JPH0753540A - Compound containing acid anhydride group and acrylic ester group and its production - Google Patents

Abstract

PURPOSE:To obtain a compound containing an acid anhydride group and an acrylic ester group useful as a polymer raw material, a raw material for coating compound improver, a polymer cross-linking agent, etc. CONSTITUTION:This compound containing an acid anhydride group and an acrylic ester group is a compound of formula I ((n) is 1-10; R and R' are H, CH3) such as 6-methyl-4-cyclohexene-1,2,3-tricarboxylic acid-3-[2-(acryloyloxy)- ethyl]ester-1,2-anhydride. The compound is obtained by reacting a sorbic acid and acrylic acid diester of an alkylene glycol with maleic anhydride. The compound can be readily homopolymerized or copolymerized with another unsaturated group-containing compound by heat, ultraviolet light or ionized radiation or in the presence of a radical polymerization initiator. The prepared polymer contains an acid anhydride group and the acid anhydride group and is treated with an amine, an alcohol, water, etc., to add other functions.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a compound having an acid anhydride group and an acrylic acid ester group or a methacrylic acid ester group at the same time, and a process for producing the same. The compound of the present invention is used as a polymer raw material, a paint modifier raw material, a polymer crosslinking agent, and the like.

[0002]

Maleic anhydride is copolymerized with styrene, ethylene, propylene, acrylic acid, various acrylic acid esters, methacrylic acid and various methacrylic acid esters. Since the copolymer has an acid anhydride group,
Reacts with amines, alcohols, and water and exhibits new functions.

[0003]

However, the copolymer thus obtained has a carbonate group directly attached to the polymer chain, so that it becomes carbonic acid, is separated from the polymer chain, is easily decomposed, and is colored. It has drawbacks.

[0004]

Means for Solving the Problems As a result of intensive studies to solve these drawbacks, the inventors of the present invention have shown that the compound is a copolymerizable compound and has a double bond and is polymerized with an acid anhydride. After finding a compound having a specific structure in which a part is separated, and further reacting the compound having a double bond such as 2-hydroxyethyl acrylate with a compound having a diene such as sorbic acid chloride to diesterify the compound. , Maleic Anhydride and Diels-Alder
It was found that it can be obtained by carrying out the reaction.

That is, the gist of the present invention is to provide a compound having an acid anhydride group and an acrylate group represented by the following general formula (I) at the same time, and an alkylene glycol sorbin represented by the following general formula (II). A method for producing a compound represented by the following general formula (I) is characterized by reacting an acid and a diester of acrylic acid with maleic anhydride.

[0006]

[Chemical 3]

The present invention will be described in detail below. In the compound having the acid anhydride group represented by the above formula (I) and the acrylic acid ester group of the present invention (hereinafter referred to as compound (I)), the acrylic acid ester group is a polymerizable acrylic acid. Alternatively, a group derived from an ester of methacrylic acid can be used.

Examples of the acid anhydride group include those having a structure derived from cyclohexene tricarboxylic acid anhydride. Examples of the linking group connecting the acrylic acid group and the acid anhydride group include groups derived from alkylene glycols such as ethylene glycol and butylene glycol.
The n of the alkylene chain in the formula (I) is 1 to 10, preferably n = 2 or 4.

The compound (I) of the present invention comprises sorbic acid of alkylene glycol represented by the above formula (II) and diester of acrylic acid (hereinafter referred to as compound (II)), and maleic anhydride. It is produced by reacting. Specifically, after reacting a hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl acrylate with a diene compound such as sorbic acid chloride to esterify the compound (II), the compound (II) with Maleic anhydride is used. Compound (I) is obtained by the Alder reaction.

The method for synthesizing the compound (II) will be described in more detail. An acrylate or methacrylate of hydroxyalkylene glycol containing a polymerization inhibitor is dissolved or dispersed in a solvent ether, tetrahydrofuran, toluene, benzene, hexane or the like. , And can be obtained by reacting with sorbic acid chloride in the presence or absence of a base. In addition, as a base,
Pyridine, triethylamine, N, N-dimethylaniline, potassium carbonate, sodium carbonate and the like can be mentioned, with preference given to N, N-dimethylaniline and pyridine. The reaction temperature may be either heated or non-heated, and preferably a temperature of 120 ° C. or less at which polymerization is difficult.

Diels-A with maleic anhydride
The lder reaction can be obtained by heating the compound (II) with maleic anhydride in the presence or absence of a solvent. Examples of the solvent include toluene, benzene, and tetrahydrofuran, and toluene is preferable. The temperature is 40 to 150 degrees, preferably 80 to 120 degrees.

The compound (I) of the present invention can be easily homopolymerized or copolymerized with another unsaturated group-containing compound in the presence of heat, ultraviolet rays, ionizing radiation or a radical polymerization initiator. The polymer thus obtained has an acid anhydride group, and it is possible to add another function by reacting it with an amine, alcohol, water or the like.

[0013]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples without departing from the gist thereof. Example 1 40 g of sorbic acid chloride obtained from sorbic acid was mixed with 37.36 g of 2-hydroxyethyl acrylate, N,
N-dimethylaniline 38.96 g, ether 200 m
1 of the mixed solution was dropped under ether reflux and reacted for 8 hours. The formed precipitate was filtered, and after removing the ether by distillation, a polymerization inhibitor was added to obtain 36 g of 1-acryloyloxy-2-sorboyloxyethane at 103 ° C./0.15 mmHg.

A mixed solution of 8 g of the obtained diester, 3.48 g of maleic anhydride and 16 ml of toluene was reacted at 80 ° C. for 2 hours and then at 100 ° C. for 8 hours. After cooling, 16 ml of hexane was added, the precipitate was filtered, and then ethyl acetate, 10
recrystallized with a mixed solution of 20 ml of hexane and 20 ml of hexane to give the desired 6-methyl-4-cyclohexene-1,2,3-tricarboxylic acid-3- [2- (acryloyloxy) ethyl] ester-1,2. -I got Unhydride. The melting point was 89.0 ° C to 90.8 ° C.

