JP2009215189A - New polymerizable compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable compound having both of a polymerizable functional group and an ultraviolet-absorbing part, being polymerizable to a high-molecular weight, which can be synthesized by a simple process without requiring the consideration about the influence of a phenolic hydroxy group, and hardly causing change with time, and to provide a method for producing the compound. <P>SOLUTION: The polymerizable compound is represented by general formula (1) (wherein, R<SP>1</SP>is hydrogen or a methyl group; R<SP>2</SP>is a linear or branched alkyl group, an alkyl group having a cyclic structure or an alkyl group having an aromatic ring at the terminal; and -X- is a divalent substituent group). In one embodiment, the polymerizable compound is obtained by bonding a (meth)acrylic acid unit to the phenolic hydroxy group side of ferulic acid at which the ultraviolet-absorbing ability is hardly changed even if the phenolic hydroxy group is capped. The method for producing the compound is also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel polymerizable compound having an ultraviolet absorbing ability and a method for producing the same. More specifically, as UV absorbers, it is used in general polymer materials such as weather-resistant polycarbonate for outdoor use, outdoor paints for automobiles, clear top coating materials, inkjet printing materials, glasses, contact lenses, light guide plates for LCD back panels, etc. The present invention relates to a novel polymerizable compound to be used.

  Conventionally, salicylate-based, hydroxybenzophenone-based, benzotriazole-based, triazine-based and benzoate-based compounds have been used as ultraviolet absorbers for polymer materials. Since most of these compounds are low molecular weight compounds, there is a problem that they are likely to bleed out when added to a polymer material and are likely to be deposited on a film.

  Moreover, since it is a low molecule, it is easily volatilized and volatilizes during the processing of the polymer material.

  In order to solve these problems, an attempt has been made to develop a high molecular weight ultraviolet absorber by introducing a polymerizable functional group into the ultraviolet absorber and polymerizing it, and hydroxybenzophenone as an ultraviolet absorber. An ultraviolet absorber having a polymerizable functional group using a benzotriazole-based compound has already been reported (Patent Documents 1 and 2). These UV-absorbing compounds are considered to stably convert UV energy into heat by keto-enol tautomerism, and the presence of a phenolic hydroxyl group is essential for the function of UV absorption. It has become.

  However, in order to proceed with a multi-step synthesis including introduction of a polymerizable functional group while leaving a free phenolic hydroxyl group in the final product, it is necessary to distinguish the reactivity with the hydroxyl group in the reagent. Since it is necessary to precisely control the reagent amount and temperature as reaction conditions, the ultraviolet absorbers described in Patent Documents 1 and 2 have disadvantages in industrial production for mass production.

  In addition, hydroxybenzophenone and benzotriazole UV absorbers cause yellowing due to oxidation of free phenolic hydroxyl groups present in their structure or reaction with residual catalyst in the resin. Things are also known.

  Accordingly, there has been a demand for an ultraviolet absorber that can be produced by a simple process without requiring special control and that can be easily changed over time such as yellowing and can be increased in molecular weight.

In addition, many UV absorbers, including hydroxybenzophenone and benzotriazole, are synthesized using many steps using petroleum-derived raw materials, which are depleted resources. Therefore, there has been a demand for the development of an ultraviolet absorber that can be produced by a simple process without using petroleum-derived raw materials.
JP 2000-119262 A JP 2002-80487 A

  An object of the present invention is a polymerizable compound having a polymerizable functional group and an ultraviolet absorbing portion, which can be increased in molecular weight, can be synthesized in a simple process without considering the influence of a phenolic hydroxyl group, and changes with time occur. An object of the present invention is to provide a polymerizable compound which is difficult to produce and a method for producing the same.

  As a result of intensive studies, the present inventors have obtained a (meth) acrylic acid unit on the phenolic hydroxyl group side of ferulic acid, which is easily obtained in nature and in large quantities and whose ultraviolet absorption capacity hardly changes even when the phenolic hydroxyl group is blocked. The present inventors have found that the above-mentioned problems can be solved by a polymerizable compound in which is bonded.

  That is, the present invention is a polymerizable compound represented by the following general formula (1).

(Wherein R ¹ represents hydrogen or a methyl group, R ² represents a linear or branched alkyl group, an alkyl group containing a cyclic structure, or an alkyl group containing an aromatic ring at the end, and —X— represents a divalent group. Represents a substituent of
In the polymerizable compound of the present invention, -X- is preferably any one of the structures represented by the following general formulas (2) to (5) or a structure in which they are combined.

(In the formula, R ³ represents an alkylene group having a linear or branched structure having 1 to 5 carbon atoms, and n represents an integer from 0 to 10.)

(In the formula, R ⁴ and R ⁵ each independently represents a linear alkyl group having 1 to 5 carbon atoms.)

(In the formula, R ⁶ represents an alkyl group having 1 to 5 carbon atoms, and j represents 0 or 1.)

(In the formula, R ⁷ represents hydrogen or an alkyl group having 1 to 3 carbon atoms. K represents an integer of 0 to 2, and l represents 0 or 1.)
In the polymerizable compound of the present invention, the structure in which —X— is a combination of the above general formulas (2) and (3) is preferably the following general formula (6).

(In the formula, R ³ is an alkylene group having a linear or branched structure having 1 to 5 carbon atoms, n is an integer from 0 to 10, and -Y- is any one of the above general formulas (3) to (5). A divalent substituent having the structure shown is shown.)
As a manufacturing method of the polymeric compound of this invention, when the above-mentioned -X- is General formula (2), a ferulic acid ester and a hydroxyalkyl group are combined with the ferulic acid origin part and the (meth) acrylic acid part. A method using an ether bond reaction with a (meth) acrylic acid having a derivative thereof or a derivative thereof (hereinafter referred to as “Production Process A”), or after an alkylene oxide chain is reacted with a ferulic acid ester to extend an alkylene oxide chain ( It is preferable to use a method of reacting a (meth) acrylic acid moiety (hereinafter referred to as “production method B”).

  Moreover, when the above-mentioned -X- is general formula (3)-(6), the manufacturing method (the (meth) acrylates which have an epoxy group or an oxetanyl group in a molecule | numerator, and ferulic acid esters are made to react ( Hereinafter, it is preferable to use “Production Method C”).

