JPH04261422A - Polyester compound and production thereof - Google Patents

Abstract

PURPOSE:To provide the subject polyester compounds having a specified structure and excellent in mold release characteristics as a release agent for thermosetting resins, i.e., free from stain of a mold, deterioration of coating properties thereof and reduction of physical properties of moldings. CONSTITUTION:Polyester compounds represented by formula I (m+m=13 or 15; r and s are 0-7 and sum of them is 1-7; Sum of j and k is 1; R1 is H or 1-4C alkyl) or formula II (m, n, r and s are same in formula I; R2 and R3 are H or 1-4C alkyl). The above-mentioned compounds have 1000-8000 average molecular weight and 5-70 hydroxyl number and can be obtained by reacting a hydroxy fatty acid or its fatty alcohol ester with a glycol.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyester compound and a method for producing the same.

These series of compounds are used as mold release agents, plasticizers, modifiers, etc. for general thermosetting resins such as unsaturated polyester resins, epoxy resins, urethane/urea resins, urea resins, and phenolic resins. Can be used.

0003

[Prior art and problems] Generally, when molding resin,
It is important that the molded product be easily released from the mold. To achieve these objectives, various external as well as internal mold release agents have been disclosed.

Among mold release agents, an internal mold release agent in particular is required to be a compound that is compatible with the raw material and has low compatibility with the cured resin. As such compounds, fatty acids or their metal salts are usually used. however,
A mold release agent having such an action accumulates in the mold during continuous mold release and causes deterioration of the surface of the molded product, so it is necessary to periodically clean the inside of the mold. Furthermore, it is difficult to wash the mold release agent from the resin surface by cleaning with an organic solvent as a pretreatment for painting the molded product.

On the other hand, esters of fatty acids have also been used as internal mold release agents. However, these esters generally have poor mold releasability, and if they are added in an amount that satisfies the mold release performance, they act as plasticizers and cause deterioration in the physical properties of the molded product. Furthermore, the substances trapped in the resin gradually seep out onto the resin surface, impairing paintability.

[0006] As described above, the internal mold release agents currently in use have various problems such as contamination inside the mold, deterioration of paintability, and deterioration of the physical properties of molded products.

[0007]

[Problems to be Solved by the Invention] The present inventors have attempted to overcome the above-mentioned problems as a mold release agent, such as contamination in the mold, deterioration in paintability, and deterioration in the physical properties of molded products. I considered it carefully.

[0008]

[Means for Solving the Problems] The present inventors have completed the present invention as a result of intensive studies to achieve the above object.

That is, the present invention provides general formula (I) (chemical formula 8)

0010

[Image Omitted] (In the formula, m and n are integers whose sum is 13 or 15,
r and s each represent an integer of 0 to 7 and the sum of the integers is 1 to 7, j and k represent an integer of the sum of 1 to 25, and R1 represents H or a C1 to C4 alkyl group. show. ) or general formula (II) (Chemical formula 9)

[0011]

[Image Omitted] (In the formula, m and n are integers whose sum is 13 or 15,
t represents an integer of 1 to 4, j and k represent integers whose sum is 1 to 25, R2 and R3 are H or C1 to C
4 represents an alkyl group, which may be the same or different from each other. ) and general formula (III) (Chemical formula 10)

0012

(In the formula, R represents H or a C1 to C4 alkyl group, and m and n represent integers whose sum is 13 or 15.) and its ester and the general formula ( IV) (Chemical formula 11)

[0013]

[Chemical formula 11] (In the formula, r and s are each integers from 0 to 7, and the sum of them is 1
It represents an integer of ~7, and R1 represents H or a C1 to C4 alkyl group. ) or general formula (V) (Chemical formula 12)

[0014]

[Formula 12] (In the formula, t represents an integer of 1 to 4, R2 and R3 represent H or a C1 to C4 alkyl group, and may be the same or different.) This is a method for producing polyester compounds represented by general formulas (I) and (II) produced by reaction.

