JPS63227625A - Copolyester and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer having excellent heat resistance and good melt moldability, by polycondensing p-hydroxybenzoic acid with p- hydroxyphenylacetic acid, etc., in a specific ratio. CONSTITUTION:30-80mol.% compound expressed by formula I or ester-forming derivative thereof is subjected to polycondensation reaction with 0-30% compound expressed by formula II or ester-forming derivative thereof and 20-70% compound expressed by formula III or ester-forming derivative thereof, preferably at 280-350 deg.C for 0.5-10hr to provide the aimed copolymer composed of 30-80% repeating units expressed by formula IV, 0-30% repeating units expressed by formula V and 20-70% repeating units expressed by formula VI and having preferably 250-350 deg.C flow temperature. The polycondensation can be carried out in solid, liquid or suspended conditions and a solvent or catalyst may be used in the polycondensation.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a new copolyester having excellent heat resistance and good melt moldability, and a method for producing the same.

<Prior Art> Attempts to obtain heat-resistant polyesters have been made for a long time, and there is much knowledge about aromatic polyesters made of aromatic dicarboxylic acids and aromatic diphenols and aromatic polyesters obtained from aromatic oxycarboxylic acids. However, heat resistance and moldability are in a contradictory relationship.
Econol E-101) manufactured by Econol is highly crystalline and has a crystallinity of 800”.
Although it is a polyester that does not decompose at all even in C and has excellent thermal stability, its melting point exceeds 500"C, and there is no organic solvent that can dissolve it, so its moldability is extremely poor. On the other hand, polyester ( Although polyester represented by PET (hereinafter referred to as PET) has excellent moldability,
In view of the current situation where PET has a melting point of 260°C and cannot be used for applications exceeding 200°C, the object of the present invention is to develop a copolyester with excellent heat resistance and moldability, especially melt moldability. To provide a method for producing the same.As a result of intensive study to solve such problems, the present inventors have found 8.
We have achieved a copolyester of the present invention that shows little decomposition even at 00°C, that is, little N1M loss, is stable, and has good melt moldability. That is, the present invention provides (1) the following formula (5), zero force and the constituent ratio (mol) of the repeating structural unit represented by (Q) (B) 80 to 80%,
(B) 0 to 80% and ((, 120 to 70% copolyester, and (A) 10 (filtered CO + (B) 100 CO + 0 100 3X dried CH 2 CO)) (However, (p is an integer of 1 or 2) (2) Compounds represented by (A'), (B') and (C') below (A') 80 to 80 mol%, (B') 0 to 8
It consists of carrying out a polycondensation reaction at a ratio of 0 mol % and (C') 20 to 70 mol %.

(A') HO<φxCOOH or its ester-forming derivative (B') HO? OOH or its ester-forming derivative (C') Ha (φΣ0C pcOOH (however,
(p is an integer of 1 or 2) or its ester-forming derivative The constituent proportion (mol) of the repeating structural unit represented by the following formula (5), @ and (Corporate) is (A) 80 to 80%, (B) 0 ~8
0% and (920-70%) Copolyester manufacturing method (A) 10o-@-co+ (B) 10-@-COtan (C) -E-0beβΣ+CHgJapaneseCO+ (however, p is 1
or an integer of 2).

The constituent proportion (mol) of each repeating structural unit represented by the above formulas (A), (B) and (C) is (A) 80 to 80%
, (B) 0 to 80% and (C) 20 to 70%, the copolyester is crystalline, has excellent heat resistance, and has good moldability. If the proportion of the structural unit (A) exceeds 80%, the copolyester will have a portion that does not melt when heated, resulting in poor moldability, and if it is less than 8096, the copolyester will have insufficient heat resistance. . If the proportion of the structural unit (B) exceeds 80%, the crystallinity of the copolyester will decrease and the heat resistance will be insufficient. If the proportion of the structural unit (C) exceeds 70%, the heat resistance of the copolyester will be insufficient, and if it is less than 20%, the moldability of the copolyester will become difficult.

Examples of the compound represented by (A') above include p-hydroxybenzoic acid, p-formoxybenzoic acid, p-acetoxybenzoic acid, p-probyloxybenzoic acid, methyl p-hydroxybenzoate, and phenyl p-hydroxybenzoate. , benzyl p-hydroxybenzoate, methyl p-acetoxybenzoate, and the like.

Examples of the compound represented by (B') above include m-hydroxybenzoic acid, m-formoxybenzoic acid, m-acetoxybenzoic acid, m-probyloxybenzoic acid, methyl m-hydroxybenzoate, and phenyl m-hydroxybenzoate. , benzyl m-acetoxybenzoate, methyl m-acetoxybenzoate, and the like.