  Since the polymerizable compound of the present invention does not need to leave a free phenolic hydroxyl group, it can be synthesized by a simple method of reacting a phenolic hydroxyl group. In addition, since the polymerizable compound of the present invention has sufficient ultraviolet absorbing ability but does not have a free phenolic hydroxyl group, the phenolic hydroxyl group can be obtained even in the polymerization step for obtaining a polymer or copolymer from a polymerizable compound. Therefore, it is possible to produce an ultraviolet absorber or a polymer material product containing the ultraviolet absorber by a simple process. In addition, even after the production of a UV absorber using the polymerizable compound of the present invention or a polymer material product containing the UV absorber, it is excellent that a change with time such as discoloration due to a phenolic hydroxyl group hardly occurs. It has properties and has great advantages in terms of product quality. Furthermore, since the polymerizable compound of the present invention can be produced by a simple process without using a petroleum-derived raw material which is a depleted resource, it is possible to suppress wasteful energy consumption and is preferable from the viewpoint of green chemistry. It is.

Hereinafter, the polymerizable compound of the present invention will be described in detail.
The polymerizable compound of the present invention is a compound having a ferulic acid moiety and a (meth) acrylic acid moiety in the molecule, and is characterized by not requiring a free phenolic hydroxyl group in order to maintain the ultraviolet absorbing ability. Therefore, it is very easy to synthesize derivatives as compared with existing hydroxybenzophenone and benzotriazole compounds. Moreover, it has the characteristic that yellowing resulting from a free phenolic hydroxyl group does not occur easily.

  The compound of the present invention is a compound having both a ferulic acid unit and a (meth) acrylic acid unit, and the portion connecting these units is a divalent substituent represented by -X- in the general formula (1). is there.

  -X- is a structure represented by the general formulas (2) to (5) and a combination structure thereof, and a suitable example of the combination structure includes a structure represented by the general formula (6).

Although the compound of the present invention has a skeleton derived from ferulic acid in the molecule, the carboxylic acid side of ferulic acid can have various ester structures for adjusting physical properties. R ^{1 in the} general formula (1) is not particularly limited, but represents a linear or branched alkyl group, specifically, methanol, ethanol, n-propanol, n-butanol, heptanol, octanol, lauryl alcohol. Esters with primary alcohols such as benzyl alcohol and 2-ethylhexyl alcohol, esters with secondary alcohols such as isopropyl, isobutyl, cyclohexyl and isonorbornyl, and esters with tertiary alcohols such as t-butyl and adamantyl Is mentioned.

  Ferulic acid has a maximum absorption wavelength in the vicinity of 320 nm, which causes deterioration of resins such as polycarbonate, and its absorption capability is very high compared to existing hydroxybenzophenone compounds. That is, the polymerizable compound of the present invention using ferulic acid is expected to be more excellent in the ability to suppress the deterioration of a resin such as polycarbonate than the conventional product.

  The ferulic acid used in the present invention is not particularly limited in origin or the like. For example, it is derived from cell walls such as rice bran oil, sugar maple, pine seeds, wheat endosperm cell walls, and rice endosperm cells. Things. That is, in the production of the polymerizable compound of the present invention, it is not necessary to use a petroleum-derived raw material that is a depleted resource for the ultraviolet absorption site.

  Ferulic acid production methods include, for example, rice crude oil and black-brown viscous pitch, oil-rich alkali foods, and a by-product rich in crude fatty acid called dark oil, and alkaline methanol, ethanol, IPA, etc. Examples of the solvent include extraction by a hydrolysis method. As a synthesis method, a method of reacting a mixture of vanillin, malonic acid and a small amount of piperidine in pyridine can be mentioned.

  Specific examples of the polymerizable compound represented by the general formula (1) are shown below as formulas (7) to (60), but the present invention is not limited to these compounds.

  In the following formula, n represents an integer from 0 to 10, and m represents an integer from 0 to 20.

(Production method)
Below, the manufacturing method (synthesis method) of the polymeric compound of this invention is explained in full detail.

  As a method for producing a polymerizable compound (having an alkyleneoxy moiety) in which the aforementioned -X- is general formula (2), a ferulic acid ester and a hydroxyalkyl group are bonded to a bond between a ferulic acid-derived moiety and a (meth) acrylic acid moiety. A method using an ether bond reaction with (meth) acrylic acid having derivatives thereof or a derivative thereof (the above-mentioned “Production A”), or after extending an alkylene oxide chain by reacting a ferulic acid ester with an alkylene oxide (meth) Examples include a method of reacting an acrylic acid part (the above-mentioned “Production Method B”).

  Moreover, as a manufacturing method of the polymeric compound whose above-mentioned -X- is General formula (3)-(6), (meth) acrylates which have an epoxy group or an oxetanyl group in a molecule | numerator, and a ferulic acid ester derivative are used. The production method (the above-mentioned “Production Method C”) to be reacted is mentioned.

  Such a method for producing a polymerizable compound of the present invention makes it possible to obtain the desired polymerizable compound from ferulic acid in only a few steps, and can be suitably used for industrial production. .

  More specifically, the above-mentioned production method A is obtained by reacting with the phenolic hydroxyl group of ferulic acid esters after making the alcoholic hydroxyl group of (poly) alkyleneoxy (meth) acrylic acid esters a preferred leaving group. ) A method of bonding an acrylic acid part and a ferulic acid part, and the above-mentioned production method B is obtained by extending an alkyleneoxy group using a cyclic ether from a phenolic hydroxyl group of a ferulic acid ester, For example, a method of synthesis by reacting with (meth) acrylic acid or (meth) acrylic acid chloride.

  As the above production method A, after converting the alcoholic hydroxyl group of (poly) alkyleneoxy (meth) acrylic acid esters to a leaving group such as a corresponding halide or tosyl group, the phenolic hydroxyl group of ferulic acid esters and Examples include the Williamson method for reacting and a method using Mitsunobu reaction in which an alcoholic hydroxyl group is activated with an azodicarboxylic acid ester and then reacted with a phenolic hydroxyl group. A method utilizing a reaction is preferably used.

