JPH09202758A - N-allyl-substituted trimellitic acid monoamide compound - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: To provide a raw material for a plasticizer, a heat resistant resin, a lubricant, an antistatic agent, a paint, an adhesive, a dispersant, a polymerizable surfactant, an admixture for cement, etc. An object of the present invention is to provide a novel N-allyl-substituted trimellitic acid monoamide compound useful as An N-allyl-substituted trimellitic acid monoamide compound represented by formula (1), a mixture thereof, or a salt thereof. Embedded image (In the formula, R represents a hydrogen atom or an allyl group.)

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel allyl compound having a trimellitic acid monoamide structure. The novel allyl compound having a trimellitic acid monoamide structure of the present invention is a hydrophobic compound soluble in an organic solvent, but since it has a carboxyl group and an amide group in the molecule, pH,
It is an amphipathic compound capable of exhibiting water solubility or water dispersibility depending on temperature conditions and the like. Furthermore, since this compound has a double bond in the molecule, it can be polymerized with various vinyl compounds in a solvent-free system, an aqueous system or an organic solvent system, and is a compound useful as a synthetic resin raw material. Specific applications of the N-allyl-substituted trimellitic acid monoamide compound and its copolymer of the present invention include plasticizers, heat resistant resins, lubricants, antistatic agents, paints, adhesives, dispersants, and polymerizable interfaces. Examples thereof include use as an activator and an admixture for cement.

[0002]

The compound according to the present invention is a novel compound which has never been reported before.

[0003]

The object of the present invention is to provide a plasticizer, heat resistant resin, lubricant, antistatic agent, paint, adhesive,
It is to provide a novel N-allyl-substituted trimellitic acid monoamide compound useful as a raw material for a dispersant, a polymerizable surfactant, an admixture for cement, and the like.

[0004]

The present invention is an N-allyl-substituted trimellitic acid monoamide compound represented by the formula (1) (formula 2), a mixture thereof, or a salt thereof.

Embedded image (In the formula, R represents a hydrogen atom or an allyl group.)

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION N- represented by the formula (1) of the present invention
The allyl-substituted trimellitic acid monoamide compound can be synthesized by a method of reacting trimellitic anhydride with allylamine and diallylamine (hereinafter referred to as allylamines). The reaction of trimellitic anhydride with allylamines is usually performed by adding allylamines to an organic solvent solution of trimellitic anhydride. As an example of an organic solvent that can be used as a reaction solvent,
Any substance capable of dissolving trimellitic anhydride and allylamines may be used, such as acetone, 2-butanone, benzene,
Examples include toluene, xylene, pentane, hexane, cyclohexane, N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, diethyl ether, dioxane, dichloromethane, dichloroethane, chloroform and the like. Methanol, ethanol, isopropanol, methicellosolve, ethyl cellosolve, 2-
Alcohol-based solvents such as ethylhexanol and cyclohexanol may cause an esterification reaction with some trimellitic anhydride, but the reactivity of trimellitic anhydride and allylamines is high, and esterification is generally performed. Since the production amount of is small, alcoholic solvents can be used for applications in which esterification does not have a large effect.

The amount of the solvent used is preferably such that the concentration of trimellitic anhydride is 1 to 90 wt%. When the amount is less than 1 wt%, the productivity is poor, and when the amount is more than 90 wt%, the effect of adding the solvent is lost. By reacting allylamine or diallylamine alone as the allylamine with trimellitic anhydride, a compound represented by the formula (1) in which R is a hydrogen atom and a compound in which R is an allyl group can be obtained. . However, allylamine and diallylamine may be obtained as a mixture depending on the production method of allylamines. The reaction with trimellitic anhydride is also possible using this allylamine mixture, and is obtained as a mixture of a compound represented by the general formula (1) in which R is a hydrogen atom and a compound in which R is an allyl group. be able to.

The amount of allylamines used is 0.8 to 1.5 equivalents, preferably 0.9, relative to trimellitic anhydride.
Use ~ 1.2 equivalents. If the amount used is less than 0.8 equivalent, the yield of the target product may be reduced, which is not preferable. Using more than 1.5 equivalents is not preferable because there is no effective difference. Since allylamines are relatively highly volatile compounds, it is preferable to use a closed reactor. When carrying out the reaction in an open system, it is necessary to trap the volatilized allylamines with a cooling pipe, but in such a case, by adding an excessive amount of allylamines trapped in advance, Allow the reaction to complete.

