JP2003128661A - Acrylate ester derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new acrylate ester derivative which is useful as a raw material for acrylic resins, thermoplastic elastomers and resin modifiers. SOLUTION: The acrylate ester derivative represented by formula (1) is provided (wherein R is H or an alkyl group).

Description

Description: TECHNICAL FIELD [0001] The present invention relates to an acrylic resin,
The present invention relates to a novel acrylate derivative that is useful as a raw material for thermoplastic elastomers, resin modifiers, and the like. It is known that acrylic ester derivatives have different physical properties due to differences in the structure of the alcohol component constituting the ester portion, and include acrylic resins, thermoplastic elastomers, resin modifiers and the like. Are used for various purposes. Therefore, by providing a novel acrylate derivative different from those conventionally known, it becomes possible to provide useful acrylic resins, thermoplastic elastomers, resin modifiers, etc. having physical properties different from those of the past. , Its significance is great. [0003] However, the present invention provides
An object of the present invention is to provide a novel acrylate derivative which is useful as a raw material for an acrylic resin, a thermoplastic elastomer, a resin modifier and the like. [0004] According to the present invention, the above-mentioned object is achieved by the following general formula (1): In the formula, R represents a hydrogen atom or an alkyl group.
Abbreviated as acrylic ester derivative (1). ). DETAILED DESCRIPTION OF THE INVENTION In the above general formula, the alkyl group represented by R is, for example, a methyl group, an ethyl group, a propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, pentyl group, hexyl group and the like. Among them, the alkyl group represented by R is preferably a methyl group or an ethyl group. Acrylic ester derivative (1) of the present invention
Is, for example, an acrylic halide derivative, preferably an acrylic chloride derivative, and 4-hydroxymethyl-
It can be produced by reacting 3,3-dimethyl-γ-butyrolactone. In addition, 4-hydroxymethyl-3,3-dimethyl-γ-butyrolactone is a known substance. For example, 2,2-dimethyl-4-pentenoic acid is reacted with hydrogen peroxide in the presence of a methyltrioxorhenium catalyst. [Journal of Molecular Catalysis (J. Mo.)
l. Catal. ), 142, 333 (1999).
Year)]. In the reaction between the acrylic acid halide derivative and 4-hydroxymethyl-3,3-dimethyl-γ-butyrolactone, the ratio of the acrylic acid halide derivative to 4-hydroxymethyl-3,3-dimethyl-γ-butyrolactone is Although not particularly limited, the acrylic acid halide derivative is usually used in an amount of 0.1 to 1 mol per 1 mol of 4-hydroxymethyl-3,3-dimethyl-γ-butyrolactone.
It is preferably in the range of 10 moles, more preferably in the range of 0.3 to 3 moles. The reaction of the acrylic halide derivative with 4-hydroxymethyl-3,3-dimethyl-γ-butyrolactone can be carried out in the presence or absence of a base. When the reaction is carried out in the presence of a base, as the base, those usually used in the production of an ester by reacting an acrylic acid halide derivative with an alcohol can be used, such as sodium hydroxide and potassium hydroxide. Metal hydroxide; triethylamine, pyridine, 4-
Aliphatic or aromatic amine compounds such as dimethylaminopyridine and dimethylaniline; and tetramethylurea. One of these bases may be used alone, or two or more may be used in combination. When a base is present, the amount used is not particularly limited,