  Examples of the solvent used in the Mitsunobu reaction include n-hexane, benzene, toluene, tetrahydrofuran, diethyl ether, chloroform, dichloromethane, ethyl acetate, and a mixed solvent thereof. Toluene is most preferably used. The reaction temperature is preferably -40 to 100 ° C, more preferably -20 to 40 ° C.

  When the polymerizable compound of the present invention is produced using the above production method B, the catalyst used for the reaction with the cyclic ether includes alkali metal hydroxide such as lithium oxide, potassium hydroxide, sodium hydroxide, cesium hydroxide and the like. Products; alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide and barium hydroxide; metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; and amines such as trimethylamine and triethylamine . Of these, metal alkoxides and amines are preferable, and triethylamine is particularly preferable. Although the usage-amount of a catalyst is not specifically limited, It is 0.01-10 mol with respect to 1 mol of ferulic acid esters, Preferably it is 0.1-3 mol.

  When the cyclic ether is added to the phenolic hydroxyl group of the ferulic acid ester using the above production method B, the ferulic acid ester, the cyclic ether and the catalyst may be charged and reacted together, or the ferulic acid ester and the catalyst may be reacted together. You may make it react by pressing-in or dripping cyclic ether to a mixture. Examples of the cyclic ether include compounds having an epoxy ring and an oxetane ring, and more specifically, ethylene oxide, propylene oxide, oxetane and the like.

  As the reaction solvent for the addition reaction, toluene, xylene, methyl ethyl ketone (MEK), acetone, tetrahydrofuran (THF), dioxane, N, N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) and the like are used. Particularly preferably, toluene or tetrahydrofuran is used. By using toluene as a reaction solvent, it is possible to use a manufacturing method suitable for industrial production with a cheaper reagent.

  The reaction temperature at the time of adding cyclic ether to ferulic acid ester is usually 0 ° C to 250 ° C, preferably 20 ° C to 180 ° C.

  Further, by reacting a compound with an extended alkylene oxide chain with (meth) acrylic acid chloride in the presence of a base or with (meth) acrylic acid in the presence of an acid catalyst, Can be manufactured.

  Moreover, when utilizing the reaction of the said manufacturing method C (ring-opening reaction of an epoxy group and an oxetanyl group), there is a method utilizing a reaction of a corresponding glycidyl compound or oxetane compound with a phenolic hydroxyl group of ferulic acid esters. Can be mentioned.

  The reaction at this time is usually carried out at a temperature in the range of 50 ° C. to 250 ° C. for about 1 to 50 hours. In the reaction, a catalyst is preferably used. Specific examples of the catalyst include amines such as triethylamine, dimethylbutylamine, tri-n-butylamine, diazabicycloundecene (DBU), diazabicyclononene (DBN), dimethylaminopyridine (DMAP), and tetramethylammonium salts. Quaternary ammonium salts such as tetraethylammonium salt, tetrabutylammonium salt and benzyltriethylammonium salt, or quaternary phosphonium salts such as tetraphenylphosphonium salt, phosphines such as triphenylphosphine, and 2-methylimidazole And imidazoles such as 2-ethyl-4-methylimidazole. In the above reaction, the catalyst may be used alone or in combination of several kinds as appropriate.

  In the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve and ethyl cellosolve, esters such as methyl cellosolve acetate and ethyl celloacetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone Solvents, aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene can be used as the reaction solvent.

  During the reaction, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, 4-methylquinoline, phenothiazine, or the like may be allowed to coexist in the reaction system as a polymerization inhibitor.

  In the reaction of the above production method C (ring-opening reaction of epoxy group and oxetanyl group), in order to suppress the polymerization reaction of acrylic acid or methacrylic acid, the reaction may be carried out under an air stream such as air. In that case, an antioxidant such as 2,6-di-t-butyl-4-methylphenol may be used in combination in order to prevent an oxidation reaction by air.

  Next, a method for applying the polymerizable compound of the present invention obtained by the above method to a polymer material product or the like will be described.

  The polymerizable compound of the present invention can be used as a polymer or copolymer containing them as a monomer by adding and applying it to a resin. In that case, it is possible to use a polymer or copolymer consisting only of the polymerizable compound of the present invention, but it is usually desirable to use a copolymer obtained by copolymerization with other monomers. .

  Addition of a polymerization reaction, a method of adding a polymer obtained in advance before coating to the resin, and mixing with the polymerizable compound of the present invention and other monomers and coating on the resin, followed by ultraviolet rays, electrons There are methods for polymerization by wire, heat and the like, and any method can be used.

  As the polymerization reaction, radical polymerization, anionic polymerization, and the like can be used, but radical polymerization is preferably used. When polymerized before use, solution polymerization, emulsion polymerization, suspension polymerization, etc. are performed using azo compounds such as azoisobutyronitrile, peroxides such as benzoyl peroxide as an initiator. Is possible.

  Also, when polymerized after mixing with other monomers and coating on resin, benzophenone, benzoin ether, acetophenone, thioxanthone, etc. as photoinitiator, benzoyl peroxide as thermal initiator, etc. It is possible to polymerize by using ultraviolet rays, heat or the like after coating using the above peroxide. In addition, when an electron beam is used, polymerization can be performed without adding an initiator.

The polymerization of the polymerizable compound can be carried out by either homopolymerization or copolymerization.
Examples of monomers used for copolymerization include styrene derivatives, (meth) acrylic acid ester derivatives, alkyl vinyl ethers, vinyl chloride, ethylene, propylene, and the like, but preferably styrene derivatives, (meth) acrylic acid esters. Is a derivative.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.

  A compound represented by the following chemical formula was synthesized.

  First, 1.4 mL of diisopropyl azodicarboxylate (40% toluene solution) was slowly added dropwise to a solution of 444 mg of ferulic acid ethyl ester, 630 mg of triphenylphosphine, and 0.26 mL of 2-hydroxyethyl acrylate under ice-cooling. did. After completion of dropping, the ice bath was removed and the mixture was stirred at room temperature for a whole day and night. The precipitated solid was filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 660 mg of the desired product.

