an acetate solvent is preferable.

  The extraction of the naphthalene polymer can be carried out, for example, by adding the extraction solvent to the reaction product after completion of the polymerization step and stirring it, and separating the organic layer.

  The addition amount of the extraction solvent at this time is not particularly limited, but usually it is preferably 5 to 100 times (v / w) the obtained naphthalene polymer, and the extraction temperature is room temperature. It is preferable.

  Moreover, the stirring method of the solution after addition of an extraction solvent is not specifically limited, Any of shaking, stirring using a rotor or a stirring blade may be sufficient.

  On the other hand, when the reaction solution is separated into two layers after completion of the polymerization step, the organic layer may be used as an extract as it is. That is, the organic solvent used for the reaction can be used as an extraction solvent as it is.

  The extraction conditions such as the extraction temperature and the stirring method during extraction in this case may be the same as those when the extraction solvent is added after the polymerization step.

  Since the low molecular weight naphthalene polymer of the present invention has a high solubility in an organic solvent, as described above, when solvent extraction is performed from the reaction product obtained in the polymerization step, the amount of the organic solvent used as the extraction solvent is small. And a low molecular weight naphthalene polymer can be efficiently extracted.

  The naphthalene polymer having more repeating units represented by the general formula (1) or (3) is more naphthalene polymer having more repeating units represented by the general formula (2) or (4). Since the solubility in the extraction solvent, particularly ethyl acetate, is large, it can be obtained more efficiently as a low molecular weight naphthalene polymer.

  In the method for producing a naphthalene polymer of the present invention, a low molecular weight naphthalene polymer having a weight average molecular weight of 3000 or less can be obtained in any of production methods 1 and 2, but the polymer of dihydroxynaphthalene is also suitable. Is obtained.

  As a preferable compound of dihydroxynaphthalene used in the present invention, 1,5-dihydroxynaphthalene or 2,7-dihydroxynaphthalene can be mentioned because the polymer exhibits preferable characteristics as a high refractive index material described later. However, it is not limited to these.

Next, the naphthalene polymer obtained in the present invention can be used as a high refractive index material. The naphthalene polymer of the present invention has a refractive index of 1.550 or more, preferably 1.600 or more. When the refractive index of the naphthalene polymer alone cannot be measured, the refractive index of the naphthalene polymer alone can be extrapolated from the refractive index in a solution state dissolved in an appropriate solvent. In order to use as a refractive index adjusting agent in the optical field or the like, it is important to have excellent transparency such as hue and light transmittance.

The naphthalene polymer of the present invention can be blended with other resins as a refractive index adjusting agent to obtain a resin composition having an increased refractive index. Examples of the other resin include resins having a difference in refractive index of 0.001 or more, preferably 0.01 or more, relative to the naphthalene polymer. Examples of such resins include nylon 66, polyacetal, polycarbonate, fluororesin, polyethylene, polypropylene, vinyl chloride resin, polystyrene, MMA resin, AS resin, petroleum resin, and the like. The blending amount of the naphthalene polymer is 1 to 60% by mass, preferably about 5 to 50% by mass.
The naphthalene polymer obtained by the production method of the present invention has various properties depending on the resin composition, but is useful in various fields as various molded articles including optical materials depending on the properties.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

(Example 1) Production of 2,7-dihydroxynaphthalene polymer by production method 1 using laccase As a reaction solvent, 50 mmol / L phosphate buffer (pH 4.5) with isopropyl alcohol at 50% by volume A mixed solvent (600 mL) was prepared. To this mixed solvent, 9.6 g (100 mmol / L) of 2,7-dihydroxynaphthalene and 18 g of laccase were added as raw materials, and polymerization was performed at a reaction temperature of 30 ° C. for 8 hours while blowing air at an air flow rate of 0.15 L / min. Reaction was performed. The reaction rate of 2,7-dihydroxynaphthalene at this time was 99.8%. After completion of the reaction, the precipitate was collected by centrifugation, dissolved in 100 mL of ethyl acetate, washed with distilled water, and then ethyl acetate was distilled off to obtain 9.6 g of the desired 2,7-dihydroxynaphthalene polymer. (Yield 100%).

