JPS5947690B2 - Allylene ester cage - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an arylene ester polymer.

An object of the present invention is to provide an arylene ester polymer resin that can be melt-molded and has excellent heat resistance and can be used for fibers, films, molded products, adhesives, paints, etc.

Traditionally, linear polyalkylene esters formed from aromatic dicarboxylic acids and aliphatic glycols, such as polyethylene terephthalate and polybutylene terephthalate resins, have been industrially produced and widely used in films, fibers, molded products, etc. As is common knowledge.

These polyesters contain rigid aromatic rings with high molecular symmetry, so they are crystalline and high melting point polymers, making them useful for fibers,
The film has high strength, high elastic modulus, and heat resistance by being oriented in the +axis or biaxial direction, and is superior to other general-purpose resins in these respects. However, for tire cords, magnetic tapes, etc., even higher strength and higher modulus of elasticity are now desired. In addition, when used as an electrical insulator, it has high heat resistance,
Improvements in dielectric constant, dielectric loss, dielectric strength, etc. are desired.
On the other hand, fully aromatic polyester resins such as polyoxybenzoate have superior properties compared to polyalkylene ester resins in terms of heat resistance, mechanical properties, electrical properties, chemical resistance, self-extinguishing properties, etc. It is also known that However, since wholly aromatic polyester resins are difficult to manufacture and process, their use is currently limited. In view of the current situation, the present inventors have made efforts to produce a polyester that is easy to manufacture, that is, can be melt polymerized, is easy to mold, that is, can be melt molded, and has high physical properties. The present invention was achieved through research. That is, the present invention provides aromatic dicarboxylic acids and/or their ester-forming derivatives 90-4.
A dicarboxylic acid mixture consisting of 0 mol% and 10 to 60 mol% of ω, ω′ monoaliphatic dicarboxylic acid (hereinafter referred to as aliphatic dicarboxylic acid) and/or its ester-forming derivative is mixed with a hydroxyl group directly bonded to an aromatic nucleus. By reacting with a hydroxy compound having two ester-forming functional groups and no other ester-forming functional group (hereinafter referred to as an aromatic dihydroxy compound) and/or its ester-forming derivative, the following two A units and B units can be formed. A copolymerized polyester consisting of two repeating structural units is obtained.

However, the above formulas X and Y are methylene group, ethylidene group, isopropylidene group, cyclohexylidene group, 1,-
- - 10-Li-S-, o=S
It represents a divalent organic group such as =o, and Ar represents a benzene ring or a naphthalene ring.

Further, m and n represent 0, 1 or 2, p and q represent 0 or 1, and s represents a transposition of 2 or more. The molar ratio of A units and B units is 90/10 to 90/10 depending on the raw material charging ratio.
It is 40/60. Typical aromatic dicarboxylic acids used in the present invention include terephthalic acid, isophthalic acid, diphenylcarboxylic acid, diphenyl ethercarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, and naphthalenedicarboxylic acid. Illustrated. Among aromatic dicarboxylic acids, especially terephthalate,
Isophthalic acid is preferred. Ester-forming derivatives of aromatic dicarboxylic acids include methyl ester, ethyl ester,
Benzyl ester, β-phenylethyl ester, β-
Lower alkyl esters such as phenoxyethyl ester,
Refers to aryl esters such as phenyl esters, acid halides, etc. Typical aliphatic dicarboxylic acids used in the present invention include succinic acid, glutaric acid, adipic acid,
pimelic acid, speric acid, azelaic acid, sebacic acid,
Examples include dodecanedioic acid.

Ester-forming derivatives of aliphatic dicarboxylic acids include methyl ester, ethyl ester, benzyl ester, β-
It refers to lower alkyl esters such as phenyl ethyl ester and β-phenoxyethyl ester, aryl esters such as phenyl ester, and acid...logonides. Preferred examples of the aromatic dihydroxy compound used in the present invention include hydroquinone, resorcinol, 1,5 or 2,
6-or 2,7-dihydroxynaphthalene, 2,2
-bis(4-hydroxyphenyl)propane, 1,1-
Bis(4-hydroxyphenyl)cyclohexane, 1,
1-bis(4-hydroxyphenyl)ethane, bis(4
-Hydroxyphenyl, tan, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl)
Examples include ether.