The NMR and MS spectrum data of the polymerizable compound obtained in Example 1 are shown below. The NMR data was measured using an AVANCE400 manufactured by Bruker. The chemical shift value of ¹ HNMR described is a value based on tetramethylsilane. The MS spectrum was measured using Mariner manufactured by PerSeptive Biosystems (the same applies to the following measurements).

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.62 (1H, d, J = 15.9 Hz), 7.06-7.10 (2H, m), 6.90 (1H, d, J = 8. 1 Hz), 6.44 (1 H, dd, J = 17.4, 1.4 Hz), 6.32 (1 H, d, J = 15.9 Hz), 6.17 (1 H, dd, J = 10.4) , 17.4 Hz), 5.86 (1H, dd, J = 10.4, 1.4 Hz), 4.55 (2H, t, J = 5.0 Hz), 4.31 (2H, t, J = 5.0 Hz), 4.26 (2H, q, J = 6.1 Hz), 3.89 (3H, s), 1.34 (3H, t, J = 6.1 Hz)
¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.2, 166.0, 150.0, 149.8, 144.3, 131.4, 128.4, 122.3, 116.4, 113.6, 110 5, 67.1, 62.7, 60.4, 56.0, 14.3.
<MS spectrum data>
ESI-TOF-MS m / e calcd for C 17 H 21 NaO 6 (M + H +) 321.13. found, 321.12.

  A compound represented by the following chemical formula was synthesized.

  A compound of formula (62) was synthesized by the same procedure as in Example 1, except that ferulic acid decyl ester (83 mg) was used instead of ferulic acid ethyl ester and 2-hydroxyethyl methacrylate was used instead of 2-hydroxyethyl acrylate. (20 mg).

  The NMR and MS spectrum data of the polymerizable compound obtained in Example 2 are shown below.

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.62 (1H, d, J = 15.9 Hz), 7.07-7.10 (2H, m), 6.92 (1H, d, J = 8. 1 Hz), 6.32 (1 H, d, J = 15.9 Hz), 6.13 (1 H, brs), 5.58 (1 H, brs), 4.53 (2 H, t, J = 4.7 Hz) , 4.32 (2H, t, J = 4.7 Hz), 4.19 (2H, t, J = 6.7 Hz), 3.89 (3H, s), 1.95 (3H, s), 1 .70 (2H, m), 1.27-1.41 (14H, m), 0.88 (3H, t, J = 6.7 Hz)
¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.3, 150.1, 149.9, 144.3, 135.9, 126.4, 126.1, 122.3, 116.4, 113.8, 110 6, 67.2, 64.7, 62.9, 56.0, 31.9, 29.5, 29.3, 28.8, 6.0, 22.7, 18.3, 14.1 .
<MS spectrum data>
ESI-TOF-MS m / e calcd for C 26 H 38 NaO 6 (M + Na +) 469.26. found, 469.22

  A compound represented by the following chemical formula was synthesized.

  First, 0.1 mL of acrylic acid chloride was slowly added dropwise to a solution of 222 mg of ferulic acid ethyl ester and 0.21 mL of triethylamine in THF (5 mL) under ice cooling. After completion of dropping, the ice bath was removed and the mixture was stirred at room temperature for a whole day and night. The reaction solution was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The organic phase was washed and dried, and then a solid was precipitated in a chloroform / hexane system to obtain 140 mg of the desired product.

  The NMR and MS spectrum data of the polymerizable compound obtained in Example 3 are shown below.

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.65 (1H, d, J = 16.0 Hz), 7.08-7.15 (2H, m), 6.63 (1H, dd, J = 17. 3, 1.3 Hz), 6.40 (1H, d, J = 16.0 Hz), 6.35 (1 H, dd, J = 17.3, 10.5 Hz), 6.04 (1 H, dd, J = 10.4, 1.2 Hz), 4.27 (2 H, q, J = 7.1 Hz), 3.86 (3 H, s), 1.35 (3 H, t, J = 7.1 Hz)
¹³ C NMR (100 MHz, CDCl ₃ ) δ 166.8, 163.8, 151.5, 143.9, 141.2, 133.5, 133.0, 127.4, 123.3, 121.2, 118 5, 111.3, 60.6, 56.0, 14.3.
<MS spectrum data>
ESI-TOF-MS m / e calcd for C 15 H 17 O 5 (M + H +) 277.11. found, 277.09.

  A compound represented by the following chemical formula was synthesized.

(Where n = 6 (average value))
Ferulic acid ethyl ester (444 mg) was used, and polyethylene glycol acrylate (number average molecular weight 375) was used instead of 2-hydroxyethyl acrylate, and the compound of formula (64) was synthesized by the same procedure as in Example 1 ( 66 mg) (with trace impurities).

The NMR data of the polymerizable compound obtained in Example 4 are shown below.
<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.62 (1H, d, J = 15.9 Hz), 7.04-7.09 (2H, m), 6.90 (1H, d, J = 8. 2 Hz), 6.43 (1 H, brd, J = 17.3 Hz), 6.31 (1 H, d, J = 15.9 Hz), 6.17 (1 H, dd, J = 10.4, 17.3 Hz) ), 5.84 (1H, brd, J = 10.4 Hz), 4.22-4.33 (6H, m), 3.88 (3H, s), 3.61-3.75 (24H, m) ), 1.34 (3H, t, J = 6.1 Hz)
¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.2, 166.2, 150.4, 149.6, 144.5, 131.9, 128.4, 128.3, 122.4, 116.0, 113 0.0, 110.1, 70.8, 70.8, 70.6, 69.5, 68.4, 63.4, 60.4, 56.0, 14.3

  A compound represented by the following chemical formula was synthesized.

  The compound of formula (65) was synthesized (205 mg) by the same procedure as in Example 1 except that ferulic acid 2-ethylhexyl ester (306 mg) was used instead of ferulic acid ethyl ester.

  The NMR data and MS spectrum data of the polymerizable compound obtained in Example 5 are shown below.

