JP2000191601A - Methacrylates and their polymers and manufacture of methacrylates - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having polymerizability, useful for synthetic raw material for various chemical substances by reacting specific ester with a specific ketone. SOLUTION: This compound is expressed by formula I or II (R1 is H or an alkyl; R2 and R3 are each an alkyl, R2 and R3 may form a ring), for example, the compound of formula III. The prescribed compound is obtained by reacting (A) methacrylic acid derivative expressed by formula IV, and (B) 1,3-diketone (e.g.; acetylacetone or the like) in the presence of a basic compound such as sodium carbonate or the like in the presence of the alkylating catalyst such as triphenylphosphine or the like, in the absence of solvent or in a solvent such as benzene or the like, at a temperature in the range of 0-150 deg.C, ordinarily for 30 min-24 h, and the ratio of the component (A)/the component (B) is 1/0.5-10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The novel methacrylate derivative of the present invention has polymerizability and is useful as a raw material for synthesizing various chemical materials or as a synthetic intermediate for pharmaceuticals or agricultural chemicals for various uses. The polymer of the present invention is useful as various chemical materials such as a metal chelate forming material.

[0002]

2. Description of the Related Art Acrylic acid and methacrylic acid derivatives have been widely used as polymerizable monomers or intermediates for synthesizing various compounds. Α-Hydroxymethyl acrylate, which is one of these derivatives, is a compound that has attracted attention for various applications due to its structural feature of having a hydroxymethyl group at the α-position of the ester group. In recent years, a method for synthesizing α-hydroxymethyl acrylate and its derivatives with high purity [JP-A-5-173]
75, 7-285906, 8-183758, 8-30
1817, 8-183755], a purification method [JP-A-9-6
7310] and techniques such as a storage method [Japanese Unexamined Patent Application Publication No. 9-136856] have been disclosed, and expectations for use development have been further increased.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel compound which is useful using α-hydroxymethyl acrylate and its derivatives as raw materials.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, by reacting α-hydroxymethyl acrylate with 1,3-diketone, The present inventors have found that a novel methacrylate derivative can be obtained, and have completed the present invention. That is, the present invention provides a methacrylic acid ester derivative represented by the following formula [1A] or [1B], a polymer obtained by polymerizing the methacrylic acid ester derivative or another copolymerizable monomer with the methacrylic acid ester derivative, and a compound represented by the following formula: The method for producing a methacrylic acid ester derivative, wherein the methacrylic acid derivative represented by [2] and 1,3-diketone are reacted in the presence of a basic compound.

[0005]

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[0006]

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However, R ¹ in the above formulas [1A] and [1B]
Represents a hydrogen atom or an alkyl group, R ² and R ³ each represent an alkyl group, and R ² and R ³ may form a ring.

Embedded image

(X in the above formula is a leaving group, and R ¹ is a hydrogen atom or an alkyl group.)

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. ○ Methacrylic ester derivative The methacrylic ester derivative of the present invention has the formula [1A]
Or [1B]. The formula [1A] is a keto type, and the formula [1B] is an enol type.
It has an enol type tautomerism. Hereinafter, the above equation 1A will be described as an example. In the above formula [1A], R ¹ is a hydrogen atom or an alkyl group. Preferred alkyl groups are linear, branched or cyclic alkyl groups having 1 to 18 carbon atoms. Preferred specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Linear alkyl groups such as octyl group, decyl group, undecyl group, tetradecyl group, and stearyl group; branched alkyl groups such as i-propyl group, i-butyl group, t-butyl group and 2-ethylhexyl group; cyclohexyl group; and isobornyl And a cyclic alkyl group such as an adamantyl group. Of these, an ethyl group, a propyl group, a butyl group, an i-propyl group, an i-butyl group, a t-butyl group, and a cyclohexyl group are more preferable.

R ² and R ³ are each an alkyl group capable of forming a ring with each other, and a preferred alkyl group has 1 carbon atom.
To 18 aliphatic or aromatic substituents, which may be branched.

The methacrylic ester derivative represented by the general formula [1A] can be easily prepared by reacting a methacrylic acid derivative represented by the following general formula [2] with 1,3-diketone in the presence of a basic compound. Can be manufactured.