The reaction of trimellitic anhydride with allylamines is carried out under normal pressure or pressure at a temperature range of 0 to 150 ° C, preferably 5 to 130 ° C, more preferably 10 to 100 ° C. If the temperature is lower than 0 ° C, the reaction proceeds slowly,
There is no effective difference if the reactions are carried out at temperatures above 0 ° C.
It is not necessary to keep the reaction temperature constant during the reaction, and the reaction temperature may be appropriately changed for the purpose of controlling the reaction rate or adjusting the viscosity of the reaction solution. The reaction time cannot be generally stated because it depends on the reaction temperature, but the reaction time is 30 minutes to 10 hours, and the reaction product is N- represented by the formula (1).
An allyl-substituted trimellitic acid monoamide compound can be obtained.

The N- represented by the formula (1) thus manufactured
The allyl-substituted trimellitic acid monoamide compound can be used as it is in the reaction solution for a desired reaction after the operation such as removing excess allylamines, but if necessary, filtration, desolvation, etc. It can be separated as a solid by a conventional method. If you need a highly pure target depending on the application, use methanol, ethanol, isopropanol,
It can be recrystallized using a solvent such as acetone, toluene, benzene, xylene and styrene. Since trimellitic anhydride is an asymmetric compound, there are two positional isomers in the reaction product with allylamines, and under normal reaction conditions, a mixture of two types is obtained. The abundance ratio of these is considered to be determined by the reaction conditions such as the reaction solvent, the reaction temperature, the reaction concentration, etc. However, the two may be used without being separated for the usual purpose of use.

The N-allyl-substituted trimellitic acid monoamide compound represented by the formula (1) thus obtained is further treated with various bases for free carboxylic acid for various purposes such as imparting water solubility. It can be converted into various salts by solvation. Examples of the salt include alkali metal salts such as sodium, potassium and cesium, alkaline earth metal salts such as calcium and magnesium, ammonium salts,
Mention may be made of salts with organic bases such as triethylammonium salts or pyridinium salts. Both the raw material and the product in the method of the present invention have a polymerizable double bond, and it is effective to use a polymerization inhibitor as necessary in order to prevent each polymerization in the production process. Is. Examples of the polymerization inhibitor include, but are not limited to, hydroquinone, methoxyphenol, t-butylcatechol, phenothiazine, thiourea, hydroxyquinoline, cuperone, N-nitrosodiphenylamine and the like.

The N-allyl-substituted trimellitic acid monoamide compound represented by the formula (1) of the present invention thus produced can be polymerized with various vinyl compounds. Equation (1)
Examples of vinyl compounds copolymerizable with the N-allyl-substituted trimellitic acid monoamide compound represented by are aromatic vinyl compounds, vinyl cyanide compounds, diene compounds,
One or more compounds selected from the group consisting of vinylcarboxylic acid compounds, unsaturated carboxylic acid amide compounds, alkyl vinyl ether compounds, and other vinyl compounds.

The method for copolymerizing the N-allyl-substituted trimellitic acid monoamide compound represented by the formula (1) of the present invention and the vinyl compound is not particularly limited, and the known method can be used. Usually, the polymerization can be carried out by maintaining a predetermined temperature in the presence of a radical polymerization initiator. As the polymerization solvent, the above vinyl compound and the formula (1) are used.
The N-allyl-substituted trimellitic acid monoamide compound represented by the formula (1) may be uniformly dissolved, and is a vinyl compound compatible with the N-allyl-substituted trimellitic acid monoamide compound represented by the formula (1), For applications requiring desolvation, solvent-free copolymerization may be preferred for the purpose of simplifying the process. The N-allyl-substituted trimellitic acid monoamide compound represented by the formula (1) has a carboxyl group in the molecule, and when it is neutralized with an alkali, it becomes soluble in water. It is also possible to carry out emulsion polymerization in the presence of a surfactant even under pH conditions insoluble in water.