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.61 (1H, d, J = 15.9 Hz), 7.07-7.10 (2H, m), 6.90 (1H, d, J = 8. 1 Hz), 6.44 (1 H, dd, J = 17.3, 1.4 Hz), 6.32 (1 H, d, J = 15.9 Hz), 6.17 (1 H, dd, J = 10.4) , 17.3 Hz), 5.86 (1H, dd, J = 10.4, 1.4 Hz), 4.55 (2H, t, J = 5.1 Hz), 4.31 (2H, t, J = 5.1 Hz), 4.11-4.13 (2H, m), 3.84 (3H, s), 1.60 (1H, m), 1.30-1.43 (8H, m), 0 .89-0.95 (6H, m).
¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.4, 166.0, 150.0, 149.8, 144.2, 131.4, 128.4, 128.0, 122.3, 116.5, 113 6, 110.5, 67.1, 66.9, 62.7, 56.0, 38.9, 30.5, 29.0, 23.8, 23.0, 14.1, 11.0 .
<MS spectrum data>
ESI-TOF-MS m / e calcd for C 23 H 33 O 6 (M + H +) 405.23. found, 405.21.

  A compound represented by the following chemical formula was synthesized.

  The compound of formula (66) was prepared by the same procedure as in Example 1, except that ferulic acid 2-ethylhexyl ester (15 g) was used instead of ferulic acid ethyl ester and 2-hydroxyethyl methacrylate was used instead of 2-hydroxyethyl acrylate. Synthesized (17.5 g) (contains traces of impurities).

  The NMR data and MS spectrum data of the polymerizable compound obtained in Example 6 are shown below.

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.62 (1H, d, J = 15.9 Hz), 7.08-7.10 (2H, m), 6.92 (1H, d, J = 8. 1 Hz), 6.33 (1 H, d, J = 15.9 Hz), 6.13 (1 H, brs), 5.58 (1 H, brs), 4.53 (2 H, t, J = 5.2 Hz) , 4.32 (2H, t, J = 5.2 Hz), 4.11-4.15 (2H, m), 3.90 (3H, s), 1.95 (3H, s), 1.65 (1H, m), 1.24-1.46 (8H, m), 0.93-0.95 (6H, m).
¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.3, 167.2, 150.0, 149.8, 144.2, 135.9, 129.0, 128.3, 128.2, 126.1, 122 .3, 116.4, 113.7, 110.5, 67.1, 66.8, 62.9, 56.0, 38.8, 30.4, 28.9, 23.7, 22.9 , 14.0, 11.0.
<MS spectrum data>
ESI-TOF-MS m / e calcd for C 24 H 34 NaO 6 (M + Na +) 441.23. found, 441.20.

  A compound represented by the following chemical formula was synthesized.

(Where n = 7 (average value))
Ferulic acid 2-ethylhexyl ester (612 mg) was used instead of ferulic acid ethyl ester, and polyethylene glycol methacrylate (number average molecular weight 360) was used instead of 2-hydroxyethyl acrylate. ) Was synthesized (134 mg) (containing a trace amount of impurities).

The NMR data of the polymerizable compound obtained in Example 7 are shown below.
<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.61 (1H, d, J = 15.9 Hz), 7.05-7.09 (2H, m), 6.90 (1H, d, J = 8. 2 Hz), 6.31 (1H, d, J = 15.9 Hz), 6.13 (1H, brs), 5.58 (1H, brs), 4.29-4.31 (2H, m), 4 20-20.23 (2H, m), 4.11-4.13 (2H, m), 3.90 (3H, s), 3.61-3.76 (28H, m), 1.95 (3H, s), 1.65 (1H, m), 1.25-1.44 (8H, m), 0.89-0.95 (6H, m).
¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.4, 167.3, 150.4, 149.6, 144.2, 136.1, 127.8, 125.7, 122.4, 116.1, 113 0.0, 110.1, 70.8, 70.6, 70.5, 69.5, 69.1, 68.4, 66.8, 63.9, 56.0, 38.9, 30.4 , 28.9, 23.8, 23.0, 22.0, 18.3, 14.0, 11.0.

  A compound represented by the following chemical formula was synthesized.

  A compound of formula (68) was synthesized in the same manner as in Example 1, except that ferulic acid cyclohexyl ester (138 mg) was used instead of ferulic acid ethyl ester and 2-hydroxyethyl methacrylate was used instead of 2-hydroxyethyl acrylate. (138 mg).

  The NMR and MS spectrum data of the polymerizable compound obtained in Example 8 are shown below.

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.61 (1H, d, J = 15.9 Hz), 7.07-7.10 (2H, m), 6.91 (1H, d, J = 8. 2 Hz), 6.32 (1H, d, J = 15.9 Hz), 6.13 (1H, brs), 5.58 (1H, brs), 4.88 (1H, m), 4.53 (2H) , T, J = 5.1 Hz), 4.32 (2H, t, J = 5.1 Hz), 3.89 (3H, s), 1.95 (3H, s), 1.91-1.94. (2H, m), 1.73-1.79 (2H, m), 1.30-1.50 (6H, m)
¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.2, 166.6, 149.9, 149.8, 144.0, 135.9, 128.4, 126.1, 122.2, 117.0, 113 7, 110.5, 72.6, 67.1, 62.9, 56.0, 31.8, 25.4, 23.8, 18.2.
<MS spectrum data>
ESI-TOF-MS m / e calcd for C ₂₂ H ₂₈ NaO ₆ (M + Na ⁺ ) 411.18. found, 411.16.

  A compound represented by the following chemical formula was synthesized.

  The compound of formula (69) was prepared in the same manner as in Example 1, except that ferulic acid isobornyl ester (165 mg) was used instead of ferulic acid ethyl ester and 2-hydroxymethyl methacrylate was used instead of 2-hydroxyethyl acrylate. Synthesized (77 mg) (contains trace amounts of impurities).

  The NMR and MS spectrum data of the polymerizable compound obtained in Example 9 are shown below.