  When the molecular weight of the obtained 2,7-dihydroxynaphthalene polymer was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 2100, and the ratio of the weight average molecular weight to the number average molecular weight (Mn) ( Mw / Mn) was 1.33. The hydroxyl equivalent was 162 g / eq.

(Example 2) Production of 2,7-dihydroxynaphthalene polymer by production method 2 using laccase The production method 1 in Example 1 described above was changed to production method 2 and extracted with ethyl acetate after the polymerization reaction. 9.5 g of the target 2,7-dihydroxynaphthalene polymer was obtained in the same manner as in Example 1 except that the procedure was performed (yield 99%).

  When the molecular weight of the obtained 2,7-dihydroxynaphthalene polymer was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 2100, and the ratio of the weight average molecular weight to the number average molecular weight (Mn) ( Mw / Mn) was 1.33. The hydroxyl equivalent was 162 g / eq.

(Example 3) Production of 1,5-dihydroxynaphthalene polymer by production method 1 using laccase Example 2 except that 2,7-dihydroxynaphthalene in Example 1 was changed to 1,5-dihydroxynaphthalene In the same manner as in Example 1, 9.5 g of the target 1,5-dihydroxynaphthalene polymer was obtained (yield 99%).

  When the obtained 1,5-dihydroxynaphthalene polymer was subjected to molecular weight measurement by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 1320, and the ratio of the weight average molecular weight to the number average molecular weight (Mn) ( Mw / Mn) was 1.58. The hydroxyl equivalent was 162 g / eq.

(Example 4) Production of 2,7-dihydroxynaphthalene polymer by production method 2 using laccase The same procedure as in Example 1 was carried out except that the reaction solvent isopropyl alcohol in Example 1 was changed to methanol. As a result, 5.7 g of 2,7-dihydroxynaphthalene polymer was obtained (yield 59%).

  When the molecular weight of the obtained 2,7-dihydroxynaphthalene polymer was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 1300, and the ratio of the weight average molecular weight to the number average molecular weight (Mn) ( Mw / Mn) was 1.30. The hydroxyl equivalent was 159 g / eq.

(Example 5) Production of 1,6-dihydroxynaphthalene polymer by production method 2 using laccase Example 2, except that 2,7-dihydroxynaphthalene in Example 1 was changed to 1,6-dihydroxynaphthalene In the same manner as in Example 1, 9.5 g of the target 1,6-dihydroxynaphthalene polymer was obtained (yield 99%).
When the molecular weight of the obtained product was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 4400, and the ratio (Mw / Mn) between the weight average molecular weight and the number average molecular weight (Mn) was 2. .44. The hydroxyl equivalent was 251 g / eq.

(Example 6) Production of 1,7-dihydroxynaphthalene polymer by production method 2 using laccase Example 2, except that 2,7-dihydroxynaphthalene in Example 1 was changed to 1,7-dihydroxynaphthalene In the same manner as in Example 1, 9.5 g of the target 1,7-dihydroxynaphthalene polymer was obtained (yield 99%).
When the molecular weight of the obtained 1,7-dihydroxynaphthalene polymer was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 2800, and the ratio of the weight average molecular weight to the number average molecular weight (Mn) ( Mw / Mn) was 2.99. The hydroxyl equivalent was 223 g / eq.

(Example 7) Production of 2,3-dihydroxynaphthalene polymer by production method 2 using laccase Example 2, except that 2,7-dihydroxynaphthalene in Example 1 was changed to 2,3-dihydroxynaphthalene In the same manner as in Example 1, 9.5 g of the target 2,3-dihydroxynaphthalene polymer was obtained (yield 99%).
When the obtained 2,3-dihydroxynaphthalene polymer was subjected to molecular weight measurement by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 8800, and the ratio of the weight average molecular weight to the number average molecular weight (Mn) ( Mw / Mn) was 1.97. The hydroxyl equivalent was 484 g / eq.

