JPH0713132B2 - Aromatic polyester resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a novel aromatic polyester resin capable of being melt-molded and having excellent mechanical properties and heat resistance.

<Prior Art> In recent years, the demand for higher performance of plastics has increased more and more, and many polymers having various new performances have been developed and put on the market, and in particular, they are characterized by a parallel arrangement of molecular chains. A liquid crystal polymer having optical anisotropy that has excellent mechanical properties has been attracting attention (Japanese Patent Publication No. 55-48).
No. 2 bulletin).

<Problems to be Solved by the Invention> However, although the mechanical properties of molded articles made from these polymers are excellent in the flow direction, they have the property of being extremely low in the flow direction and in the direction perpendicular to the film.
It was found that the mechanical properties of molded products such as resins have a large anisotropy.

On the other hand, an aromatic polyester composed of bisphenol A and terephthalic acid and isophthalic acid is isotropic, and its mechanical properties have little anisotropy, but mechanical properties are poor due to poor symmetry of bisphenol A and isophthalic acid structures. Was found to be defective.

Therefore, the present invention aims to obtain a molded article having a small amount of anisotropy and good mechanical properties if an aromatic polyester having a relatively good molecular structure with symmetry and being isotropic can be obtained. As a subject, various aromatic polyesters have been studied, and it has been found that the aromatic polyester having the following structure is specifically isotropic and can be melt-molded at 400 ° C. or less, and the present invention has been completed.

<Means for Solving the Problems> That is, the present invention comprises a main constituent component of a repeating unit represented by the following structural unit (I), and when dissolved in pentafluorophenol at a concentration of 0.1 g / dl at 60 ° C. The present invention provides a melt-moldable aromatic polyester resin having a logarithmic viscosity of 0.4 to 20 dl / g.

(However, R in the formula is Represents one or more groups selected from the following, and X and Y are X = Y =
H, shows the X = Y = Cl, X = Cl and Y = H, one or more groups selected from a combination of X = OCH ₃ and Y = H. In the aromatic polyester resin of the present invention, the structural unit (I) is cyclohexylhydroquinone, methylbenzylhydroquinone, dimethylbenzylhydroquinone, 4,4'-dihydroxydiphenyl ether, 2-
One or more dihydroxy compounds selected from (P-hydroxyphenyl) ethanol, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4, 4'-dicarboxylic acid, 1,2-
From one or more dicarboxylic acids selected from bis (2,6-dichlorophenoxy) ethane-4,4'-dicarboxylic acid and 1,2-bis (2-methoxyphenoxy) ethane-4,4'-dicarboxylic acid It means the structural unit of the produced polyester, respectively.

The aromatic polyester of the present invention has a melting point of 400 ° C. or less, and a molded product such as a fiber, a film, or a resin having excellent mechanical properties can be easily obtained by ordinary melt molding.

Aromatic polyesters obtained by using, for example, methylhydroquinone or chlorohydroquinone instead of the dihydroxy compound of the present invention have optical anisotropy, and give 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid and / or
Or nuclear-substituted 1,2-bis (phenoxy) ethane-4,4'-
500 ° C if terephthalic acid is used instead of dicarboxylic acid
Since the above-mentioned high melting point is obtained, the object of the present invention cannot be achieved, and the object of the present invention can be achieved only by the aromatic polyester resin of the present invention.

In the present invention, in addition to the dioxy compound and the dicarboxylic acid component, in a small proportion, terephthalic acid, a dicarboxylic acid component such as 4,4'-diphenyldicarboxylic acid, hydroquinone, chlorohydroquinone, methylhydroquinone, 4,4'-dihydroxy. It is also possible to further copolymerize a diol component such as biphenyl, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene and an oxycarboxylic acid such as p-oxybenzoic acid.

The aromatic polyester resin of the present invention has an intrinsic viscosity of 60.
The logarithmic viscosity is 0.40 to 20.0 when dissolved at a concentration of 0.1 g / dl in pentafluorophenol at ℃. Intrinsic viscosity is 0.
When it is less than 40, the strength of the obtained molded product is low, and when it is more than 20.0, the melt molding becomes difficult.

The aromatic polyester resin of the present invention can be produced according to the conventional polyester polycondensation method, and the production method is not particularly limited, but typical production methods include, for example, the following (1) to
(3) Method is mentioned.

(1) A method of producing from the above aromatic diol, acetic anhydride and the above aromatic dicarboxylic acid by a decondensation polycondensation reaction.

(2) A method for producing the acylated product of the aromatic diol and the aromatic dicarboxylic acid by deacetic acid polycondensation reaction.

(3) A method for producing from the above-mentioned aromatic dicarboxylic acid diphenyl ester compound and the above aromatic diol by dephenol polycondensation reaction.

In particular, the method (1) or (2) is preferable in that the polycondensation reaction proceeds without a catalyst, and acetic acid
Metal compounds such as tin, tetrabutyl titanate, lead acetate and antimony oxide, cobalt acetate, sodium acetate can also be used.

The aromatic polyester resin of the present invention thus obtained has a temperature of 400 ° C.
It can be melt-molded below and can be subjected to normal melt-molding such as extrusion molding, injection molding, compression molding and blow molding, and can be processed into fibers, films, three-dimensional molded products, containers, hoses, etc. Yes, and can be easily blended with other thermoplastic polymers.

At the time of molding, with respect to the aromatic polyester resin of the present invention, glass fiber, carbon fiber, a reinforcing agent such as asbestos,
Additives such as a filler, a nucleating agent, a pigment, an antioxidant, a stabilizer, a plasticizer, a lubricant and a release agent can be added to impart desired properties to the molded article.

Molded articles obtained from the novel aromatic polyester resin of the present invention are characterized in that they can be melt-molded at 400 ° C or lower and have excellent mechanical properties.

<Example> The present invention will be further described by the following examples.

Example 1 13.75 g (5 × 10 ^-2 mol) of cyclohexylhydroquinone diacetate and 18.6 g (5) of 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid were placed in a polymerization test tube.
(× 10 ^-2 mol) was charged and the deacetic acid polycondensation reaction was carried out under the following conditions. First, the reaction was carried out in a nitrogen gas atmosphere at 250 to 330 ° C. for 2 hours, the pressure was reduced to 3 mmHg, and the mixture was further heated for 0.5 hour. When the polycondensation reaction was completed, a theoretical amount of acetic acid was distilled,
A brown polymer was obtained.

The theoretical structural formula of this polymer is as follows, and the elemental analysis results of the polyester showed good agreement with the theoretical values as shown in Table 1.

However, the oxygen content (%) is (100% -C% -H% -Cl%)
Calculated from As a result of confirming the melting point and the optical anisotropy by placing this polyester on a sample stage of a polarizing microscope and raising the temperature, it was found that the melting point was 235 ° C. and it was optically isotropic.

Differential scanning calorimeter (Perkin Elmer II type)
The glass transition temperature was 133 ° C., but the melting peak could not be detected.

The intrinsic viscosity (measured in pentafluorophenol at 60 ° C) was 1.0.

Example 2 As in Example 1, 4,4'-diacetoxydiphenyl ether 14.3 g (5 x 10 ^-2 mol) and 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid 18.5 g ( 5
(× 10 ^-2 mol) was charged and reacted in a nitrogen atmosphere at 250 to 310 ° C for 2 hours, then depressurized to 0.8 mmHg and further heated for 1 hour to complete the polycondensation reaction, and a theoretical amount of acetic acid was distilled off. A brown polymer was obtained.

The theoretical structural formula of this polymer is as follows, and the elemental analysis values of the polyester showed good agreement with the theoretical values as shown in Table 2.

However, the oxygen content (%) is (100% -C% -H% -Cl
%).

The polyester was placed on a sample stage of a polarizing microscope and heated to confirm the optical anisotropy. As a result, it was found that the melting point was 286 ° C. and it was optically isotropic.

When the polymer was measured with a differential calorimeter, the glass transition temperature was 118 ° C, the melting point was 270,287 ° C, the heat of fusion was 8.0 cal / g, the crystallization temperature was 202.5 ° C, and the heat of crystallization was 6.94 cal / g.

The intrinsic viscosity (measured in pentafluorophenol at 60 ° C) was 1.6.

Example 3 2- (p-acetoxyphenyl) -1-in a polymerization test tube
(Acetoxy) ethane 11.1 g (5 × 10 ^-2 mol) and 1,2
18.6 g (5 × 10 ^-2 mol) of -bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid was charged and the deacetic acid polycondensation reaction was carried out under the following conditions. First, 25 in a nitrogen gas atmosphere
After reacting at 0 to 330 ° C for 1.5 hours, the pressure was reduced to 1.5 mmHg, and the mixture was further heated for 1.0 hour to complete the polycondensation reaction. About the theoretical amount of acetic acid was distilled off to obtain a brown polymer.

The theoretical structural formula of this polymer is as follows, and the elemental analysis values of the polyester showed good agreement with the theoretical values as shown in Table 3.

However, the oxygen content (%) is (100% -C% -H% -Cl
%).

The polyester was placed on a sample stage of a polarization microscope and the temperature was raised to confirm the optical anisotropy. As a result, the melting point was 245 ° C.,
It was found to be optically isotropic.

When the polymer was measured with a differential scanning calorimeter, the glass transition temperature was 97 ° C, the melting point was 199,245 ° C, the heat of fusion was 3.1,9.5 cal / g, the crystallization temperature was 197 ° C, and the heat of crystallization was 6.9 cal.

The intrinsic viscosity (measured in pentafluorophenol at 60 ° C) was 1.2.

Example 4 A polymerization test tube was charged with 10.7 g of methylbenzyl hydroquinone (5
× 10 ^-2 mol) or dimethylbenzylhydroquinone 1
1.9 g (5 x 10 ^-2 mol) and 1, 2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid 18.5 g (5 x 10
^-2 mol) was charged and reacted in a nitrogen atmosphere at 250 to 330 ° C. for 1 hour, then depressurized to 2 mmHg, and further heated for 1 hour to complete the polycondensation reaction. A polymer was obtained.

These polymers are optically isotropic above 300 ° C,
The glass transition temperatures were 121 and 125 ° C., respectively, as measured by a differential scanning calorimeter. The intrinsic viscosities (measured in pentafluorophenol at 60 ° C) were 1.7 and 1.1, respectively.

<Effects of the Present Invention> The aromatic polyester resin of the present invention can be melt-molded at 400 ° C. or lower, and a molded product having little anisotropy and good mechanical properties can be obtained, which is used for engineering plastics and other uses. can do.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-61-106622 (JP, A) JP-A-60-188420 (JP, A) JP-A-62-39625 (JP, A) JP-B-63- 33773 (JP, B2) JP 63-35172 (JP, B2) JP 62-45891 (JP, B2)

Claims (1)

[Claims] 1. A logarithmic viscosity of 0.4 to 20 when dissolved at a concentration of 0.1 g / dl in pentafluorophenol at 60 ° C., which is composed of main constituent components of a repeating unit represented by the following structural unit (I).
Melt-moldable aromatic polyester resin characterized by dl / g. (However, R in the formula is Represents one or more groups selected from the following, and X and Y are X = Y =
One or more groups selected from the combination of H, X = Y = Cl, X = H and Y = Cl, X = OCH ₃ and Y = H are shown. )