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.56 (1H, d, J = 15.5 Hz), 7.06-7.09 (2H, m), 6.91 (1H, d, J = 8. 2 Hz), 6.32 (1 H, d, J = 15.5 Hz), 6.13 (1 H, brs), 5.58 (1 H, brs), 4.79-4.82 (1 H, m), 4 .53 (2H, t, J = 5.2 Hz), 4.32 (2H, t, J = 5.2 Hz), 3.90 (3H, s), 1.95 (3H, s), 1.55 -1.90 (3H, m), 0.82-1.28 (4H, m), 1.07 (3H, s), 0.90 (3H, s), 0.87 (3H, s).
¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.2, 166.7, 150.0, 149.9, 143.9, 135.9, 128.4, 126.1, 122.3, 117.0, 113 7, 110.6, 81.0, 67.1, 62.9, 56.0, 48.9, 47.0, 45.1, 38.9, 33.8, 27.1, 21.1 , 20.0, 11.5.
<MS spectrum data>
ESI-TOF-MS m / e calcd for C ₂₆ H ₃₄ NaO ₆ (M + Na ⁺ ) 465.23. found, 465.22.

  A compound represented by the following chemical formula was synthesized.

  A compound of formula (70) was synthesized (65 mg) by the same procedure as in Example 1 except that ferulic acid t-butyl ester (63 mg) was used instead of ferulic acid ethyl ester.

  The NMR and MS spectrum data of the polymerizable compound obtained in Example 10 are shown below.

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.52 (1H, d, J = 15.9 Hz), 7.07-7.08 (2H, m), 6.89 (1H, d, J = 8. 2 Hz), 6.44 (1 H, dd, J = 17.3, 1.4 Hz), 6.25 (1 H, d, J = 15.9 Hz), 6.15 (1 H, dd, J = 10.4) , 17.3 Hz), 5.86 (1H, dd, J = 10.4, 1.4 Hz), 4.55 (2H, t, J = 5.1 Hz), 4.31 (2H, t, J = 5.1 Hz), 3.89 (3H, s), 1.53 (9H, s)
¹³ C NMR (100 MHz, CDCl ₃ ) δ 166.5, 166.0, 149.8, 149.7, 143.3, 131.4, 128.5, 128.0, 122.1, 118.3, 113 6, 110.4, 80.3, 67.1, 62.7, 55.9, 28.2.
<MS spectrum data>
ESI-TOF-MS m / e calcd for C 19 H 24 NaO 6 (M + Na +) 371.15. found, 371.13.

  A compound represented by the following chemical formula was synthesized.

  First, 39 μL of benzyl-methyl-imidazole as a catalyst was added to a toluene (20 mL) solution of 1.1 g of ferulic acid ethyl ester, 0.82 mL of glycidyl methacrylate and 5 mg of hydroquinone, and the mixture was stirred overnight under reflux. Next, the residue obtained by concentrating the reaction solution was purified by silica gel column chromatography to obtain 705 mg of the desired product (including a trace amount of other isomers).

  The NMR and MS spectrum data of the polymerizable compound obtained in Example 11 are shown below.

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.62 (1H, d, J = 15.9 Hz), 7.05-7.09 (2H, m), 6.90 (1H, d, J = 8. 2 Hz), 6.32 (1 H, d, J = 15.9 Hz), 6.15 (1 H, brs), 5.61 (1 H, brs), 4.06-4.50 (7 H, m), 3 .88 (3H, s), 1.96 (3H, s), 1.34 (3H, t, J = 5 Hz).
¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.3, 167.1, 149.9, 149.8, 144.2, 135.8, 128.5, 126.2, 122.2, 116.5, 114 1, 110.3, 70.7, 68.4, 65.3, 60.4, 55.8, 18.3, 14.3.
<MS spectrum data>
ESI-TOF-MS m / e calcd for C ₁₉ H ₂₅ O ₇ (M + H ⁺ ) 365.16. found, 365.15.

  A compound represented by the following chemical formula was synthesized.

  The compound of formula (72) was prepared by the same procedure as in Example 11 using ferulic acid 2-ethylhexyl ester (306 mg) instead of ferulic acid ethyl ester and tetrabutylammonium bromide instead of benzyl-methyl-imidazole. Synthesized (262 mg) (contains trace isomers).

  The NMR and MS spectrum data of the polymerizable compound obtained in Example 12 are shown below.

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.61 (1H, d, J = 15.9 Hz), 7.06-7.10 (2H, m), 6.91 (1H, d, J = 8. 2 Hz), 6.33 (1H, d, J = 15.9 Hz), 6.15 (1 H, brs), 5.61 (1 H, brs), 4.06 to 4.37 (7 H, m), 3 .88 (3H, s), 1.96 (3H, s), 1.64-1.67 (1H, m), 1.31-1.46 (8H, m), 0.91-0.95 (6H, m)
¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.4, 167.3, 149.8, 144.1, 135.8, 128.6, 126.5, 122.3, 116.6, 114.1, 110 .2, 70.7, 68.4, 66.7, 65.3, 55.8, 38.8, 30.4, 28.9, 23.8, 23.0, 18.3, 14.0 , 11.0.
<MS spectrum data>
ESI-TOF-MS m / e calcd for C 25 H 36 NaO 7 (M + Na +) 471.24. found, 471.20.

  A compound represented by the following chemical formula was synthesized.

  The compound of formula (73) was synthesized by the same procedure as in Example 11 using ferulic acid cyclohexyl ester (138 mg) instead of ferulic acid ethyl ester and tetrabutylammonium bromide instead of benzyl-methyl-imidazole. (85 mg) (contains trace isomers).

  The NMR and MS spectrum data of the polymerizable compound obtained in Example 13 are shown below.

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.60 (1H, d, J = 15.9 Hz), 7.06-7.10 (2H, m), 6.90 (1H, d, J = 8. 2Hz), 6.31 (1H, d, J = 15.9 Hz), 6.15 (1H, brs), 5.61 (1H, brs), 4.90 (1H, m), 4.30-4 .37 (3H, m) 4.06-4.16 (2H, m), 3.87 (3H, s), 1.96 (3H, s), 1.90-1.95 (2H, m) , 1.76-1.81 (2H, m), 1.20-1.56 (6H, m).
¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.4, 166.5, 149.8, 143.9, 135.8, 128.6, 126.2, 122.3, 117.2, 114.1, 110 .2, 72.7, 70.7, 68.4, 66.7, 65.3, 55.8, 31.8, 30.4, 25.4, 23.8, 18.2.
<MS spectrum data>
ESI-TOF-MS m / e calcd for C 23 H 30 NaO 7 (M + Na +) 441.19. found, 441.16.