(Example 8) Production of 2,6-dihydroxynaphthalene polymer by production method 2 using laccase Example 2, except that 2,7-dihydroxynaphthalene in Example 1 was changed to 2,6-dihydroxynaphthalene In the same manner as in Example 1, 9.5 g of the target 2,6-dihydroxynaphthalene polymer was obtained (yield 99%).
When the molecular weight of the obtained 2,6-dihydroxynaphthalene polymer was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 4900, and the ratio of the weight average molecular weight to the number average molecular weight (Mn) ( Mw / Mn) was 2.29. The hydroxyl equivalent was 144 g / eq.

(Example 9) Production of a copolymer of 2,7-dihydroxynaphthalene and 2-naphthol As a reaction solvent, a mixture obtained by mixing 50 mmol / L acetate buffer (pH 4.5) with isopropyl alcohol to 50% by volume A solvent (600 mL) was prepared. Into this mixed solvent, 4.8 g (50 mmol / L) of 2,7-dihydroxynaphthalene and 4.3 g (50 mmol / L) of 2-naphthol were added as raw materials, 18 g of laccase was added, and the air flow rate was 0.15 L. The polymerization reaction was carried out at a reaction temperature of 30 ° C. for 8 hours while blowing air at / min. At this time, the residual ratios of 2,7-dihydroxynaphthalene and 2-naphthol were 0.1% or less, respectively. After completion of the reaction, the precipitate was collected by centrifugation, dissolved in 100 mL of ethyl acetate, washed with distilled water, and then ethyl acetate was distilled off to obtain 9.0 g of a solid (99% yield).
When the molecular weight of the obtained product was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 1400, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight (Mn) was 1. .27.

(Example 10) Production of copolymer of 2,7-dihydroxynaphthalene and 5-hydroxyindane Example 4 was changed except that 4.3 g of 2-naphthol in Example 9 was changed to 4.0 g of 5-hydroxyindane. In the same manner as in 9, 8.7 g of a solid was obtained (yield 99%).
When the molecular weight of the obtained product was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 1600, and the ratio of the weight average molecular weight to the number average molecular weight (Mn) (Mw / Mn) was 1. .34.

(Example 11) Production of copolymer of 2,7-dihydroxynaphthalene and 4-hydroxyphenylmethacrylamide Other than changing 4.3 g of 2-naphthol in Example 9 to 5.3 g of 4-hydroxyphenylmethacrylamide In the same manner as in Example 9, 10.1 g of a solid was obtained (yield 100%).
When the molecular weight of the obtained product was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 2700, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight (Mn) was 1. .41.

(Example 12) Production of copolymer of 2,7-dihydroxynaphthalene and 4-hydroxyphenylethyl acrylate Other than changing 4.3 g of 2-naphthol in Example 9 to 5.8 g of 4-hydroxyphenylethyl acrylate In the same manner as in Example 9, 10.5 g of a solid was obtained (yield 99%).
When the molecular weight of the obtained product was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 2800, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight (Mn) was 1. .74.

(Example 13) Production of copolymer of 2,7-dihydroxynaphthalene and vanillyl alcohol acrylate ester In addition to changing 4.3 g of 2-naphthol in Example 9 to 6.2 g of vanillyl alcohol acrylate ester In the same manner as in Example 9, 10.9 g of a solid was obtained (yield 99%).
When the molecular weight of the obtained product was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 1600, and the ratio of the weight average molecular weight to the number average molecular weight (Mn) (Mw / Mn) was 1. .43.

(Example 14)
The 2,7-dihydroxynaphthalene polymer obtained in Example 1 was dissolved in N, N-dimethylformamide (DMF) to prepare a 2,7-dihydroxynaphthalene polymer / DMF solution having a solid content of 50 wt%. did. The cast film | membrane was obtained after apply | coating on the glass plate using the applicator and heat-drying. The film thickness was 3.6 μm. The refractive index (nD ₂₅ ) was measured and found to be 1.610.