A general polymerization initiator can be used as the polymerization initiator. If necessary, a chain transfer agent or a polymerization rate adjusting agent can be used. Monomers used for polymerization,
The polymerization initiator, solvent, chain transfer agent, etc. may be charged into the reaction vessel at one time at the time of starting the polymerization, but one or more components may be mixed alone or in a solvent depending on the progress of the polymerization. You may add the thing one by one. The N-allyl-substituted trimellitic acid monoamide compound represented by the formula (1) of the present invention and the copolymer obtained by polymerizing the same with other vinyl compounds are plasticizers, heat-resistant resins, antistatic agents, and lubricants. It can be used in a wide range of fields such as agents, paints, adhesives, dispersants, surfactants and cement admixtures.

[0014]

The present invention will be described in detail below with reference to Examples.
The present invention is not limited to these examples. Example 1: N-monoallyl trimellitic acid monoamide 100.0 g (0.52 mol) of trimellitic acid anhydride and acetone in a 500 ml four-neck separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel. 200
ml was added and dissolved at room temperature. At room temperature, 29.7 g (0.52 mol) of allylamine was added dropwise over 30 minutes.
After stirring for 5 hours at room temperature, the precipitated crystals were filtered and dried. Crystal yield 116.9 g (yield 90.1%) Elemental analysis value; C: 57.83% H: 4.45% N: 5.62% (calculated value: C ₁₂ H ₁₁ NO ₅ ) C: 57.64% H: 4.19% N: 5.35% (measured value) Melting point; 175 ° C. ¹ H-NMR (CDCl ₃ ) δ (ppm): 3.8-4.0 (m, 2H), 5.1-5.4 (m, 2H),
5.8-6.2 (m, 1H), 7.6-8.7 (m, 4H) IR analysis of the obtained crystal, characteristic absorption band due to the acid anhydride group of the raw material trimellitic acid anhydride of 1780 cm ^-1 (C = O stretching) disappeared, and only an absorption band derived from a carboxylic acid (C = O stretching) at 1700 cm ^-1 was observed.

Example 2: N, N-diallyl trimellitic acid monoamide 100.0 g (0.52) of trimellitic anhydride was placed in a 500 ml four-neck separable flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel. Mol), acetone 150
ml was added and dissolved at room temperature. At room temperature, 50.6 g (0.52 mol) of diallylamine was added dropwise over 30 minutes. After stirring overnight at room temperature, the precipitated crystals were filtered and dried under vacuum. Yield 73.9 g (yield 49.1%) Elemental analysis value; C: 62.27% H: 5.23% N: 4.84% (calculated value: C ₁₅ H ₁₅ NO ₅ ) C: 62.46% H: 5.00% N: 4.52 % (Measured value) Melting point; 155 ° C. ¹ H-NMR (CDCl ₃ ) δ (ppm): 3.1-4.4 (m, 4H), 4.6-6.1 (m, 6H),
7.5-8.5 (m, 3H), 11.1 (s, 2H) was subjected to IR analysis of the obtained crystals, 1700 cm ^-1 carboxylic acid (C = O stretching), amide 1640cm ^-1 (C = O stretching ) Was observed.

[0016]

INDUSTRIAL APPLICABILITY The N-allyl-substituted trimellitic acid monoamide compound of the present invention is an amphipathic compound which is soluble in an organic solvent but is highly soluble in water depending on pH and temperature conditions. Since this compound has a polymerizable double bond in the molecule, it can be polymerized with other vinyl compounds to produce a copolymer. This copolymer and the N-allyl-substituted trimellitic acid monoamide compound of the present invention are plasticizers, heat resistant resins, antistatic agents, lubricants, paints, adhesives,
It can be used for various purposes such as a dispersant, a surfactant, and a cement admixture.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshihiko Takagi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Masaru Tanabe 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Inside Chemical Co., Ltd.

Claims (1)

[Claims] 1. An N-allyl-substituted trimellitic acid monoamide compound represented by formula (1) (formula 1), a mixture thereof, or a salt thereof. Embedded image (In the formula, R represents a hydrogen atom or an allyl group.)