Usually, it is preferably in the range of 0.01 to 100 mol, more preferably in the range of 0.1 to 10 mol, per 1 mol of 4-hydroxymethyl-3,3-dimethyl-γ-butyrolactone. The reaction between the acrylic halide derivative and 4-hydroxymethyl-3,3-dimethyl-γ-butyrolactone can be carried out in the presence or absence of a solvent. When the reaction is carried out in the presence of a solvent, usable solvents are not particularly limited as long as they are inert to the reaction, for example, saturated hydrocarbons such as pentane, hexane and octane; aromatic hydrocarbons such as toluene and xylene; Methylene chloride,
Halogenated hydrocarbons such as 1,2-dichloroethane are exemplified. One of these solvents may be used alone, or two or more thereof may be used in combination. When a solvent is present, the amount of the solvent used is not particularly limited, but it is usually 4-hydroxymethyl-3,3-.
0.1 part by mass of dimethyl-γ-butyrolactone is 0.1% by mass.
It is preferably in the range of 0.1 to 100 parts by mass,
More preferably, it is in the range of 30 parts by mass. The reaction between the acrylic acid halide derivative and 4-hydroxymethyl-3,3-dimethyl-γ-butyrolactone is usually in the range of -50 to 200 ° C., preferably in the range of 0 to 100 ° C. Is more preferred. [0014] The reaction time is 4 hours.
The amount varies depending on the amount ratio of -hydroxymethyl-3,3-dimethyl-γ-butyrolactone, the presence or absence of a base or a solvent, the type and amount used, the reaction temperature, etc.
Minutes to 10 hours. The acrylate derivative (1) thus obtained can be isolated and purified by a method usually used in the isolation and purification of organic compounds, and its purity can be further increased. For example, the reaction mixture is optionally washed to remove the base, or concentrated if necessary to remove the solvent, and then purified by distillation or column chromatography. Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Example 1 10.4 g (0.1 mol) of 4-hydroxymethyl-3,3-dimethyl-γ-butyrolactone, 10.1 g (0.1 mol) of triethylamine and 0.2 g (1. 6 mmol) in methylene chloride 1
After 10.5 g (0.1 mol) of methacryloyl chloride was added to the solution dissolved in 00 ml under ice cooling over 1 hour, the reaction mixture was stirred for 1 hour under ice cooling. The reaction mixture is mixed with 50 ml of water and 20 aqueous saturated sodium hydrogen carbonate solution.
After sequentially washing with ml, the mixture was concentrated. The obtained residue was purified by silica gel column chromatography (developing solvent: hexane / methylene chloride = 1/1 (volume ratio)) to give 4-methacryloyloxy-3,3-dimethyl-γ-butyrolactone having the following physical properties. 17.1 g (81% yield) was obtained. ¹ H-NMR (300 MHz, CDC
l ₃ , TMS) δ: 6.13 (s, 1H), 5.63
(S, 1H), 4.41 (dd, 1H, J = 11.5,
3.2 Hz), 4.35 (dd, J = 5.9, 3.2H)
z), 4.25 (dd, 1H, J = 11.5, 5.9H
z), 2,43 (s, 2H), 1.95 (s, 3H),
1.27 (s, 3H), 1.15 (s, 3H) Example 2 In Example 1, 10.5 g of methacryloyl chloride (0.
Acryloyl chloride 9.05 g (0.
The reaction and isolation and purification procedures were performed in the same manner as in Example 1 except for using 1 mol) of 4-acryloyloxy-3,3-dimethyl-γ-butyrolactone 1 having the following physical properties.
4.8 g (75% yield) were obtained. ¹ H-NMR (300 MHz, CDC
l ₃ , TMS) δ: 6.44 (dd, 1H, J = 17.
3,1.4 Hz), 6.15 (dd, 1H, J = 17.
3, 10.4 Hz), 5.90 (dd, 1H, J = 1
0.4, 1.4 Hz), 4.42 (dd, 1H, J = 1)
1.7, 3.0 Hz), 4.34 (dd, J = 6.6,
3.0 Hz), 4.25 (dd, 1H, J = 11.7,
6.6 Hz), 2,43 (s, 2H), 1.27 (s,
3H), 1.14 (s, 3H) According to the present invention, a novel acrylate ester which is useful as a raw material for acrylic resins, thermoplastic elastomers, resin modifiers, etc. Derivatives can be provided.

Claims (1)

Claims: 1. The following general formula (1): (Wherein, R represents a hydrogen atom or an alkyl group).