JP3176448B2 - Manufacturing method of aromatic polyester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel aromatic polyester and a method for producing the same.

[0002]

2. Description of the Related Art Many polyesters using aromatic diol components and dicarboxylic acid components have been known, such as polyesters of hydroquinone and isophthalic acid, polyesters of hydroquinone and terephthalic acid, and p-hydroxybenzoic acid. Polyester has been proposed,
Since the softening point or melting point is too high and too close to the decomposition temperature, there is a problem in formability.

[0003]

An object of the present invention is to provide a novel aromatic polyester which is heat-resistant and has a high glass transition point, but is easily melt-molded due to a large difference between a thermal decomposition temperature and a melting point, and a method for producing the same. is there.

[0004] The present invention provides an aqueous medium containing resorcinol and an organic medium in which 2,7-naphthalenedicarboxylic acid halide is dissolved in an organic solvent immiscible with the aqueous medium.
An equation characterized by performing an interfacial degeneration reaction by contacting in the presence of a phase transfer catalyst

Embedded image And a method for producing an aromatic polyester having a repeating unit represented by the formula:

According to the interfacial polycondensation method, a polymer having less coloring and a high degree of polymerization is generally obtained as compared with the polymer obtained by the melt transesterification method, and thus this polymerization method is most preferable. Water is usually used as the aqueous medium used to dissolve resorcinol. The concentration of resorcinols in the aqueous medium is not strictly limited, but is generally 0.1 to 10 mol / l,
Preferably within the range of 0.2 to 5 mol / l. In addition, the aqueous phase preferably contains a neutralizing agent for trapping and neutralizing hydrogen halide by-produced in the polycondensation reaction. Examples of such a neutralizing agent include sodium hydroxide, Alkali metal or alkaline earth metal hydroxides, carbonates or bicarbonates such as potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, etc. Sodium is preferred. These neutralizing agents can usually be present in the aqueous phase at a concentration of about 0.5-2M, preferably about 0.9-1.1M. On the other hand, as the 2,7-naphthalenedicarboxylic acid halide in the organic phase, any of chloride, bromide and fluoride may be used, but chloride is generally preferred and can be used to dissolve these acid halide components. Examples of the organic solvent include halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and sym-tetrachloroethane, and benzene, toluene, anisole, chlorobenzene, acetophenone, and the like.
Aromatic hydrocarbons such as benzonitrile and nitrobenzene are included, but toluene is particularly preferred. The concentration of the naphthalenedicarboxylic acid halide in these solvents is not particularly limited, but generally, the concentration of 2,7-naphthalenedicarboxylic acid halide is 0.05 to 1 mol / mol.
It is appropriate that the amount be within the range of 0.1, particularly 0.1 to 0.5 mol / l. Further, as a phase transfer catalyst,
For example, tetrabutylammonium chloride (TBA
C), benzyltriethylammonium chloride, benzyltriphenylphosphonium bromide (CTBP
B), 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6 and the like can be used, and among them, benzyltriethylammonium chloride can be advantageously used. These catalysts are usually present in an amount of 0 to 4 mol%, preferably 1 to 4 mol%, based on the acid chloride component.
It can be used within the range of ３3 mol%. The contact between the aqueous phase and the organic phase is usually performed with stirring. The reaction can be generally carried out at a temperature from room temperature to about 100 ° C., preferably at room temperature, under normal pressure for about 5 to about 120 minutes. The mixing ratio of the aqueous phase and the organic phase is usually
It is appropriate that the amount of resorcinol in the aqueous phase is adjusted to 1 to 1.5 mol per 1 mol of the total amount of the acid halide component in the organic phase.

The method for producing the aromatic polyester of the present invention is not limited to the above-mentioned interfacial polycondensation method, but is a per se known melt transesterification method (for example, see Japanese Patent Publication No. 50-31818).
Can be done at The method for producing the aromatic polyester of the present invention by the melt transesterification method comprises: (a) converting resorcinol into a diester, mixing the diester with 2,7-naphthalenedicarboxylic acid, and melting and reacting in the presence of a transesterification catalyst; , (B) resorcinol to 2,
It can be carried out by a method of mixing with 7-naphthalenedicarboxylic acid diaryl ester, melting and reacting in the presence of a transesterification catalyst. Examples of the resorcinol diester usable here include resorcinol diacetate, propionate, benzoate and the like. As the diaryl ester of 2,7-naphthalenedicarboxylic acid, diphenyl ester is particularly preferred. This transesterification method is carried out at a temperature at which both monomer components are melted, generally at 180 ° C. or higher, preferably at 25 ° C.
The reaction can be carried out under an arbitrary pressure, preferably under reduced pressure, at a temperature of 0 ° C. or higher and in a range where the monomer component does not thermally decompose, more preferably in a range of 280 to 310 ° C. Further, as a transesterification catalyst that can be used in the reaction, for example, titanium compounds such as titanium tetrabutoxide, titanium tetraethoxide, and titanyl oxalate are preferable, and in addition, antimony trioxide, zinc acetate, manganese acetate, and the like. Can also be used.
These are used in an amount of 0.0,
It is convenient to use it in an amount of from about 0.5 to 1.0 mol%, especially about 0.05 to 0.5 mol%.