  A compound represented by the following chemical formula was synthesized.

  4-hydroxybutyl acrylate glycidyl ether in place of glycidyl methacrylate, tetrabutylammonium bromide in place of benzyl-methyl-imidazole as a catalyst, dimethylformamide in place of toluene as a solvent, and the same procedure as in Example 11 was performed. 74) was synthesized (280 mg, 71% yield).

  The NMR and MS spectrum data of the polymerizable compound obtained in Example 14 are shown below.

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.62 (1H, d, J = 15.9 Hz), 7.05-7.10 (2H, m), 6.92 (1H, d, J = 8. 3 Hz), 6.40 (1 H, dd, J = 17.3, 1.4 Hz), 6.32 (1 H, d, J = 15.9 Hz), 6.10 (1 H, dd, J = 17.3). , 10.4 Hz), 5.82 (1H, dd, J = 10.4, 1.4 Hz), 5.61 (1H, brs), 4.05-4.29 (7H, m), 3.88. (3H, s), 3.53-3.64 (4H, m), 1.64-1.78 (4H, m), 1.34 (3H, t, J = 7.1 Hz).
¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.1, 166.2, 150.1, 149.7, 144.3, 130.6, 128.4, 128.2, 122.3, 116.3, 113 7, 110.2, 71.4, 71.0, 70.6, 68.9, 64.2, 60.4, 55.8, 26.0, 25.4, 14.3.
<MS spectrum data>
ESI-TOF-MS m / e calcd for C ₂₂ H ₃₀ NaO ₈ (M + Na ⁺ ) 445.18. found, 445.14.

  A compound represented by the following chemical formula was synthesized.

  Cyclomer-A-200 in place of glycidyl methacrylate, tetrabutylammonium bromide in place of benzyl-methyl-imidazole as a catalyst, dimethylformamide in place of toluene as a solvent, and the same procedure as in Example 11 was performed. 76) (including isomers) was synthesized (284 mg, 60% yield).

  The NMR and MS spectrum data of the polymerizable compound obtained in Example 15 are shown below.

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.62 (1H, d, J = 15.9 Hz), 7.05-7.19 (2H, m), 6.92-6.96 (1H, m) 6.35-6.45 (1H, m), 6.32 (1H, d, J = 15.9 Hz), 6.09-6.16 (1 H, m), 5.83-5.86 ( 1H, m), 5.61 (1H, brs), 4.03-4.29 (6H, m), 3.88 (3H, s), 3.53-3.64 (4H, m), 1 .50-2.30 (7H, m), 1.26 (3H, t, J = 7.1 Hz)
<MS spectrum data>
ESI-TOF-MS m / e calcd for C 22 H 28 NaO 7 (M + Na +) 427.17. found, 427.15.

  A compound represented by the following chemical formula was synthesized.

  According to the method of Example 11 using 3-ethyl-3- (methacryloyloxymethyl) oxetane instead of glycidyl methacrylate, tetraphenylphosphonium bromide instead of benzyl-methyl-imidazole as a catalyst, and sulfolane instead of toluene as a solvent. Oil was obtained by the above method. As a result of measuring the MS spectrum of the obtained oily substance, it was confirmed that there was a molecular weight peak that could be identified as the target substance.

<MS spectrum data>
ESI-TOF-MS m / e calcd for C 22 H 30 NaO 7 (M + Na +) 427.19. found, 427.09.

  The following experiment was conducted as a method for introducing a (meth) acryloyl group after extending an alkyleneoxy group from a phenolic hydroxyl group of a ferulic acid ester using a cyclic ether.

  Ferulic acid ethyl ester 2.2 g, triethylamine 0.14 mL, ethylene oxide (0.88 mol / L in toluene) and solvent toluene (20 mL) were placed in a pressure-resistant glass container and heated at 120 ° C. for 6 hours. After completion of the reaction, the solid was filtered. The residue obtained by concentrating the filtrate was generated by silica gel column chromatography to obtain the compound of formula A (710 mg).

  0.06 mL of methacryloyl chloride was added at 0 ° C. to 133 mg of Compound A into which ethyleneoxy group was introduced and 0.1 mL of triethylamine (5.0 mL). The reaction solution was stirred overnight at room temperature. The reaction solution was poured into a saturated aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. After washing and drying the organic phase, 62 mg of the desired product was obtained by precipitating a solid in a chloroform / hexane system.

  The NMR and MS spectrum data of the polymerizable compound obtained in Example 17 are shown below.

<NMR data>
¹ H NMR (400 MHz, CDCl ₃ ) δ 7.62 (1H, d, J = 15.9 Hz), 7.05-7.10 (2H, m), 6.91 (1H, d, J = 8. 1 Hz), 6.32 (1 H, d, J = 15.9 Hz), 6.13 (1 H, brs), 5.58 (1 H, brs), 4.53 (2 H, t, J = 5.2 Hz) , 4.31 (2H, t, J = 5.2 Hz), 4.28 (2H, q, J = 7.2 Hz), 3.88 (3H, s), 1.95 (3H, s), 1 .34 (3H, t, J = 7.2 Hz)
¹³ C NMR (100 MHz, CDCl ₃ ) δ 167.2, 167.1, 150.0, 149.8, 144.3, 135.9, 128.3, 126.1, 122.3, 116.3, 113 7, 110.5, 67.1, 62.9, 60.4, 56.0, 18.3, 14.3.
<MS spectrum data>
ESI-TOF-MS m / e calcd for C 18 H 22 NaO 6 (M + Na +) 357.13. found, 357.08.

(Evaluation of UV absorption characteristics of polymerizable compounds)
The ultraviolet absorption spectrum of the polymerizable compound obtained in Example 5 and Example 12 and the ultraviolet absorption spectrum of a commercially available hydroxybenzophenone compound as a comparative example were measured. The measurement results are shown in FIG.