[0012]

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In the general formula [2], X is a leaving group. Preferred leaving groups are hydroxyl, chlorine, bromine,
Iodine atom, acetyloxy group, monochloroacetyloxy group, dichloroacetyloxy group, trifluoroacetyloxy group, 2-chlorobenzoyloxy group, 4-nitrobenzoyloxy group, methanesulfonyloxy group,
A benzenesulfonyloxy group and a p-toluenesulfonyloxy group, among which a hydroxyl group, a chlorine atom, an acetyloxy group, a methanesulfonyloxy group, a benzenesulfonyloxy group, and a p-toluenesulfonyloxy group are more preferable. The methacrylic acid derivative represented by the general formula [2] may be prepared in advance or used in a reaction system.

The preferred 1,3-diketone in the present invention is acetylacetone,
2,4-hexanedione, 2,4-heptanedione, 3,
5-heptanedione, 1,3-cyclopentanedione,
1,3-cyclohexanedione and dimedone.

The reaction molar ratio of the 1,3-diketone to the methacrylic acid derivative represented by the above formula [2] is stoichiometrically 1: 1, but from 1: 5 to 5: 1. May be reacted. However, if the molar ratio exceeds this range, it becomes difficult to isolate and purify the product, which is not preferable.

Preferred basic compounds are sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, sodium hydride, sodium metal, disodium phosphate, tripotassium phosphate, n-butyllithium, s-butyllithium, t-butyllithium. Butyllithium, n-butylmagnesium chloride, s-butylmagnesium chloride, t-
Butylmagnesium chloride, triethylamine, diisopropylethylamine, N, N-dimethylbenzylamine, pyridine, 2,6-lutidine, 2,4,6-collidine, tetramethylethylenediamine and diazabicyclo [2.2.2] octane; These can be used alone or in combination of two or more.

The preferred amount of the basic compound is based on the methacrylic acid derivative represented by the general formula [2].
It is 0.5 to 10 equivalents, preferably 1 to 5 equivalents. When the amount is less than these ranges, the effect is insufficient, and when the amount is more than these ranges, the production cost is undesirably high.

In the reaction of the methacrylic acid derivative represented by the general formula [2] with 1,3-diketone (this reaction), a known alkylation catalyst such as triphenylphosphine, tetrabutylammonium bromide or potassium iodide is added. May be.

This reaction can be carried out without a solvent or in a solvent. The preferred solvent is not limited as long as it does not hinder the progress of this reaction. Benzene, toluene, pentane, cyclohexane, dichloromethane, chloroform, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetic acid ethyl,
Diethyl ether, tetrahydrofuran, 1,4-dioxane, water and a mixed solvent thereof.

The preferred reaction temperature in this reaction is 0 ° C.
To 150 ° C, preferably room temperature to 120 ° C. When the reaction temperature is too low, the progress of the reaction is slow, and when the reaction temperature is too high, the decomposition reaction of the raw material or the product tends to proceed.

The preferred reaction time in this reaction is usually from 30 minutes to 24 hours, depending on the reaction conditions.

The methacrylate derivative represented by the general formula [1A] obtained by this reaction can be easily isolated and purified by a conventional method such as solvent extraction, distillation, reprecipitation, recrystallization and high performance liquid chromatography. Can be.

Polymer of Methacrylate Derivative Next, a polymer obtained by polymerizing the methacrylate derivative of the present invention or another copolymerizable monomer with the methacrylate derivative will be described. The polymer of the present invention is produced by polymerizing the methacrylic acid ester derivative represented by the general formula [1A] alone or in combination, or by copolymerizing with a compound copolymerizable with these derivatives. The method of polymerization or copolymerization is not particularly limited, and for example, a known polymerization method such as a method using a radical initiator, a method using an ultraviolet ray, a method using an electron beam, and a method using heating can be used.

Preferred copolymerizable compounds are known polymerizable compounds such as acrylic acid derivatives, methacrylic acid derivatives and styrene derivatives, and one or more of these can be used. In addition, the monomer composition ratio in the case of copolymerization is not particularly limited, but it is preferable that the methacrylic acid ester derivative represented by the general formula [1A] be 0.5 mol% or more of all the monomers. More preferably, the content is 2 mol% or more.

The preferred degree of polymerization is that the number average molecular weight is 1,0.
00 to 100,000.

The methacrylic acid ester derivative of the present invention or a polymer obtained by polymerizing the methacrylic acid ester derivative and another copolymerizable monomer may be used as a crude product after the completion of the polymerization reaction. After purification by standard methods such as extraction and reprecipitation,
It can be used for various applications.