Examples of the compound represented by (C') above include p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-formoxyphenylacetic acid, p-acetoxyphenylacetic acid, p-7cetoxyphenylprobionic acid, p-
-Probyloxyphenylacetic acid, p-probyloxyphenylprobionic acid, methyl p-hydroxyphenylacetate,
Examples include ethyl p-hydroxyphenylpropionate, phenyl p-hydroxyphenylacetate, and methyl p-acetoxyphenylbrobionate.

The copolyester obtained by using 10 to 80 mol% of salicylic acid in place of the compound represented by (B') does not exhibit good physical properties, and the homopolyester obtained from the compound represented by (C') does not exhibit good physical properties. Although it was crystalline, it decomposed immediately after melting and did not exhibit good moldability.

The copolyester of the present invention has the above-mentioned (A'), (B'
) and (C') are subjected to a polycondensation reaction in a polymerization tank, and these compounds may be added to the polymerization tank either all at once or in portions. The reaction can be carried out at normal pressure, reduced pressure or a combination thereof, and the process can be carried out batchwise, continuously or in a combination thereof. The mode of polycondensation is bulk, solution or suspension, and a solvent and a catalyst can be used.

In addition, the reaction (
For example, it is also possible to carry out the polycondensation reaction (for example, the esterification reaction) in the same polymerization tank prior to the polycondensation reaction, and then carry out the polycondensation reaction.

The temperature of the polycondensation reaction in the present invention is preferably 250 to 890°C, more preferably 280 to 850°C. If the temperature is lower than 260°C, the reaction is difficult to occur, and the temperature is lower than 890°C.
If it exceeds C, side reactions such as decomposition may occur. It is possible to adopt multiple reaction temperatures, and in some cases,
It is also possible to adopt a method in which cooling is started immediately after the maximum temperature is reached by only raising the temperature.

The time for the polycondensation reaction is preferably 0.5 to 10 hours at the reaction temperature.

Examples of the solvent used in the polycondensation reaction include high-boiling hydrocarbons, ethers, silicone oil, fluorine oil, etc., and examples of the polycondensation catalyst include Ge1Sn and 5b1Ti.
Metal compounds such as Furthermore, a method of polycondensation in a solvent using a phosphorus compound and an amine compound as a catalyst can also be adopted (see Japanese Patent Laid-Open No. 45921/1983).

The polycondensation reaction of the present invention can also be carried out in the presence of stabilizers, additives, etc.

Of the polyesters of the present invention, those that are soluble in solvents,
Alternatively, if the terminal group of the copolyester can be quantified, it may be possible to measure the molecular weight of the copolyester, and the preferred number average molecular weight is 7,000 to 7,000.
1,000,000. However, some of the copolyesters of the present invention do not have good strength or reproducibility. Therefore, the flow temperature was used instead of the molecular chain of the obtained copolyester. Here, the flow temperature refers to the melt fluidity of a thermoplastic resin due to heating, and the lower the temperature, the greater the melt fluidity, and the lower the molecular weight, the better the moldability. .

The flow temperature was measured using a capillary rheometer (manufactured by Takashi Seisakusho).
Measured with flow tester ■ CFT-500 model), 4
The sample was heated and melted at a heating rate of °C/min, with an inner diameter of 1wm under a load of 100kg/cd,
It is expressed as the temperature at the point (lO) at which the viscosity of the molten resin is 48,000 poise when extruded from a nozzle with a length of 10 m.

The flow ffi degree of the copolyester of the present invention is 1.1200.
-880°C, preferably 250-850°C.

Those having a flow temperature of less than 200° C. have a low molecular weight and poor heat resistance, and may have problems with moldability or have insufficient physical properties of molded products. Furthermore, it is often impossible to mold products with a flow temperature exceeding 880''C, and problems of thermal decomposition arise when the temperature is raised to high temperatures.

<Effects of the Invention> According to the present invention, the above formulas (A), (B) and (C)
A copolyester containing a specific proportion of repeating structural units represented by is excellent in heat resistance and moldability;
It can be obtained by polycondensation reaction of the compound represented by in a specific ratio. As shown in the comparative examples described below, when the proportion of monomers used is outside the specific proportion range of the present invention, the moldability and/or heat resistance of the obtained copolyester is not good. In contrast, in the examples of the present invention, copolyesters having excellent moldability and heat resistance are obtained.

The copolyester of the present invention is crystalline and stable during melt molding and use at high temperatures. This copolyester, this copolyester and glass fiber, mica,
Compositions with inorganic materials such as talc, potassium titanate, wollastonite, calcium carbonate, silica, quartz, iron oxide, graphite, and carbon fiber have excellent mechanical properties, electrical properties, chemical resistance, and oil resistance. It can be used for mechanical parts, electrical/electronic parts, automobile parts, etc.