The ester-forming derivative of an aromatic dihydroxy compound refers to an ester formed from an aromatic dihydroxy compound and a low molecular weight organic acid such as benzoic acid, acetic acid, or propionic acid. Each of these aromatic dicarboxylic acid components, aliphatic dicarboxylic acid components, and aromatic dihydroxy compound components may be used alone or in combination of two or more.

In the method of the present invention, the molar ratio of the aromatic dicarboxylic acid component to the aliphatic dicarboxylic acid component is in the range of 90/10 to 40/60. When this ratio is greater than 90/10, the melting point of the polyester becomes high, which is inconvenient for melt polymerization and melt molding. If the ratio is smaller than 40/60, the objects of the present invention cannot be achieved in terms of heat resistance, mechanical properties, refractory chemical properties, etc., which is also disadvantageous. One of the preferred embodiments of the present invention is that the ratio of the aromatic dicarboxylic acid component to the aliphatic dicarboxylic acid component is 55/45 to 45/
55 (particularly preferably 50/50). In this case, the aromatic dicarboxylic acid units and aliphatic dicarboxylic acid units become statistically regular in the random polymer,
It is particularly preferred in terms of polyester properties (thermal properties, mechanical properties, crystallinity, etc.) and manufacturing properties (melting behavior, etc.). Further, in the method of the present invention, the aromatic dihydroxy compound is contained in an amount of 90 to 130 mol%, preferably 95 to 105% by mole based on the total acid components.
mol % (particularly preferably 100 mol %) is used. This is a necessary condition to obtain high molecular weight. When producing the arylene ester polymer of the present invention, any method generally known as a polyester production method,
For example, the following method can be adopted.

(1) Aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and diesters of aromatic dihydroxy compounds (e.g., diacetate) are heated at normal pressure in an inert gas atmosphere to perform a transesterification reaction to form a low polymer. , and then polycondensation of the low polymer at high temperature and reduced pressure.

(2) heating a diester of an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid (e.g. diphenyl ester) and an aromatic dihydroxy compound at normal pressure in an inert gas atmosphere;
A method in which a transesterification reaction is performed to form a low polymer, and then the low polymer is polycondensed at high temperature and under reduced pressure.

(3) Aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and aromatic dihydroxy compounds are heated to form a low polymer by heating in an inert atmosphere at normal pressure (or pressurization), and then the low polymer is heated at a high temperature. , a method of carrying out a polycondensation reaction under reduced pressure.

When performing polycondensation using this method, addition of diaryl carbonate (eg diphenyl carbonate) accelerates the reaction. Furthermore, when producing the polyester of the present invention, a compound having trifunctional or higher functional ester-forming groups is used to the extent that it does not substantially inhibit the physical properties of the polyester of the present invention, that is, 10 mol% or less, preferably 3 mol% or less. (e.g. bentaerythritol, glycholorol, pyromellitic acid, trimellitic acid, etc.), alkylene glycols, polyalkylene glycols (e.g. ethylene glycol,
1,4-butadiol, hexamethylene glycol, neopentyl glycol, polyethylene glycol, polyteuramethylene glycol), etc. may be added.

However, when alkylene glycol is added, either the hydroxyl groups at both ends are esterified with the aliphatic dicarboxylic acid used before addition, or the alkylene glycol is added at the same time so that it immediately reacts with the dicarboxylic acid component in the reaction system for esterification.
In carrying out the above reaction, catalysts and stabilizers commonly used in polyester production can be used.

