JPH06122757A - Aromatic polyester and its preparation - Google Patents

Abstract

PURPOSE:To obtain an aromatic polyester having heat resistance and excellent moldability by performing the interfacial polycondensation of 4,4'- hexafluoroisopropylidenediphenol with 2,7-naphthalenedicarboxylic acid halide in a specified manner. CONSTITUTION:This aromatic polyester comprising repeating units of the formula is obtained by performing the interfacial polycondensation by contact of an aqueous medium containing 4,4'-hexafluoroisopropylidenediphenol with an organic medium prepared by dissolving 2,7-naphthalenedicarboxylic acid halide in an organic solvent immiscible with the above aqueous medium in the presence of a phase transfer catalyst. This resin has high strengths and high modulus and can be extensively used in applications such as moldings, films, fibers, coating materials and adhesives in the electrical field, the automobile field, the mechanical filed, the medical field or the sundry field.

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 Conventionally, many polyesters using aromatic type diol components and dicarboxylic acid components are known, and polyesters of hydroquinone and isophthalic acid, polyesters of hydroquinone and terephthalic acid, isophthalic acid, terephthalic acid And polyesters of bisphenol-A have been proposed. These have excellent heat resistance, but are insoluble in various solvents and have poor moldability. Further, there is a problem that the moldability is excellent but the heat resistance is poor.

[0003]

[Objective] An object of the present invention is to provide a novel aromatic polyester excellent in moldability because it is heat resistant and soluble in various solvents, and a process for producing the same.

[0004]

The first aspect of the present invention is the formula

[Chemical 2] And an aromatic polyester having a repeating unit represented by: A second aspect of the present invention is an aqueous medium (aqueous phase) containing 4,4'-hexafluoroisopropylidenediphenol.
And an organic medium (organic phase) obtained by dissolving 2,7-naphthalenedicarboxylic acid halide in an organic solvent immiscible with the aqueous medium in the presence of a phase transfer catalyst to carry out an interfacial polycondensation reaction. The present invention relates to a method for producing an aromatic polyester according to claim 1.

According to this 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 the 4,4'-hexafluoroisopropylidene diphenol. The concentration of 4,4'-hexafluoroisopropylidene diphenols in the aqueous medium is not strictly limited, but is generally 0.1 to 10 mol / l, preferably 0.2 to 5 mo.
A range of 1 / l is convenient. Further, this aqueous phase preferably contains a neutralizing agent for trapping and neutralizing hydrogen halide by-produced in the polycondensation reaction. As such a neutralizing agent, sodium hydroxide, Examples thereof include hydroxides, carbonates or hydrogen carbonates of alkali metals or alkaline earth metals such as potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate and sodium hydrogen carbonate. Sodium is preferred. These neutralizing agents can be usually present in the aqueous phase at a concentration of about 0.5 to 2M, preferably about 0.9 to 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 suitable and can be used to dissolve these acid halide components. As the organic solvent, for example,
Halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and sym-tetrachloroethane and aromatic hydrocarbons such as benzene, toluene, anisole, chlorobenzene, acetophenone, benzonitrile and nitrobenzene are included, Toluene is particularly suitable. The concentration of the naphthalene dicarboxylic acid halide in these solvents is not particularly limited, but the concentration of 2,7-naphthalenedicarboxylic acid halide is generally 0.05 to 1 mol / l, and particularly 0.1 to 0.5 mo.
It is suitable to set it within the range of 1 / l. Further, as the phase transfer catalyst, for example, tetrabutylammonium chloride (TBAC), benzyltriethylammonium chloride, benzyltriphenylphosphonium bromide (CTBPB), 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 usually range from 0 to based on the acid chloride component.
It can be used within a range of 4 mol%, preferably 1 to 3 mol%. The contact between the aqueous phase and the organic phase is usually performed with stirring. The reaction can be performed generally at 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 1 to 1.5 of 4,4'-hexafluoroisopropylidenediphenol in the aqueous phase with respect to 1 mol of the total amount of the acid halide component in the organic phase. It is suitable to adjust so that the amount becomes mol.

The method for producing the aromatic polyester of the present invention is not limited to the above-mentioned interfacial polycondensation method, but a known melt transesterification method (see, for example, Japanese Patent Publication No. 50-31918).
Can be done at. The method for producing an aromatic polyester of the present invention by the melt transesterification method is (a) converting 4,4'-hexafluoroisopropylidene diphenol into a diester, mixing the diester with 2,7-naphthalenedicarboxylic acid, and performing transesterification. Melt and react in the presence of a catalyst, or (b) mix 4,4'-hexafluoroisopropylidene diphenol with 2,7-naphthalene dicarboxylic acid diaryl ester and melt and react in the presence of a transesterification catalyst. Can be done by method. Examples of the diester of 4,4'-hexafluoroisopropylidene diphenol that can be used here include diacetate, propionate and benzoate of 4,4'-hexafluoroisopropylidene diphenol. As the diaryl ester of 2,7-naphthalenedicarboxylic acid, diphenyl ester is particularly preferable. This transesterification method is carried out at a temperature at which both monomer components are melted, generally 180 ° C. or higher, preferably 2
It can be carried out under any pressure, preferably under reduced pressure, at a temperature of 50 ° C. or higher and in a range in which the monomer component is not thermally decomposed, more preferably in a range of 280 to 310 ° C. Further, as the transesterification catalyst that can be used in the reaction, for example, titanium tetrabutoxide, titanium tetraethoxide, titanium compounds such as titanyl oxalate are suitable, but in addition, antimony trioxide, zinc acetate, manganese acetate and the like. Can also be used. It is convenient to use these in a catalytic amount, for example, 0.005 to 1.0 mol%, particularly 0.05 to 0.5 mol% based on the total amount of the acid components.