In addition, the maximum absorption wavelength around 320 nm of each compound and the value of the molar extinction coefficient at that wavelength are shown below.
Compound of Example 5 320 nm (ε = 17700) (EtOH)
Compound of Example 12 321 nm (ε = 19500) (EtOH)
Hydroxybenzophenone compound 324 nm (ε = 7900) (EtOH)
From FIG. 1, it can be seen that the spectra of the polymerizable compounds of the present invention obtained in Examples 5 and 12 are almost the same, and the difference other than the ferulic acid moiety does not significantly affect the absorption spectrum. It can also be seen that the absorption wavelength peak is substantially the same as the absorption wavelength of the hydroxybenzophenone compound B. Furthermore, the molar absorbance coefficient of the polymerizable compound of the present invention obtained in Examples 5 and 12 is about twice that of hydroxybenzophenone compound B, and has a very effective ultraviolet absorbing ability in this wavelength region. I understand.

(Comparative example)
The measurement results of the ultraviolet absorption spectrum of the polymerizable compound C synthesized from p-hydroxycinnamic acids which are also used as an ultraviolet absorber and the polymerizable compound of the present invention obtained in Example 1 are shown in FIG. The maximum absorption wavelength of each compound and the value of the molar extinction coefficient at that wavelength are shown below.

Compound of Example 1 318 nm ε = 16600 (EtOH)
Polymerizable compound C 308 nm ε = 20900 (EtOH)
From FIG. 2, it can be seen that the compound of the present invention has an absorption band on the long wavelength side as compared with Compound C, and the absorption near 320 nm, which is one of the causes of photodegradation, is high.

(Polymerization reaction example 1)
A polymerization reaction (60 ° C., 18 hours) was carried out using azobisisobutyronitrile (AIBN) (26 mg) as an initiator in the compound obtained in Example 1 (141 mg), methyl methacrylate (0.28 mL) and THF. It was. The obtained reaction solution was poured into methanol, and the obtained solid was reprecipitated and purified with a THF / MeOH system to obtain 296 mg of a polymer.
The molar composition ratio in the copolymer is ferulic acid unit-containing acrylate: methyl methacrylate (MMA) = 1: 8.2, and the molecular weight of the obtained polymer (measurement solvent: THF, converted to polystyrene) is as follows. Met.
Mn = 25350
Mw = 71460

(Polymerization reaction example 2)
The compound (423 mg) obtained in Example 1 was subjected to a polymerization reaction (60 ° C., 18 hours) in THF using AIBN (1 mg) as an initiator. The obtained reaction solution was poured into methanol, and the obtained solid was reprecipitated and purified with a THF / MeOH system to obtain 110 mg of a polymer.

The molecular weight (measurement solvent: THF, polystyrene conversion) of the obtained polymer was as follows.
Mn = 20210
Mw = 43255

(UV absorption spectrum of polymer)
FIG. 3 shows the results of ultraviolet absorption spectrum measurement using the polymer obtained in Example 19 as a thin film. Moreover, the spectrum in the solution state of the compound of Example 1 which is a compound before superposition | polymerization is also shown as a comparative example (since the measuring methods of each spectrum differ, only the comparison of an absorption wavelength).

  FIG. 3 shows that the compound of the present invention has the same absorption ability as that before the polymerization even after the polymerization.

  As mentioned above, although the Example of this invention was described, the claim of this invention is not limited above, The range of this invention is shown by a claim.

  The polymerizable compound of the present invention is used as an ultraviolet absorber for outdoor use weather-resistant polycarbonate, outdoor paints for automobiles, clear top coating materials, ink jet printing materials, glasses, contact lenses, light guide plates for liquid crystal back panels, etc. Is done.

It is a figure which shows the ultraviolet absorption spectrum of the polymeric compound of Example 5 and Example 12. 2 is a diagram showing an ultraviolet absorption spectrum of the polymerizable compound of Example 1. FIG. It is a figure which shows the ultraviolet absorption spectrum of the polymer of Example 19.

Claims (9)

The polymeric compound represented by following General formula (1).

(In the formula, R ¹ represents hydrogen or a methyl group, R ² represents a monovalent substituent, and —X— represents a divalent substituent.) The polymerizable compound according to claim 1, wherein R ² is a linear or branched alkyl group, an alkyl group containing a cyclic structure, or an alkyl group containing an aromatic ring at the terminal. The polymerizable compound according to claim 1, wherein —X— is one of the structures represented by the following general formulas (2) to (5), or a structure obtained by combining them.

(In the formula, R ³ represents an alkylene group having a linear or branched structure having 1 to 5 carbon atoms, and n represents an integer of 0 to 10.)

(In the formula, R ⁴ and R ⁵ each independently represents a linear alkyl group having 1 to 5 carbon atoms.)

(In the formula, R ⁶ represents an alkyl group having 1 to 5 carbon atoms, and j represents 0 or 1.)

(Wherein R ⁷ represents hydrogen or an alkyl group having 1 to 3 carbon atoms, k represents an integer of 0 to 2, and l represents 0 or 1)   The polymerizable compound according to claim 1, wherein —X— is a structure represented by the general formula (2).   The polymerizable compound according to claim 1, wherein -X- is a structure represented by the general formula (3), (4) or (5). The polymerizable compound according to claim 1, wherein —X— is a structure represented by the following general formula (6).

(In the formula, R ³ is an alkylene group having a linear or branched structure having 1 to 5 carbon atoms, n is an integer from 0 to 10, and -Y- is any one of the above general formulas (3) to (5). A divalent substituent having the structure shown is shown.)   5. The method according to claim 4, wherein an ether bond reaction between a ferulic acid ester and a (meth) acrylic acid having a hydroxyalkyl group or a derivative thereof is used for bonding the ferulic acid-derived moiety and the (meth) acrylic acid moiety. The manufacturing method of the polymeric compound of description.   The method for producing a polymerizable compound according to claim 4, wherein the (meth) acrylic acid part is reacted after the alkylene oxide chain is extended by reacting the ferulic acid ester with the alkylene oxide.   The method for producing a polymerizable compound according to claim 5 or 6, wherein a (meth) acrylate having an epoxy group or an oxetanyl group in a molecule is reacted with a ferulic acid ester.

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