The obtained compound has the following physical properties. Infrared absorption spectrum (NaBr tablet) 1615,1640 (CH ₂ = CH- stretching vibration of acrylic ester) 1715,1725 (C = O stretching vibration of ester) 1775,1840 (C = O stretching vibration of acid anhydride) Nuclear magnetic resonance spectrum ( ¹ H-NMR, 250 MHz, CDCl ₃ ).

[0016]

[Chemical 4]

[0017]

[Table 1] a: 3H 1.42d J = 7.4 b: 1H 2.45m c: 1H 3.18m d: 1H 3.40d, de: 1H 4.01d, d f: 4H 4.40mg : 1H × 5 5.8-6.5m

Example 2 40 g of sorbic acid chloride was mixed with 46.36 g of 4-hydroxybutyl acrylate and 3 g of N, N-dimethylaniline.
8.96 g, polymerization inhibitor 0.2 g, ether 200 ml
The mixture was added dropwise under ether reflux and reacted for 8 hours. The precipitate formed is filtered and 15 (w / w)%
It was washed with H ₂ SO ₄ , 10% Na ₂ CO ₃ , washed until the pH became neutral, and the ether layer was dried over MgSO ₄ . 72 g of diester 1-acryloyloxy-4-sorboyloxybutane was obtained.

10 g of this diester, 4.1 g of maleic anhydride, 20 ml of toluene and 0.1 g of a polymerization inhibitor (tertiary butyl catechol) were reacted at 80 ° C. for 2 hours and then at 100 ° C. for 8 hours. The reaction product is ethyl acetate 1
It was extracted with 00 ml and hexane 200 ml and concentrated. Further, it was recrystallized from a mixed solution of 20 ml of ethanol and 50 ml of hexane to give the desired 6-methyl-4-cyclohexene-1,2,3-tricarboxylic acid-3- [4
-(Acryloyloxy) butyl] ester-1,2-
6.2 g of unhydride was obtained. Melting point is 62-64 ° C
Met.

The obtained compound has the following physical properties. Infrared absorption spectrum (NaBr tablet) 1620 (CH ₂ = CH- stretching vibration of acrylic acid ester) 1714 (C = O stretching vibration of ester) 1762,1836 (C = O stretching vibration of acid anhydride) Nuclear magnetic resonance spectrum ( ¹ H-NMR, 250 MHz, CDCl ₃ )

[0021]

[Chemical 5]

[0022]

[Table 2] a: 3H 1.42d J = 7.4 b: 4H 1.82m c: 1H 2.47m d: 1H 3.18m e: 1H 3.40d, d f: 1H 4.01d, d g : 4H 4.18 to 4.37m h: 1H x 5 5.8 to 6.5m

Example 3 In place of 2-hydroxyethyl acrylate of Example 1, 41.9 g of 2-hydroxyethyl methacrylate was used, and 0.2 g of a polymerization inhibitor (tertiary butyl catechol) was added. The reaction was carried out for 12 hours in the same manner as in. The formed precipitate was filtered, washed with 15% sulfuric acid, saturated sodium carbonate water and brine, and then the ether was distilled off. Add a polymerization inhibitor and distill it to 1 at 93 ° C / 0.15mmHg.
34 g of methacryloyloxy-2-sorboyloxyethane were obtained.

A mixed solution of 5 g of the obtained diester, 2.3 g of maleic anhydride, 10 ml of toluene and 50 mg of a polymerization inhibitor (tertiary butyl catechol) was reacted at 80 ° C. for 2 hours, 100 ° C. for 8 hours. Hexane 10 after cooling
ml, toluene 5 ml was added, the precipitate was decanted and removed, and recrystallized with a mixed solution of ethanol 5 ml and hexane 15 ml to obtain the desired 6-methyl-4-cyclohexene-1,2,3-tricarboxylic acid 1 , 2
4.22 g of -anhydride-3- [2- (methacryloyloxy) ethyl] ester were obtained. Melting point 79.8
The temperature was 8 ° C to 81.8 ° C.

The obtained compound has the following physical properties. Infrared absorption spectrum (NaBr tablet) 1632 (CH ₂ = CH- stretching vibration of acrylic ester) 1709,1734 (C = O stretching vibration of ester) 1772,1839 (C = O stretching vibration of acid anhydride) Nuclear magnetic Resonance spectrum ( ¹ H-NMR, 250 MHz, CDCl ₃ )

[0026]

[Chemical 6]

[0027]

[Table 3] a: 3H 1.43d J = 7.4 b: 3H 1.94s c: 1H 2.47m d: 1H 3.32m e: 1H 3.41d, d f: 1H 4.01d, d g : 2Hx2 4.47m h: 1Hx2 5.60, 6.13s i: 1H 5.86m j: 1H 6.44m

[0028]

The compound (I) of the present invention contains heat, ultraviolet rays,
It can be easily homopolymerized or copolymerized with another unsaturated group-containing compound in the presence of ionizing radiation or a radical polymerization initiator, and is used as a polymer raw material, a coating modifier raw material, a polymer cross-linking agent and the like.

Claims (2)

[Claims] 1. A compound having both an acid anhydride group represented by the following general formula (I) and an acrylate group. [Chemical 1] 2. The acid anhydride group according to claim 1, wherein a diester of alkylene glycol represented by the following general formula (II) with sorbic acid and acrylic acid is reacted with maleic anhydride. The manufacturing method of the compound which has an acrylate group simultaneously. [Chemical 2]