(Example 15)
When the refractive index of the 1,5-dihydroxynaphthalene polymer obtained in Example 3 was measured in the same manner as in Example 14, the film thickness was 3.4 μm, and the refractive index (nD ₂₅ ) was measured. 1.590.
(Example 16) to (Example 24)
The dihydroxynaphthalene polymer and copolymer obtained in Examples 5 to 13 were dissolved in N, N-dimethylformamide (DMF) to prepare a DMF solution having a solid content of 50 wt%. The cast film | membrane was obtained after apply | coating on the glass plate using the applicator and heat-drying. Table 1 shows the results of measuring the film thickness and refractive index (nD ₂₅ ).

(Comparative Example 1) Method according to Non-Patent Document 1 Production of 1-naphthol polymer by production method 1 using horseradish peroxidase As a reaction solvent, 50% by volume of methanol in 50 mM phosphate buffer (pH 7.0) A mixed solvent of 1000 mL was prepared. To this mixed solvent, 1.44 g (10 mM) of 1-naphthol and 12 g of horseradish peroxidase were added as raw materials, and a polymerization reaction was performed at a reaction temperature of 30 ° C. for 6 hours. At that time, 30% hydrogen peroxide solution was taken in a syringe joined with a Teflon (registered trademark) tube and dropped into the reaction solution using a syringe pump.
After completion of the reaction, the precipitate was collected by centrifugation, washed with water, freeze-dried, then dissolved in 100 ml of ethyl acetate at room temperature, and the ethyl acetate was distilled off to obtain 1-naphthol polymer as the target product. .44 g was obtained (yield 100%).

When the obtained 1-naphthol polymer was subjected to molecular weight measurement by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 18000, and the ratio of the weight average molecular weight to the number average molecular weight (Mn) (Mw / Mn). ) Was 1.20.
As described above, it was confirmed that the production method of the present invention using the dihydroxynaphthalene of the present invention can easily produce a naphthalene polymer having a weight average molecular weight of 3000 or less, and these polymers have a high refractive index. I found it.

The production method of the present invention can provide a naphthalene polymer having a weight average molecular weight of 3000 or less. In addition, the naphthalene polymer is useful as a raw material for highly refractive materials and has applications as various optical materials.

Claims (10)

General formula (1), (2), (3) or (4)

A naphthalene polymer for high refractive index materials having a structure represented by   The naphthalene polymer for high refractive index materials according to claim 1, wherein the structure represented by the general formulas (1) to (4) is derived from 1,5-dihydroxynaphthalene or 2,7-dihydroxynaphthalene. . General formula (1), (2), (3) or (4)

In the production of a naphthalene polymer for a high refractive index material having a structure represented by
A step of polymerizing dihydroxynaphthalene constituting the repeating unit represented by the general formulas (1) to (4) in water or in a mixed solvent of water and one or more organic solvents in the presence of an oxidoreductase. The manufacturing method of the naphthalene polymer for high refractive index materials which has this.   The manufacturing method of the naphthalene polymer for high refractive index materials of Claim 3 which has the process of carrying out the solvent extraction of the obtained polymerization reaction product after the said process to superpose | polymerize.   The method for producing a naphthalene polymer for a high refractive index material according to any one of claims 3 and 4, wherein the oxidoreductase is oxidase or peroxidase. The method for producing a naphthalene polymer for a high refractive index material according to claim 5, wherein the oxidase or peroxidase is at least one selected from the group consisting of manganese peroxidase, horseradish peroxidase and laccase.   The manufacturing method of the naphthalene polymer for high refractive index materials as described in any one of Claims 3 thru | or 6 in which the 1 or more types of organic solvent used for the mixed solvent in the said process to superpose | polymerize contains a water-soluble organic solvent.   The method for producing a naphthalene polymer for a high refractive index material according to claim 7, wherein the water-soluble organic solvent is a water-soluble alcohol.   The method for producing a naphthalene polymer for a high refractive index material according to claim 8, wherein the water-soluble alcohol is methanol, ethanol, isopropyl alcohol, or ethylene glycol.   The method for producing a naphthalene polymer for a high refractive index material according to any one of claims 4 to 9, wherein a solvent used for solvent extraction of the polymerization reaction product is an acetate ester.