JPH05125166A - Novel polyester compound - Google Patents

Abstract

(57) [Summary] [Structure] The present invention relates to a fatty acid 3 containing a hydroxyl group.
To 15 mol and 1 mol of an aliphatic dicarboxylic acid, a polyester compound having an amino group at the end of a molecule formed by reacting 2 equivalents or more of a polyamine with 1 equivalent of a condensate having an ester group at the end of the molecule I will provide a. [Effect] A novel high molecular weight polyester compound having an amino group at the terminal can be produced by a simple process. The polyester compound is liquid or has a sufficiently low softening point and is substantially liquid at the use temperature.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a novel ester group-containing condensate having a hydroxyl group-containing fatty acid as a substrate, which is modified with an aromatic amine and / or an aliphatic amine and / or an alicyclic amine. It relates to active hydrogen compounds for polyurethane / urea and / or polyurea resins.

[0002]

Polyurethane resins generally comprise a polyisocyanate compound having two or more isocyanate groups,
It is well known that it can be obtained by reaction with a compound having two or more active hydrogen-containing groups. The active hydrogen-containing compounds are roughly classified into so-called polyether polyols such as polyester polyols, poly (oxypropylene ether) polyols, poly (oxyethylene-propylene ether) polyols, acrylic polyols, castor oil derivatives, tall oil derivatives, and others. There are hydroxyl compounds. Generally, polyester polyols have high physical properties, but as the molecular weight increases, the viscosity also increases and the crystallinity increases, and the reaction injection molding method (hereinafter referred to as RIM method), which is one of the molding methods for polyurethane resins, has a low viscosity. Therefore, polyether polyols have been used. Recently, aromatic diamines have been used as chain extenders instead of low molecular weight diols having a hydroxyl group (eg ethylene glycol) as chain extenders in order to improve productivity due to faster reactivity and higher physical properties. A method for producing a polyurethane / polyurea resin molded article by the RIM method is disclosed (German Patent Publication No. 2622952). Furthermore, a technique of a polyurea resin molded product by the RIM method using a polyether polyamine obtained by aminating the hydroxyl group of the polyether polyol constituting the soft segment is disclosed (US Patent Publication No. 44330).
67). However, a polyester compound in which the terminal is modified with an amino group has not been used in the conventional polyurethane industry. Because the polyester compound itself has a high viscosity, or is solid at almost room temperature, and if the terminal of the polyester compound is an amino group, it is hydrogen bond of the amino group, and the compound is sure to be solid. It was because it was imagined that there would be difficulties. However, as a result of diligent studies by the present inventors, it was found that a polyester of a fatty acid substrate having a hydroxyl group is a liquid in spite of its high molecular weight. In Japanese Patent Application No. 02-246282, Prepolymer 1 of an isocyanate-terminated prepolymer obtained by reacting an ester condensate of a fatty acid having a hydroxyl group with an alkanediol and an organic polyisocyanate
A patent application has been filed for a resin composition having self-releasing properties and reactivity with isocyanate obtained by reacting polyamine and / or polyimine in an amount of 2 equivalents or more per equivalent. The operation and steps were complicated to obtain the compound. As described above, in the polyurethane industry, there is a demand for a novel isocyanate-reactive compound that is easy to use, has higher physical properties, and is easily released.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a novel compound having an amino group at the terminal of a molecule. This polyester compound can be synthesized by a simple operation. And, although it is a high molecular weight polyamine compound containing a terminal amino group, it has a low liquid or softening point and is substantially liquid at the operating temperature.

[0004]

According to the present invention, a polyester condensate of a terminal carboxylic acid is synthesized by esterification of a fatty acid having a hydroxyl group and a dicarboxylic acid, and 2 equivalents or more per 1 equivalent of the polyester condensate produced. The purpose is to add a polyamine and subsequently carry out amidation to obtain a polyester compound having an amino group at the terminal of a novel molecule.