<Examples> Examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 910.8 F (A, 6 moles) of p-hydroxybenzoic acid and 1008 F of p-hydroxyphenylacetic acid were placed in a polymerization tank that had an anchor-type stirring blade and had a small clearance between the tank wall and the stirring blade. .2f (A, 6 mol) and acetic anhydride 1
480f (14°5 mol) was charged. The contents were heated to 150"C with stirring under a nitrogen atmosphere, and refluxed at this temperature for 6 hours. Thereafter, the temperature was raised to 820°C with stirring, and a polycondensation reaction was carried out at this temperature for 8 hours. Acetic acid was distilled out of the system when the temperature was raised, but this acetic acid was a by-product of acetylation of the phenolic hydroxyl groups of both monomers mentioned above with acetic anhydride, and a polycondensation reaction of both acetylated monomers. This was a by-product.Then, while maintaining the system at B torr with a vacuum pump, polymerization was further carried out at 820°C for 1 hour.The reaction mixture was cooled and taken out, and 1681 g of light yellowish brown polymer was obtained. (97.8% of the theoretical yield).This material was finely pulverized using a pulverizer, and the resulting finely powdered polymer was 270%
"C" for 12 hours under reduced pressure.

The flow temperature of the dried polymer was 295°C.

Furthermore, when this polymer was heated in air at a heating rate of 10°C/min, no weight loss was observed up to 800°C, and the temperature at which it showed a 2.5% weight loss (hereinafter referred to as 2.5% weight loss The polymer temperature was 405"C. This polymer was melt-extruded using a screw extruder with a diameter of 20mm to obtain a yellow-brown molded product. The needle penetration temperature measured using a thermomechanical analyzer TMA-DT-80 model under conditions of a temperature increase rate of 10°C/min and a load of 209 was 880''C. Note that this measurement condition corresponds to V ca of 10 to 10 in terms of the load of softening point measurement.

Examples 2 to 8, Comparative Examples 1 to 2 Using the same equipment as in Example 1, the usage ratio (molar ratio) of p-hydroxybenzoic acid and p-hydroxyphenylacetic acid was 9.
0/10 (Comparative Example 1), 65/85 (Example 2), 85
/65 (Example 8) and 10/90 (Comparative Example 2), and polycondensation was carried out in the same manner as in Example 1. The results, including those of Example 1, are shown in the table below, and it can be seen that the copolyester according to the present invention is superior.

* p-Hydroxybenzoic acid/p-hydroxyphenylacetic acid Example 4 Using the same equipment as in Example 1, p-hydroxybenzoic acid phenyl 1412N (A, 6 mol), m-hydroxybenzoic acid phenyl 885f (1.8 mol) ) and p-hydroxyphenyl acetate phenyl 8214 (8.6 mol) were charged, and polymerization was carried out in the same manner as in Example 1 while removing phenol by-produced by the polycondensation reaction. In this example, the usage ratio (molar ratio) of each monomer was 55/15.
/80. A light tan polymer x482F (99.5% of the theoretical yield) was obtained. The same post-treatment as in Example 1 was carried out to obtain a polymer having a flow temperature of 288°C. The weight loss of this polymer up to 800°C is 0.0%,
The 2.5% weight loss temperature was stable at 895''C. When the temperature was increased at 25°C/min under polarized light, melting anisotropy was exhibited at 880°C or higher.

Example 5 p-hydroxybenzoic acid 188 was added to an apparatus similar to Example 1.
F (1,0 mol), p-hydroxyphenylpropionic acid 166f (1,0 mol) and acetic anhydride 224IC2
, 2 mol) was charged, the temperature was raised to 820°C under a nitrogen atmosphere, and after polymerization at this temperature for 2 hours, the system was heated to 12 torr.
Polymerization was further carried out for 80 minutes under reduced pressure. The reaction mixture was cooled and then ground, and the resulting powder was heated at 260"C for 12
By drying under reduced pressure for an hour, powdered polymer 286
94.4% of the theoretical IC yield was obtained.

The polymer can be melted by heating, the flow temperature is 292°C, and the weight loss up to 800°C is 0.
The 0% and 2.5% weight loss temperatures were 887°C.

(17 completed)

Claims (2)

[Claims] (1) The constituent proportion (mol) of repeating structural units represented by the following formulas (A), (B) and (C) is (A) 30 to 80%,
(B) 0-30% and (C) 20-70% copolyester. (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (C) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, p is an integer of 1 or 2) (2) Compounds represented by (A'), (B') and (C') below (A') 30 to 80 mol%, (B') 0 to 3
(A') ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or its ester-forming derivative (B') ▲ Numerical formula, There are chemical formulas, tables, etc. ▼ or its ester-forming derivatives (C') ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (where p is an integer of 1 or 2) or its ester-forming derivatives (formula (A)), The constituent ratio (mol) of the repeating structural units represented by (B) and (C) is (A) 30 to 80%, (B)
A method for producing a copolyester having 0 to 30% and (C) 20 to 70%. (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (C) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, p is an integer of 1 or 2)