In the production of the aromatic polyester of the present invention, in addition to resorcinol, for example, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, 2-methyl-1,2 3-propanediol, neopentyl glycol, 2-ethyl-2
Diols such as -methyl-1,3-propanediol, triethylene glycol, 2,2,4,4-tetramethylcyclobutanediol, and / or as a dicarboxylic acid component, in addition to 2,7-naphthalenedicarboxylic acid,
For example, isomers of other naphthalenedicarboxylic acids other than 2,7-naphthalenedicarboxylic acid; dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, adipic acid, sebacic acid, and / or p-oxybenzoic acid, m-
Oxybenzoic acid, 3-chloro-4-oxybenzoic acid, 3
A small amount of an oxyacid such as -methoxy-4-benzoic acid, 2,6-oxynaphthoic acid, or 1,4-oxynaphthoic acid, which does not substantially impair the physical properties of the aromatic copolyester of the present invention. For example, it may be blended in an amount of 15 mol% or less.

The aromatic polyester of the present invention has a high glass transition temperature, excellent heat resistance, and excellent moldability, and is a molded product in the fields of electricity, automobiles, machinery, and medical miscellaneous goods. It can be widely used for applications such as films, fibers, paints and adhesives. When used for such an application, the aromatic copolyester of the present invention includes a reinforcing agent such as glass fiber, carbon fiber, and asbestos; a filler, a nucleating agent, a flame retardant, a pigment, an antioxidant, and a heat stable material. Additives such as an agent, an ultraviolet absorber, a coloring inhibitor, a plasticizer, a lubricant, and a mold release agent, or can be kneaded with another thermoplastic resin.

[0009]

Next, the present invention will be described more specifically with reference to examples. In addition, the measurement of the physical property followed the following method. Viscosity ηinh: 0.1 g of polymer was dissolved in 20 ml of phenol / tetrachloroethane (50/50) (0.
5 g / dl), of which 10 ml is taken in an Ostwald viscometer, placed in a thermostat at 30 ° C., and the fall time is measured (t). Next, the same measurement is performed using only the measurement solvent (t ₀ ).
From these values, the intrinsic viscosity ηinh is determined using the following equation.

Ηinh = 1n (t / t ₀ ) /0.5 Note) As a standard of t ₀ , measure with a viscometer for about 120 seconds. Glass transition point (Tg) and melting point Tm: Measured using a differential scanning calorimeter (DSC-20, manufactured by Seiko Instruments Inc.). About 10 mg of the obtained polymer was precisely weighed in an aluminum pan, and the temperature was increased from 50 ° C. to 400 ° C. in a nitrogen gas stream.
The temperature was raised at a rate of ° C / min, and the first inflection point peak was defined as Tg.
The endothermic peak point was defined as Tm. Thermal decomposition temperature: It was measured using a differential thermogravimetric simultaneous measurement device (Tg / DTA-20 type) manufactured by Seiko Denshi Kogyo. Approximately 10 mg is precisely weighed in a platinum pan, and an air gas flow of 10 ° C. /
The temperature was raised in minutes and the 10% wt reduction point was taken as the thermal decomposition temperature.

Example 1 In a three-necked flask equipped with a mechanical stirrer, 20.4 ml of a 1 M aqueous sodium hydroxide solution was taken, and 1.104 g (10 mmol) of resorcinol and 0.06 g of benzyltriethylammonium chloride were added and dissolved. To this solution was added 2,7-naphthalenedicarbonyl dichloride.
A solution of 531 g (10 mmol) dissolved in 48 ml of toluene is added all at once with stirring, and the mixture is stirred at room temperature for 100 minutes with a stirring speed of 800 rpm. Thereafter, the polymerization solution is allowed to stand and separated to separate a toluene solution containing the polymer, which is then washed with acetic acid water, further washed with ion-exchanged water, and then poured into acetone to precipitate the polymer. The precipitated polymer was filtered, washed with water, and dried under reduced pressure. The intrinsic viscosity ηinh of the polymer is 0.66 dl / g, the glass transition temperature Tg is 161 ° C, the melting point Tm is 219 ° C, and the thermal decomposition temperature is 43.
5 ° C.

Example 2 2,7-Naphthalenedicarbonyl dichloride 2.531
The same method as in Example 1 was repeated except that a solution of g (10 mmol) in 13 ml of nitrobenzene was used. The intrinsic viscosity ηinh of the obtained polymer is 0.1.
It was 18 dl / g.

[0012]

The aromatic polyester obtained by the interfacial polycondensation method of the present invention not only has a high glass transition temperature and excellent heat resistance, but also has a melting point and a thermal decomposition temperature of 219 ° C and 435 ° C, which are far from each other. In melt molding, an excellent molded product is obtained without coloring and deterioration in physical properties due to thermal decomposition.

────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Toshio Yamauchi 3-5-2 Kasumigaseki, Chiyoda-ku, Tokyo Showa Shell Sekiyu KK (72) Inventor Osamu Nojiri 3-5-2 Kasumigaseki, Chiyoda-ku, Tokyo Showa (56) References JP-A-3-203925 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. An aqueous medium containing resorcinol,
A method comprising contacting an aqueous medium in which 7-naphthalenedicarboxylic acid halide is dissolved with an organic medium in which a 7-naphthalenedicarboxylic acid halide is dissolved in an immiscible organic solvent in the presence of a phase transfer catalyst to carry out an interfacial degeneration reaction. ] A method for producing an aromatic polyester having a repeating unit represented by the formula: