JPH07695B2 - Aromatic polyester - Google Patents

Description

TECHNICAL FIELD The present invention relates to an aromatic polyester excellent in mechanical strength such as heat resistance, flexural rigidity, tensile strength and impact resistance, and high temperature hydrolysis resistance. More specifically, it relates to an aromatic polyester capable of forming a molded body or fibers excellent in these properties.

[Conventional technology]

Paraoxybenzoic acid polyester is conventionally known as an aromatic polyester having excellent heat resistance. The polyester has drawbacks such as that it is difficult to obtain a polyester having a large molecular weight, and that it is not possible to adopt a usual melt molding method such as injection molding or extrusion molding because thermal decomposition is remarkable during melting. Is industrially rarely used.

Also, as an attempt to improve these drawbacks of the paraoxybenzoic acid polyester, many aromatic polyesters obtained by co-condensing various aromatic dicarboxylic acid components and various aromatic diol components have been proposed (for example, JP-A-47-47870, JP-A-47-11697, JP-A-55-66924, JP-A-54-50594, JP-A-54
-77691, JP-A-55-144024, JP-A-56-9922
5, JP 56-136818 JP, JP 56-141317 JP, JP 57-87423 JP, JP 58-1720 JP,
JP-A-58-29819, JP-A-58-29820, JP-A-58-29820
58-32630, JP 59-62630, JP 55-135
134 publication, JP 56-47423 JP, JP 56-50921 JP, JP 56-50922 JP, JP 58-67719 JP,
JP-A-53-35794, JP-A-58-53920, JP-A-SHO
53-91721, JP-A-58-194530, JP-A-59-41
328, JP-A-50-66593, JP-A-50-108392, JP-A-58-65629, JP-A-59-918117, JP-A-53-24391, JP-A-55-149321,
JP-A-52-98087, JP-A-52-98088, JP-A-52-98088
52-121619, JP-A-53-47492, JP-A-53-11
0696, JP-A-53-136098, JP-A-54-43296
JP-A-54-136098, JP-A-56-59843, JP-A-58-45224, etc.]. According to these methods proposed in the prior art, the melt moldability is improved because the polycondensation surely causes the melting at a lower temperature than the paraoxybenzoic acid polyester, but
Along with this, heat resistance is lowered, and further, mechanical properties such as flexural rigidity, tensile strength and impact resistance are lowered, and chemical resistance and water resistance are often lowered.

[Problems to be solved by the invention]

The present inventors have conducted extensive studies on a novel aromatic polyester excellent in heat resistance, melt moldability, bending rigidity, tensile strength, and impact resistance, and as a result, found that a paraoxybenzoic acid component unit was selected. An aromatic polyester having a specific composition comprising an oxybenzoic acid component unit (A), a specific aromatic diol component unit (B), and a specific aromatic dicarboxylic acid component unit (C) as the main components, achieves the above object. The present invention has been achieved and has reached the present invention.

[Means for solving problems]

According to the present invention, (A) an oxybenzoic acid component unit whose main component is a paraoxybenzoic acid component unit is in a range of 50 to 90 mol%, and (B) a main component is a dihydroxynaphthalene component unit or a dihydroxydiphenyl ether component unit. Aromatic diol component unit is in the range of 5 to 25 mol%, and (C) aromatic dicarboxylic acid component unit containing dicarboxyphenyl ether component unit as the main component is 5 to 25 mol%
The oxybenzoic acid component unit (A), the aromatic diol component unit (B) and the aromatic dicarboxylic acid component unit (C) are randomly arranged, respectively, and are substantially amorphous. The softening point (Ts) measured by a thermomechanical analyzer (TMA) is 250 to 450 ° C, and the melt viscosity measured at 250 to 450 ° C, 100sec ^-1 is in the range of 10 ² to 10 ⁶ poises. A melt-moldable aromatic polyester is provided.

The oxybenzoic acid component unit (A) containing a paraoxybenzoic acid component unit as a main component constituting the aromatic polyester of the present invention may be composed of only the paraoxybenzoic acid component unit, or in addition to the paraoxybenzoic acid component unit. It does not matter if it contains a small amount of the unit component of metaoxybenzoic acid. The content of the paraoxybenzoic acid component unit in the oxybenzoic acid component unit (A) is, for example, 90 mol% or more, preferably 95 mol% or more.

The content of the oxybenzoic acid component unit (A) constituting the aromatic polyester of the present invention is in the range of 50 to 90 mol%, preferably 60 to 85 mol%.