[0027]

The present invention will be described below in detail with reference to examples.

[0028]

Example 1 A compound represented by the following formula [3] (compound [3] using ethyl α-methylsulfonyloxymethyl acrylate; hereinafter, a compound represented by formula [i] is similarly referred to as compound [i]) Where i is a positive integer).

[0029]

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The specific synthesis method is as follows. 24.5 g of ethyl α-hydroxymethyl acrylate (18
8 mmol) and 42.8 g (423 mm) of triethylamine.
ol) in a solution of 100 g of toluene at −20 ° C. with 23.7 g (207 mmol) of methanesulfonic acid chloride in toluene 5
0 g of the solution was added dropwise, and the mixture was stirred for 1 hour under ice-cooling and reacted at room temperature for further 16 hours to synthesize a compound in which X in the general formula [2] is a methylsulfonyloxy group and R1 is an ethyl group. Next, 22.0 g of dimedone (157 mm
ol) and diazabicyclo [2.2.2] octane
76 g (15.7 mmol) was added, and the mixture was stirred at 75 ° C. for 3 hours. After cooling, the mixture was extracted with ethyl acetate and washed with 0.5N hydrochloric acid and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and the residue was recrystallized from acetonitrile to obtain 25.2 g of a pale yellow crystalline compound (yield: 64%). The compound obtained as described above is 1H-NM
By R and IR analyses, it was confirmed to be compound [3].

Chemical shift of 1H-NMR and IR
Are shown below. 1H-NMR (CDCl ₃ ) δ: 1.05 (6H, s), 1.33 (3H,
t), 2.20 (2H, s), 2.33 (2H, s), 3.23 (2H, s), 4.26 (2H, q), 6.1
0 (1H, s), 6.23 (1H, s), 9.80 (1H, s) IR (KBr) cm ^-1 : 2960,2560,1720,1640,1550,135
0,1250,1210,1160,1050

[0032]

Example 2 Ethyl α-acetyloxymethyl acrylate (this compound is a compound in which X in the general formula [2] is an acetyloxy group and R1 is an ethyl group)
Was used to synthesize compound [3]. The specific synthesis method is as follows. 1.68 g (12.0 mmol) of dimedone
To a solution of 35 ml of tetrahydrofuran was added a solution of 3.82 g (36.0 mmol) of sodium carbonate in 35 ml of water. Next, ethyl α-acetyloxymethyl acrylate [synthesis method is described in D. Avci, et al., J. polym. Sci., Part.
A: Polym. Chem. 32, 2937 (1994)], and 4.40 g (25.8 mmol) were added dropwise. After reacting at room temperature for 16 hours, the mixture was extracted with ethyl acetate,
Washed with N hydrochloric acid and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and the residue was recrystallized from acetonitrile to obtain 0.90 g of a pale yellow crystalline compound (yield: 30%). The compound obtained as described above is
1H-NMR and IR analysis confirmed that the compound was compound [3].

[0033]

Example 3 Compound [3] was synthesized using ethyl α-hydroxymethyl acrylate. The specific synthesis method is as follows. 3.00 g (21.4) of dimedone and 5.90 g (55.7 mmol) of sodium carbonate in water 50
In a ml solution, ethyl α-hydroxymethyl acrylate (this compound is a compound in which X in the general formula [2] is a hydroxy group and R1 is an ethyl group) 6.6.
9 g (51.4 mmol) were added dropwise. After reacting at 70 ° C. for 6 hours, the mixture was extracted with ethyl acetate and washed with 0.5N hydrochloric acid and water. After drying the organic layer over anhydrous magnesium sulfate,
After concentrating and purifying by silica gel column chromatography, the residue was recrystallized from acetonitrile to obtain 0.14 g of a colorless crystalline compound (yield: 3%). The compound obtained as described above has 1H-NMR
And by IR analysis, it was confirmed to be the compound [3].