Particularly preferred catalysts for the present invention are the production methods (1) and (3) described above.
), hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, metallic magnesium, potassium titanyl oxalate, antimony trioxide, and in the case of production method (2), titanium tetra-n
-butoxide, titanium-tetra-IsO-propoxide, dibutyltin dilaurate, and dibutylthioxide. These are usually 0.00% relative to the acid component.
1-1 mol% (preferably 0.01-10.1 mol%)
use. If the resulting polyester has a high melt viscosity in the late stage of polymerization and it is difficult to obtain a polymer with a high degree of polymerization, solid phase polymerization may be used in combination.

Preferred arylene ester polymers obtained in the present invention are shown below in terms of structural units and their molar ratios.

Specific examples include the following:

The arylene ester polymer obtained in the present invention is a fiber,
It can be widely used in fields that require heat resistance, radiation resistance, etc. as films, molded products, adhesives, paints, varnishes, etc. The arylene ester polymer of the present invention also contains crystal nucleating agents, fillers, pigments, glass fibers, carbon fibers, antioxidants,
Stabilizers, plasticizers, lubricants, and other additives may also be included. Some of the arylene ester polymers obtained in the present invention can also be used as reinforcing materials to increase the strength and modulus of other plastics. The present invention will be described below with reference to specific examples.

Parts in the examples indicate parts by weight, and various properties of the polymers were determined by the following method 'CIAU'. (1) Tm (crystal melting point) Using a micro melting point meter manufactured by Yanagimoto Seisakusho, increase the temperature at a rate of about 1° C./min, and read the temperature in the dark field under polarized light.

(2) Ts (softening point) Using a thermomechanical analyzer (TMA) manufactured by Perkin Elma,
3f! The softening point is read when the load is applied and the temperature is raised at 10°C/min.

This value correlates with the glass transition temperature. (3) Tg (Glass Transition Point) Measured using a differential scanning calorimeter, model DSC-IB, manufactured by PerkinElmer Co., Ltd., at a heating rate of 1 C/Min.

(4) [η] (Intrinsic viscosity) Phenol/Sym ptetrachloroethane = 60/40
(Weight ratio) Measured at 30°C.

Example 1 A predetermined amount (see Table 1) of hydroquinone diacetate (HQ-
(abbreviated as Ac), isophthalic acid (abbreviated as IPA), aliphatic dicarboxylic acid and metallic magnesium powder as a catalyst.
．． 0015 parts, and while blowing nitrogen gas, 250 parts
It was heated to 260°C.

The reaction was continued at this temperature for 3 hours while the produced acetic acid was distilled out of the system. Initially, the isophthalic acid existed as a solid, but as the esterification proceeded, it melted and finally became a homogeneous liquid. Then 260℃~270℃150m
After reacting with Hg for 15 minutes, it was transferred to a glass tube with branches, and a polycondensation reaction was performed at 285° C. and 0.21 nHg for 3.5 hours.

Table 1 shows the physical properties of the obtained polymer. When these resins were melt-formed at C 290 to 320 and rapidly cooled, strong films were obtained from all the resins.

Example 2 In a 100 cc glass flask equipped with a distillation device, 4.984 parts of terephthalic acid, 4.384 parts of adipic acid, 2.
Add 18.7 parts of 2-bis-(4,4'-diacetyloxyphenyl)propane and 0.0015 parts of magnesium powder, and heat to 260'C for 2.5 hours while blowing nitrogen gas.
The mixture was further heated at 265 °C for 7 hours.

Claims (1)

[Claims] 1 A dicarboxylic acid mixture consisting of 90 to 40 mol% of aromatic dicarboxylic acid and/or its ester-forming derivative and 10 to 60 mol% of ω, ω aliphatic dicarboxylic acid and/or its ester-forming derivative is added to the aromatic nucleus. A method for producing an arylene ester polymer, which comprises reacting with a dihydroxy compound having two directly bonded hydroxyl groups and no other ester-forming functional group and/or an ester-forming derivative thereof.