A feature of the polyester compound of the present invention is that when used as a mold release agent during resin molding, it exhibits excellent mold release properties without affecting the inherent physical properties of the resin. Further, problems such as contamination of the mold and deterioration of paintability due to seepage from the resin do not occur.

A specific method for producing the polyester compound of the present invention will be described below.

The polyester compound of the present invention can be obtained by reacting a hydroxy fatty acid or a lower alcohol ester thereof with a glycol.

In the present invention, the hydroxy fatty acids and esters thereof used include 8-hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, 11-hydroxystearic acid,
12-hydroxystearic acid, 8-hydroxypalmitic acid, 9-hydroxypalmitic acid, 10-hydroxypalmitic acid, 11-hydroxypalmitic acid, 12
-Hydroxypalmitic acid, as well as their methyl esters, ethyl esters, propyl esters, isopropyl esters, butyl esters, isobutyl esters, etc. can be used. Industrially, it is difficult to use these high-purity products, and usually a compound containing 5 to 15% of a fatty acid or its ester that does not have a hydroxyl group derived from the raw material is used, but the It has no effect on polyester compounds.

[0019] In addition, the glycols used include:
Compounds represented by general formula (II) include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, etc. can be used. As the compound represented by general formula (III), 2,3
-Butanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, etc. can be used.

The amount of glycol used is preferably 0 to 30 parts by weight per 100 parts by weight of hydroxy fatty acid and its ester used in the reaction. When a condensation reaction is carried out with such a composition, a polyester compound having an average molecular weight of 1,000 to 8,000 and a hydroxyl number of 5 to 70 is finally obtained. As mentioned above, hydroxy fatty acids contain about 5 to 15% of fatty acids that do not have hydroxy groups, and because they act as condensation terminators, their molecular weight is 8,000.
The extent is the limit. If the molar ratio of glycol to hydroxy fatty acid or its ester is high, the molecular weight will not increase, resulting in high viscosity and low fluidity, so when used as a mold release agent, it will have poor compatibility with raw materials and the viscosity of raw materials will increase. It becomes high and interferes with moldability.

The reaction temperature for condensation is not particularly limited;
The temperature may be 00 to 250°C, preferably 170 to 210°C. Although the reaction proceeds without a catalyst, the reaction time required for condensation can be shortened by adding a catalyst.

Examples of catalysts include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, which are commonly used as esterification catalysts, organic acids such as p-toluenesulfonic acid and methanesulfonic acid, and alkoxy titanium and acidic ion exchange resins. etc. can be used.

Although the reaction proceeds under normal pressure, it is preferable to carry out the reaction under reduced pressure because the condensation time can be shortened by removing water and lower alcohols produced by the condensation from the system. The degree of pressure reduction may be about 10 to 100 mmHg.

The reaction time varies from 20 to 50 minutes depending on the reaction temperature and the type of hydroxy fatty acid and its ester used.
0 hours is sufficient.

The end point of the reaction can be determined by measuring the molecular weight and hydroxyl value by gel column chromatography. After completion of the reaction, the obtained ester condensate can be used as it is as a mold release agent.

[0026]

[Action] When the polyester compound of the present invention obtained in this way is used as a mold release agent during resin molding, it exhibits excellent mold release properties without affecting the physical properties of the molded product or the paintability after molding. give.

[0027]

EXAMPLES The method for synthesizing the polyester compound of the present invention will be explained in detail below using Examples, but the present invention is not limited thereto. Example 1 In a container equipped with a stirrer and a reflux condenser, 600 g of 12-hydroxystearic acid (purity 87%, other main components are stearic acid), 1.3 l of methanol, and 3 g of p-toluenesulfonic acid were charged, Reflux was performed for 3 hours. After the reaction is complete, excess methanol is distilled off and the residue is soaked in hot water (70~
The mixture was washed four times with 700 ml (80°C) and dehydrated to obtain methyl ester. To this, 1,6-hexanediol 3
3.7 g and 0.05 ml of tetrabutoxy titanium were charged and heated at a temperature of 190 to 200°C and normal pressure for 10 hours.
The reaction was carried out at 20 mmHg for 30 hours to obtain a polyester compound.