[0034]

Example 4 Compound [3] was synthesized using ethyl α-acetyloxymethyl acrylate. The specific synthesis method is as follows. 1.68 g of dimedone (12.0 mm
ol) in 50 ml of tetrahydrofuran was added 0.50 g (12.5 mmol) of 60% oily sodium hydride, and 1
After stirring for 0 minutes, 2.20 g (12.8 mmol) of acetic acid ester of ethyl α-hydroxymethyl acrylate was added dropwise. After stirring at room temperature for 1 hour, 0.50 g (12.5 mmol) of 60% oily sodium hydride was added again, and after stirring for 10 minutes, 2.20 g (12.8 mmol) of acetic acid ester of α-hydroxymethyl acrylate was added dropwise. . 16 at room temperature
After reacting for an hour, the mixture was extracted with ethyl acetate and washed with 0.5N hydrochloric acid and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, purified by silica gel column chromatography, and the residue was recrystallized from acetonitrile to obtain 0.45 g of a colorless crystalline compound (yield: 15%). ). The compound obtained as described above has 1
H-NMR and IR analysis confirmed that the compound was compound [3].

[0035]

Example 5 A compound represented by the following formula [4] was synthesized using ethyl α-methylsulfonyloxymethyl acrylate.

[0036]

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The specific synthesis method is as follows. 60.0 g of ethyl α-hydroxymethyl acrylate (46
1 mmol) and 105 g of triethylamine (1.04 m
ol) at 150 ° C. was added dropwise to a solution of 58.1 g (507 mmol) of methanesulfonic acid chloride in 100 g of toluene at −20 ° C., stirred for 1 hour under ice-cooling, and allowed to react at room temperature for further 16 hours to obtain a compound of the general formula [ 2], wherein X is a methylsulfonyloxy group, and R1 is an ethyl group. Next, 43.0 g (383 mmol) of 1,3-cyclohexanedione and 4.30 g (38.3 mmol) of diazabicyclo [2.2.2] octane were added, and the mixture was stirred at 75 ° C. for 3 hours. After cooling, the mixture was extracted with ethyl acetate and washed with 0.5N hydrochloric acid and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and the residue was recrystallized from acetonitrile to obtain 43.3 g of a pale yellow crystalline compound (yield: 50%). The compound obtained as described above was confirmed to be the compound [4] by 1H-NMR and IR analysis.

1H-NMR chemical shift and IR
Are shown below, and the 1H-NMR chart is shown in FIG. 1H-NMR (CDCl ₃ ) δ: 1.32 (3H, t), 1.91 (2H,
m), 2.32 (2H, t), 2.46 (2H, m), 3.21 (2H, s), 4.25 (2H, q), 6.1
1 (1H, s), 6.22 (1H, s), 9.90 (1H, s) IR (KBr) cm ^-1 : 2960,2600,1710,1640,1570,136
0,1270,1250,1190,1070,1020

[0039]

Example 6 A mixture of keto-enol isomers represented by the following formulas [5A] and [5B] was synthesized using ethyl α-methylsulfonyloxymethyl acrylate.

[0040]

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[0041]

Embedded image The specific synthesis method is as follows. 60.0 g (461 mmol) of ethyl α-hydroxymethyl acrylate, 0.15 g of hydroquinone, and triethylamine 105
g (1.04 mol) in a 250 g solution of toluene,
At 0 ° C., 58.1 g of methanesulfonic acid chloride (507 mm
ol) in 125 g of toluene was added dropwise, and the mixture was stirred for 1 hour under ice-cooling, and further reacted at room temperature for 16 hours. Next, 46.2 g (461 mmol) of acetylacetone and 1.87 g (9.24 mmol) of tributylphosphine were added, and the mixture was stirred at room temperature for 1 hour and further at 65 ° C. for 3 hours. After cooling, the mixture was extracted with ethyl acetate and washed with 0.1N hydrochloric acid and water. After the organic layer was dried over anhydrous magnesium sulfate, 0.2 g of hydroquinone was added and dissolved. The solvent was concentrated and distilled under reduced pressure (94-103 ° C, 4 mmHg) to obtain 18.4 g of a colorless liquid compound (yield 19%). The compound obtained as described above was confirmed by 1H-NMR to be a keto-enol isomer mixture (molar ratio 9:11) represented by the above formulas [5A] and [5B].

The chemical shifts of 1H-NMR are shown below. (Keto-type isomer) 1H-NMR (CDCl ₃ ) δ: 1.28 (3H, t), 2.22 (6H,
s), 2.83 (2H, d), 4.00 (1H, t), 4.17 (2H, q), 5.63 (1H, s), 6.2
1 (1H, s) (enol type isomer) 1H-NMR (CDCl ₃ ) δ: 1.31 (3H, t), 2.06 (6H,
s), 3.25 (2H, s), 4.26 (2H, q), 5.44 (1H, s), 6.24 (1H, s)

[0043]

Example 7 Using t-butyl α-methylsulfonyloxymethyl acrylate, keto-enol isomer mixtures represented by the following formulas [6A] and [6B] were synthesized.