In the production of the aromatic polyester of the present invention, the diol component is, for example, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, in addition to 4,4'-hexafluoroisopropylidenediphenol. , Heptanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-2-methyl-1,
3-propanediol, triethylene glycol, 2,
As diols such as 2,4,4-tetramethylcyclobutanediol and / or dicarboxylic acid component, 2,
In addition to 7-naphthalenedicarboxylic acid, for example, 2,7
Other isomers of naphthalene dicarboxylic acid other than naphthalene dicarboxylic acid; terephthalic acid, isophthalic acid, diphenyl sulfone dicarboxylic acid, diphenoxyethane dicarboxylic acid, dicarboxylic acids such as adipic acid, sebacic acid, and / or p-oxybenzoic acid , M-oxybenzoic acid, 3-chloro-4-oxybenzoic acid, 3-methoxy-
A small amount of oxyacid such as 4-benzoic acid, 2,6-oxynaphthoic acid and 1,4-oxynaphthoic acid, which does not substantially impair the physical properties of the aromatic copolyester of the present invention, for example, 15 You may mix | blend in the quantity of mol% or less.

The aromatic polyester of the present invention has a high glass transition temperature and excellent heat resistance, is soluble in various organic solvents and has excellent moldability, and further has high strength and high elastic modulus. Therefore, it can be widely used for applications such as molded articles, films, fibers, paints, adhesives, etc. in the fields of electricity, automobiles, machines, and medical miscellaneous goods. When used for such applications, the aromatic copolyester of the present invention contains a reinforcing agent such as glass fiber, carbon fiber and asbestos; a filler, a nucleating agent, a flame retardant, a pigment, an antioxidant, a heat stabilizer. Additives such as agents, ultraviolet absorbers, anti-coloring agents, plasticizers, lubricants, release agents, etc. can be blended, or they can be kneaded with other thermoplastic resins.

[0009]

EXAMPLES Next, the present invention will be described more specifically by way of examples. The physical properties were measured according to the following methods. Viscosity ηinh: 0.1 g of the polymer was dissolved in 20 ml of phenol / tetrachloroethane (50/50) (0.
5 g / dl), 10 ml of which is placed in an Ostwald viscometer, put in a thermostatic layer at 30 ° C., and the drop time is measured (t). Next, the same measurement is performed using only the measurement solvent (t ₀ ).
The intrinsic viscosity ηinh is calculated from these values using the following formula.

## EQU1 ## ηinh = 1n (t / t ₀ ) /0.5 Note) As a guide for t ₀ , measure with a viscometer for about 120 seconds. Glass transition point (Tg): measured using a differential scanning calorimeter (DSC-20 type) manufactured by Seiko Instruments Inc. About 10 mg of the obtained polymer was precisely weighed in an aluminum pan, heated from 50 ° C. to 400 ° C. at 10 ° C./min in a nitrogen gas stream, and the first inflection point peak was taken as Tg. Thermal decomposition temperature: Measured using a differential thermogravimetric simultaneous measurement device (Tg / DTA-20 type) manufactured by Seiko Denshi Kogyo KK Precisely weigh about 10 mg in a platinum pan, and air gas flow 10 ° C /
The temperature was raised at min and the 10% wt weight loss point was set as the thermal decomposition temperature. Softening temperature: Measured using a Shimadzu thermomechanical analyzer (TMA-40 type). A sample having a thickness of about 50 μm is placed on the sample table, and a quartz glass needle having a diameter of 0.5 mm is placed on the sample with a load of 5 g. The temperature is raised at 10 ° C./min in a nitrogen gas stream, and the temperature at which the quartz glass needle starts to penetrate the sample is measured. Solubility: The measurement solvent was placed in a test tube, 1 to 3% of the polymer was put therein, and the mixture was allowed to stand at room temperature for 24 hours, and the solubility was visually determined. Further, after being left for 24 hours, those which were melted by heat and in which the polymer did not precipitate even when cooled were regarded as melted. Tensile strength, elongation, tensile modulus: ASTM D-using RTM-25rtm manufactured by Toyo Baldwin
822-83. Film length 120m
m, width 100 mm, and 10 mm both ends are bonded with paper so that the test piece does not slip from the grip. Measure the thickness at 5 points with a thickness gauge and use the average as the thickness. Clamp with the test piece grip and adjust the distance between grips to 100 mm. Load at a pulling speed of 50 mm / min with a load of 10 kg-
Record the elongation curve and calculate the tensile strength and elongation from the following formula.