That is, in the present invention, a condensate having an ester group of a carboxylic acid at the terminal of a molecule produced from 3 to 15 mol of a fatty acid containing a hydroxyl group and 1 mol of an aliphatic dicarboxylic acid is used as an aromatic diamine and / or Alternatively, the present invention provides a polyester compound having an amino group at the terminal of a molecule obtained by reacting with an aliphatic diamine and / or an alicyclic diamine. Hereinafter, a specific method for producing the polyester compound having an amino group at the terminal of the molecule of the present invention will be described. The polyester compound having an amino group at the terminal of the molecule of the present invention comprises a reaction in which a hydroxy fatty acid and a dicarboxylic acid are reacted and an amide is synthesized from the obtained terminal carboxylic acid polyester condensate and polyamine.

The hydroxy fatty acids used in the present invention are 8-hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid and 11-hydroxystearic acid.
Hydroxystearic acid, 12-hydroxystearic acid, 8-hydroxypalmitic acid, 9-hydroxypalmitic acid, 10-hydroxypalmitic acid, 11-hydroxypalmitic acid, 12-hydroxypalmitic acid,
Ricinoleic acid or the like can be used. 12-hydroxystearic acid and ricinoleic acid are particularly preferable. Also, mixtures of these are preferred. Industrially, it is difficult to use these high-purity products, and normally, a lower compound containing a fatty acid having no hydroxyl group derived from a raw material of 5 to 15% is used. It has no effect on. The dicarboxylic acid used is
A dicarboxylic acid having 2 to 20 carbon atoms can be used. For example,
Oxalic acid, malonic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, dodecanedioic acid, eicosanedioic acid, etc. can be used. Adipic acid is preferred. The dicarboxylic acid is preferably 1 mol with respect to 3 to 15 mol of the hydroxy fatty acid used in the reaction. When the condensation reaction is performed with such a composition, the average molecular death amount is 1000 to 8000 and the acid value is 125.
-12.5 mg KOH / g polyester condensate is obtained.
The reaction temperature for conducting the condensation is not particularly limited and is 100 ° C to 25 ° C.
It may be 0 ° C, preferably 170 ° C to 210 ° C. The reaction proceeds even without a catalyst, but the time required for condensation can be shortened by adding a catalyst. As the catalyst, there are used inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, etc., which are commonly used as esterification catalysts, organic acids such as p-toluenesulfonic acid, methanesulfonic acid, etc., as well as alkoxytitanium, acidic ion exchange resins, etc. it can. The reaction proceeds even under normal pressure, but the condensation time can be shortened by removing water generated by condensation from the system. The degree of vacuum may be about 10 to 100 mmHg. The reaction time depends on the reaction temperature, the molar ratio of the raw materials used, etc.
0 to 50 hours is sufficient. The end point of the reaction can be determined by measuring the molecular weight by gel column chromatography and the hydroxyl value and the acid value. After completion of the reaction, 2 equivalents or more of polyamine is added to 1 equivalent of the polyester condensate, and the amidation reaction is subsequently performed on the obtained polyester condensate.

The polyamine used for the amidation may be an aromatic, aliphatic or alicyclic polyamine, or a mixture thereof. Examples of the aliphatic polyamine include ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, and diethylenetriamine. Examples of the alicyclic polyamine include 1,2-
Cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, piperazine,
N- (2-aminoethyl) piperazine, N, N'-bis (2-aminoethyl) piperazine and the like can be used. Aromatic polyamines are preferable, and aromatic diamines represented by the formulas [1], [2] and [3] (Chemical formulas 4 to 6) are particularly preferable. A mixture of one or more of these is also preferred.