Yield: 590g Acid value: 0.4 Hydroxyl value: 10 Average molecular weight: about 3000 Example 2 700g of 12-hydroxystearic acid (purity 87%, other main components) was placed in a container equipped with a stirrer and reflux condenser. is stearic acid), 27.5 g of 1,6-hexanediol,
Charge 0.05ml of tetrabutoxy titanium and
10-20mmHg for 7 hours at a temperature of 200℃ and normal pressure
The reaction was carried out for 37 hours to obtain a polyester compound.

Yield: 670 g Acid value: 1.2 Hydroxyl value: 28.8 Average molecular weight: about 45,000 Example 3 In a container equipped with a stirrer and a reflux condenser, 515 g of 9(10)-hydroxystearic acid and 1. 2 liters and 3 g of p-toluenesulfonic acid were charged and refluxed for 3 hours. After the reaction was completed, excess methanol was distilled off, and the residue was washed four times with 700 ml of warm water (70 to 80°C) and dehydrated to obtain a methyl ester. To this, 33.7 g of 1,6-hexanediol, 0.05 g of tetrabutoxytitanium
ml at normal pressure at a temperature of 190 to 200°C.
The reaction was carried out for 30 hours at 10 to 20 mmHg to obtain a polyester compound.

Yield: 490g Acid value: 0.7 Hydroxyl value: 15 Average molecular weight: about 3000

[0031]

Effects of the Invention According to the present invention, when used as a mold release agent for general thermosetting resins such as unsaturated polyester resins, epoxy resins, urethane/urea resins, urea resins, and phenolic resins, physical properties and paintability can be improved. It is possible to provide a novel polyester compound having excellent mold releasability without affecting the production of the same, and a method for producing the same.

Claims (3)

[Claims] Claim 1: General formula (I) (Chemical formula 1) [Chemical formula 1] (In the formula, m and n are integers whose sum is 13 or 15,
r and s each represent an integer of 0 to 7 and the sum of the integers is 1 to 7, j and k represent an integer of the sum of 1 to 25, and R1 represents H or a C1 to C4 alkyl group. show. ) or general formula (II) (Chemical formula 2) [Chemical formula 2] (In the formula, m and n are integers whose sum is 13 or 15,
t represents an integer of 1 to 4, j and k represent integers whose sum is 1 to 25, R2 and R3 are H or C1 to C
4 represents an alkyl group, which may be the same or different from each other. ) A polyester compound represented by Claim 2: Claim 1, characterized in that the average molecular weight is 1000 to 8000 and the hydroxy number is 5 to 70.
The polyester compound described. 3. General formula (III) (Chemical formula 3) [Chemical formula 3] (In the formula, R represents H or a C1 to C4 alkyl group, and m and n represent integers whose sum is 13 or 15. ) or its ester and the general formula (IV) (Chemical formula 4) [Chemical formula 4] (In the formula, r and s are each an integer of 0 to 7, and the sum thereof is 1.
It represents an integer of ~7, and R1 represents H or a C1 to C4 alkyl group. ) or an alkanediol represented by the general formula (V) (Chemical formula 5) [Chemical formula 5] (In the formula, t represents an integer of 1 to 4, R2 and R3 represent H or a C1 to C4 alkyl group, and the same General formula (I) (Chemical formula 6) [Chemical formula 6] (In the formula, m and n have a sum of 13 or an integer that is 15,
r and s each represent an integer of 0 to 7 and the sum of the integers is 1 to 7, j and k represent an integer of the sum of 1 to 25, and R1 represents H or a C1 to C4 alkyl group. show. ) or general formula (II) (Chemical formula 7) [Chemical formula 7] (In the formula, m and n are integers whose sum is 13 or 15,
t represents an integer of 1 to 4, j and k represent integers whose sum is 1 to 25, R2 and R3 are H or C1 to C
4 represents an alkyl group, which may be the same or different from each other. ) A method for producing a polyester compound represented by