[Equation 2] Tensile strength (kgf / mm ² ) = maximum load k
gf / cross-sectional area mm ²

## EQU00003 ## Elongation (%) = (elongation mm-100 mm) / 100 mm The film is cut into a length of 270 mm and a width of 10 mm, and both ends are
A test piece is prepared by bonding 0 mm with paper. Measure the thickness at 5 points with a thickness gauge and use the average as the thickness. Grip the test piece with the grip and adjust the distance between the grips to 250 mm. The load-elongation curve is recorded at a tensile speed of 25 mm / min with a load of 10 kg, and the tensile elastic modulus is calculated from the following formula.

[Equation 4] Tensile elastic modulus (kgf / mm ² ) = 1 mm Load required to stretch kgf / mm · 250 mm / cross-sectional area mm ²

Example 1 20.4 ml of 1M sodium hydroxide aqueous solution was placed in a three-necked flask equipped with a mechanical stirrer, and 3,362 g of 4,4'-hexafluoroisopropylidenediphenol.
(10 mmol) and 0.06 g of benzyltriethylammonium chloride are added and dissolved. 2,7 in this solution
-Naphthalene dicarbonyl dichloride 2.531 g (1
0 mmol) in 28 ml of nitrobenzene is added at once with stirring and stirred at room temperature for 100 minutes at a stirring speed of 800 rpm. Thereafter, the polymerization solution is allowed to stand and separate to separate the polymer-containing nitrobenzene solution, which is then washed with acetic acid water and further 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. 3 g of the obtained polymer was completely dissolved in 20 ml of tetrachloroethane, and this solution was placed on a glass plate whose surface was washed.
Cast using a glass rod. Place this glass plate horizontally in a vacuum dryer for 12 hours at room temperature, 12 hours at 80 ° C,
A film was prepared by drying at 150 ° C. for 24 hours. The intrinsic viscosity ηinh of the polymer, the glass transition temperature Tg, the softening temperature, the thermal decomposition temperature, the solubility, and the properties of the film are shown in Table 1 below.
~ 2.

Comparative Example 1 20.4 ml of 1M sodium hydroxide aqueous solution was placed in a three-necked flask equipped with a mechanical stirrer, and 2,284 g (10 mmol) of 4,4'-isopropylidenediphenol.
And benzyltriethylammonium chloride 0.06g
Add and dissolve. To this solution, 2.531 g (10 mmol) of 2,7-naphthalene dicarbonyl dichloride was added 4
A solution dissolved in 2 ml of nitrobenzene is added at once with stirring and stirred at room temperature for 100 minutes at a stirring speed of 800 rpm. Thereafter, the polymerization solution is allowed to stand and separate to separate the polymer-containing nitrobenzene solution, which is then washed with acetic acid water and further 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. 3 g of the obtained polymer
Is completely dissolved in 20 ml of tetrachloroethane, and this solution is cast on a glass plate whose surface has been washed using a glass rod. Place the glass plate horizontally in a vacuum dryer for 12 hours at room temperature, 12 hours at 80 ° C, 24 hours at 150 ° C.
It was dried for an hour to make a film. The intrinsic viscosity ηinh of the polymer, the glass transition temperature Tg, the softening temperature, the thermal decomposition temperature, the solubility, and the properties of the film are shown in Table 1 below, and the tensile strength, elongation, and tensile elastic modulus are shown in Table 2 below. (Below margin)

[0012]

[Table 1] *: A = o-chlorophenol, B = sym-tetrachloroethane, C = chloroform, D = pyridine, E =
1,2-dichloroethane, F = anisole, G = o-dichlorobenzene, H = acetophenone, I = acrylonitrile, J = nitrobenzene, K = phenol, L = m
-Cresol, M = N-methyl-2-pyrrolidone, N =
Dimethylacetamide, O = THF, P = phenol /
sym-tetrachloroethane (50/50)

[Table 2]

[0013]

[Effect] The aromatic polyester of the present invention is a novel aromatic polyester, has a high glass transition temperature and excellent heat resistance, and is soluble in various organic solvents, so that it can be easily molded. I have In addition, this resin is colorless and transparent and has excellent mechanical properties such as high strength and high elastic modulus.

Front page continuation (72) Inventor Shigenori Sakuma 3-5 Kasumigaseki, Chiyoda-ku, Tokyo Showa Shell Sekiyu Co., Ltd. (72) Yoshio Kadokura 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Showa Shell Petroleum Co., Ltd.

Claims (2)

[Claims] 1. The formula: An aromatic polyester having a repeating unit represented by: 2. Correlation between an aqueous medium containing 4,4′-hexafluoroisopropylidenediphenol and an organic medium in which 2,7-naphthalenedicarboxylic acid halide is dissolved in an organic solvent immiscible with the aqueous medium. The method for producing an aromatic polyester according to claim 1, wherein the interfacial polycondensation reaction is carried out by bringing them into contact with each other in the presence of a transfer catalyst.