[0008]

[Chemical 4]

[0009]

[Chemical 5](R in the formula₁, R₂, R₃, R_Four, R_FiveIs a hydrogen atom or 1 carbon atom
R in the alkyl group of 10 ₁, R₂, R₃At least of
One in the ortho position to at least one amino group
It is in. )

[0010]

[Chemical 6] (In the formula, R ₆ , R ₇ , R ₈ and R ₉ are hydrogen atoms or having 1 to 1 carbon atoms.
The alkyl group of 0, n represents the integer of 1-10. ) The reaction temperature of the amidation reaction is not particularly limited and is 100 ° C to 250 ° C.
It is preferably 170 ° C to 210 ° C. The reaction proceeds even without a catalyst, but it is also possible to add a catalyst. The reaction time varies depending on the reaction temperature and the amine used, but 20 to 50 hours is sufficient. The end point of the reaction can be determined by infrared spectroscopy analysis by the disappearance of the carboxylic acid and the formation of an amide bond. After completion of the reaction, excess amine can be removed by distillation, extraction, etc. to obtain a polyester compound having an amino group at the terminal of the molecule. The amine used can be used as a chain extender, a cross-linking agent or other active hydrogen compound. In this case, the unreacted amine can be directly used for the reaction with the isocyanate without removing it. The polyester compound having an amino group at the terminal of the molecule of the present invention thus obtained is
It is liquid at room temperature or has a low softening point, and it is substantially liquid at the temperature of use, and the polyurethane / urea resin or polyurea resin using this shows easy releasability from the mold.

[0011]

EXAMPLES Hereinafter, the synthesis method of the polyester compound having an amino group at the terminal of the molecule of the present invention will be described with reference to Examples. Example 1 1000 g of 12-hydroxystearic acid, 69.5 g of adipic acid and 0.05 g of titanium tetrabutoxide were charged into a container equipped with a stirrer, a reflux condenser, a Dean-Stark water separator and a nitrogen introducing tube, and a nitrogen atmosphere was introduced. Below 190
The mixture was heated to ° C and stirred for 18 hours. Then, under reduced pressure (10m
The mixture was heated and stirred at mHg) for 7 hours. When the product was analyzed, a polyester condensate of a terminal carboxylic acid having an acid value of 68.5 mgKOH / g and an average molecular weight of 1600 was obtained. To this was added 600 g of an 80:20 mixture of 1-methyl-3,5-diethyl-2,4 diaminobenzene and 1-methyl-3,5 diethyl-2,6 diaminobenzene to give an additional 1
The mixture was heated and stirred at 90 ° C. for 25 hours. Infrared spectroscopy confirmed the disappearance of the carboxylic acid and the formation of an amide bond. It was confirmed by analysis of acid value that the amidation ratio was almost quantitative.

[0012]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a novel polyester compound having an amino group at the terminal of a molecule that provides easy release from a mold and high physical properties, and a method for producing the same.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Toshiaki Moriya 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Tsutomu Kumazawa 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chem Within the corporation

Claims (4)

[Claims] 1. A fatty acid 3-1 containing a hydroxyl group.
By reacting a condensate having an ester group of a carboxylic acid at the end of a molecule prepared from 5 mol and 1 mol of an aliphatic dicarboxylic acid with an aromatic polyamine and / or an aliphatic polyamine and / or an alicyclic polyamine A polyester compound having an amino group at the terminal of the obtained molecule. 2. The polyester compound having an amino group at the terminal of the molecule according to claim 1, wherein the fatty acid containing a hydroxyl group is ricinoleic acid and / or 12-hydroxystearic acid. 3. The polyester compound having an amino group at the terminal of the molecule according to claim 1, wherein the aliphatic dicarboxylic acid is adipic acid. * 4. A polyamine to be reacted with a condensate having a carboxylic acid ester group at the end of the molecule is a compound represented by the following formulas [1], [2] and [3] (chemical formulas 1 to 3). The polyester compound having an amino group at the terminal of the molecule according to claim 1, which is one kind or a mixture of two or more kinds selected. [Chemical 1] [Chemical 2] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atoms or carbon atoms 1
At least 1 of R ₁ , R ₂ and R ₃ with 10 to 10 alkyl groups
Is in the ortho position to at least one amino group. ) [Chemical 3] (In the formula, R ₆ , R ₇ , R ₈ and R ₉ are hydrogen atoms or having 1 to 1 carbon atoms.
An alkyl group of 0 and n represents an integer of 110. )