[0044]

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[0045]

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The specific synthesis method is as follows. t-
39.6 g of butyl α-hydroxymethyl acrylate
(250 mmol), 0.20 g of hydroquinone and 63.2 g (625 mmol) of triethylamine in toluene 15
0 g solution at −20 ° C. in methanesulfonic acid chloride 3
A solution of 4.4 g (300 mmol) in 100 g of toluene was added dropwise, and the mixture was stirred under ice-cooling for 1 hour and reacted at room temperature for further 16 hours. X in the general formula [2] was a methylsulfonyloxy group, and R1 was t- A compound that is a butyl group was synthesized. Next, 12.0 g of acetylacetone (120 mmo
l) and 2.83 g of tributylphosphine (14.0 m
mol), and the mixture was stirred at room temperature for 1 hour and at 70 ° C. for 5 hours. After cooling, the mixture was extracted with ethyl acetate and washed with water. After the organic layer was dried over anhydrous magnesium sulfate, 0.2 g of hydroquinone was added and dissolved. After the solvent was concentrated, the residue was distilled under reduced pressure (94-110 ° C, 4 mmHg) to obtain 3.24 g of a colorless liquid compound (yield: 5%). The compound obtained as described above was analyzed by 1 H-NMR to obtain the compound of the above formula [6]
A] and the keto-enol isomer mixture represented by [6B] in a molar ratio of 1: 1.1).

The chemical shifts of 1H-NMR are shown below. (Keto-type isomer) 1H-NMR (CDCl ₃ ) δ: 1.50 (9H, s), 2.20 (6H,
s), 2.80 (2H, d), 4.00 (1 H, t), 5.57 (1 H, s), 6.12 (1 H, s) (enol type isomer) 1H-NMR (CDCl ₃ ) δ: 1.54 (9 H, s) ), 2.08 (6H,
s), 3.22 (2H, s), 5.36 (1H, s), 6.15 (1H, s)

[0048]

Example 8 A compound represented by the following formula [7] was synthesized using t-butyl α-methylsulfonyloxymethyl acrylate.

[0049]

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The specific synthesis method is as follows. t-
1.90 g of butyl α-hydroxymethyl acrylate
(12.0 mmol), 2.73 g of triethylamine (2
(7.0 mmol) in 10 g of toluene was added dropwise at 0 ° C. with 1.51 g (13.2 mmol) of methanesulfonic acid chloride in 10 g of toluene, reacted at 0 ° C. for 1 hour, and further reacted at room temperature for 16 hours. A compound in which X in the formula [2] is a methylsulfonyloxy group and R1 is a t-butyl group was synthesized. Next, 1.13 g (10.1 mmol) of 1,3-cyclohexanedione and 0.45 g (4.0 mmol) of diazabicyclo [2.2.2] octane were added, and the mixture was stirred at 75 ° C. for 3 hours. After cooling, the mixture was extracted with ethyl acetate and washed with 0.1N hydrochloric acid and water. The organic layer was dried over anhydrous magnesium sulfate and concentrated. The obtained residue was subjected to silica gel column chromatography to obtain 0.83 g of a pale yellow crystalline compound (33% yield). The compound obtained as described above was confirmed to be the compound [7] by 1H-NMR.

Chemical shift of 1H-NMR and IR
Are shown below. 1H-NMR (CDCl ₃ ) δ: 1.46-1.52 (9H, m), 1.8
7-1.97 (2H, m), 2.33-2.43 (4H, m), 3.20 (2H, s), 6.02 (1H,
s), 6.13 (1H, s), 10.12 (1H, br) IR (KBr) cm ^-1 : 3390,2950,2630,1700,1630,157
0,1360,1270,1220,1190,1140,1070,1010

[0052]

Example 9 The compound of the present invention (compound [4]) obtained in Example 5 was copolymerized with methyl methacrylate. The specific synthesis method is as follows. Compound [4] 4.4
9 g (20.0 mmol), methyl methacrylate 5.00 g
(49.9 mmol) and azobisisobutyronitonyl 3
28 mg (2.00 mmol) of toluene 10 g and N,
After nitrogen gas was introduced into a 5 g solution of N-dimethylformamide for 15 minutes, the mixture was stirred at 65 ° C. for 3 hours. After cooling, the reaction mixture was added dropwise to 250 ml of diethyl ether with stirring, and the resulting precipitate was recovered and dried under reduced pressure. The yield was 2.02 g. As a result of 1H-NMR analysis, the precipitate thus obtained was a copolymer of compound [4] and methyl methacrylate [monomer composition ratio (compound [4]: methyl methacrylate) = 1: 5] Was confirmed. The glass transition temperature (Tg) of the copolymer obtained as described above determined by differential scanning calorimetry (DSC analysis) was 74 ° C. The number average molecular weight determined by gel osmotic pressure chromatography (GPC analysis) was 6,100.

[0053]

Example 10 The compounds of the present invention (compound [5A] and compound [5B]) obtained in Example 6 were copolymerized with styrene. The specific synthesis method is as follows. 2.13 g (10.0 mmol) of a keto-enol isomer mixture of compound [5A] and compound [5B], 1.04 g of styrene
(10.0 mmol) and azobisisobutyronitonyl 8
2 mg (0.50 mmol) at 60 ° C. for 3 hours, further 80
Stirred at C for 3 hours. After cooling, the reaction mixture was dissolved in dichloromethane (10 ml) and added dropwise to n-hexane (150 ml) with stirring. The resulting precipitate was collected and dried under reduced pressure. The yield was 1.84 g. As a result of 1H-NMR analysis, the precipitate obtained as described above was subjected to copolymerization of styrene with a keto-enol isomer mixture of compound [5A] and compound [5B] [monomer composition ratio (compound [5A] And a mixture of keto-enol isomers of compound [5B]: styrene) = 1: 12.4]. The glass transition temperature (Tg) of the copolymer obtained by the DSC analysis was 56 ° C. The number average molecular weight determined by gel osmotic pressure chromatography (GPC analysis) was 4,400.

[0054]

Example 11 The compound [7] of the present invention obtained in Example 8 was copolymerized with styrene. The specific synthesis method is as follows. 505 mg (2.0 mmol) of compound [7],
After dissolving 3.47 g (33.3 mmol) of styrene and 27 mg (0.17 mmol) of azobisisobutyronitonyl in 12 g of ethyl acetate and bubbling nitrogen for 15 minutes,
The mixture was stirred at 70 ° C. for 7 hours. After cooling, the reaction mixture was added dropwise to 450 ml of methanol with stirring, and the resulting precipitate was collected and dried under reduced pressure. The yield was 0.63 g.
As described above, a copolymer of compound [7] and styrene was obtained. The copolymer obtained as described above had a glass transition temperature (Tg) of 148 ° C. by DSC analysis (in addition,
The homopolymer of styrene has a temperature of 91 ° C, and the homopolymer of compound [7] has a temperature of 88 ° C. ). The number average molecular weight by gel osmotic pressure chromatography (GPC analysis) is 1
8,600.

[0055]

The novel methacrylate derivative of the present invention has polymerizability and is useful for various uses as a raw material for synthesizing various chemical materials or as a synthetic intermediate for pharmaceuticals or agricultural chemicals. The polymer of the present invention is useful as various chemical materials such as a metal chelate forming material and a heat resistant material.

[Brief description of the drawings]

FIG. 1 is a 1 H-NMR chart of a compound obtained in Example 5.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA01 AA02 AB46 AB82 AB84 AC24 AC44 BA02 BA28 BA32 BA51 BA69 BA92 BB11 BB12 BB20 BB21 BB24 BB31 BC10 BR10 BT12 4J100 AL31P AL31Q BA03P BA11P BA12Q BC23P CA04

Claims (3)

[Claims] 1. A methacrylate derivative represented by the following formula [1A] or [1B]. Embedded image Embedded image However, R ¹ in the above formulas [1A] and [1B] represents a hydrogen atom or an alkyl group, R ² and R ³ each represent an alkyl group, and R ² and R ³ may form a ring. . 2. A polymer obtained by polymerizing a methacrylate derivative represented by the above formula [1A] or [1B] or a copolymerizable monomer thereof with another copolymerizable monomer. 3. The method for producing a methacrylic ester derivative according to claim 1, wherein the methacrylic acid derivative represented by the following formula [2] is reacted with 1,3-diketone in the presence of a basic compound. . Embedded image (X in the above formula is a leaving group, and R ¹ is a hydrogen atom or an alkyl group.)