The aromatic diol component unit (B) constituting the aromatic polyester of the present invention is an aromatic diol component unit containing a dihydroxynaphthalene component unit or a dihydroxydiphenyl ether component unit as a main component, and a dihydroxynaphthalene component unit or dihydroxydiphenyl component unit. It may consist of an ether component unit alone, or may contain a small amount of another aromatic diol component unit in addition to the dividroxynaphthalene component unit or dihydroxydiphenyl ether component unit. The dihydroxynaphthalene component unit in the aromatic diol component unit is 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4
-Dihydroxynaphthalene, 1,5-dihydroxynaphthalene and the like can be exemplified, and as the dihydroxydiphenyl ether component unit, 4,4'-dihydroxydiphenyl ether, 3,4'-dihydroxydiphenyl ether, 3,3 ' -Dihydroxydiphenyl ether and the like can be exemplified. The content of the dihydroxynaphthalene component unit or the dihydroxydiphenyl ether component unit in the aromatic diol component unit is, for example, 90 mol% or more, preferably 95 mol% or more.

The aromatic diol component units other than the dihydroxynaphthalene component unit or the dihydroxydiphenyl ether component unit contained in the aromatic diol component unit (B) include hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, bis ( 4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2
Examples thereof include aromatic diol component units having 6 to 15 carbon atoms such as -bis (4-hydroxyphenyl) propane.

The content of the aromatic diol component unit (B) constituting the aromatic polyester of the present invention is in the range of 5 to 25 mol%, preferably 7.5 to 20 mol%.

The aromatic dicarboxylic acid component unit (C) constituting the aromatic polyester of the present invention is an aromatic dicarboxylic acid component unit containing a dicarboxydiphenyl ether component unit as a main component, and is composed of only a dicarboxydiphenyl ether component unit. In addition to the dicarboxydiphenyl ether component unit, a small amount of other aromatic dicarboxylic acid component unit may be contained. Examples of the dicarboxydiphenyl ether unit include 4,4'-dicarbocidiphenyl ether, 3,4'-dicarboxydiphenyl ether, and 3,3'-dicarbodidiphenyl ether. The content of the dicarboxydiphenyl ether component unit in the aromatic dicarboxylic acid component unit (C) is, for example, 90 mol% or more, preferably 95 mol%.
It is the above range.

Examples of the aromatic dicarboxylic acid component unit other than the dicarboxydiphenyl ether component unit contained in the aromatic dicarboxylic acid component unit (C) include 4,4′-dicarboxydiphenyl, terephthalic acid, isophthalic acid, 2,6 Examples thereof include aromatic dicarboxylic acid component units having 8 to 15 carbon atoms such as -dicarboxynaphthalene and 2,7-dicarboxynaphthalene.

The content of the aromatic dicarboxylic acid component unit (C) constituting the aromatic polyester of the present invention is in the range of 5 to 25 mol%, preferably 7.5 to 20 mol%.

In the aromatic polyester of the present invention, the oxybenzoic acid component unit (A) has the general formula [I] [Wherein, as in the above-mentioned formula, a 1,4-bond is the main component and may also contain a 1,3-bond], and the aromatic diol component unit (B) is represented by the general formula [II ] -O-Ar'-O- [II] [wherein -Ar'-is the same as above. And may further contain a divalent aromatic hydrocarbon having 6 to 15 carbon atoms), and the aromatic dicarboxylic acid component unit (C) is represented by the general formula [III] [In the formula, -Ar ² -is the same as above. Is a main component and may further contain a divalent aromatic group having 6 to 13 carbon atoms). In the aromatic polyester of the present invention, the oxybenzoic acid component unit (A), the aromatic diol component unit (B) and the aromatic dicarboxylic acid component unit (C) are randomly arranged to form an ester bond. , Forming a cotton-like aromatic polyester. The oxybenzoic acid component unit (A) may be arranged at the molecular end of the aromatic polyester, or the aromatic diol component unit (B) may be arranged at the molecular end of the aromatic dicarboxylic acid. The acid component unit (C) may be arranged. Further, the carboxyl group at the molecular end of the aromatic polyester of the present invention is methanol,
It may be esterified with a monohydric alcohol such as ethanol or isopropanol or a monohydric phenol such as phenol or cresol. Similarly, the hydroxyl group at the molecular end is a monovalent carboxylic acid such as acetic acid, propionic acid or benzoic acid. It may be esterified with an acid.

The melt viscosity of the aromatic polyester of the present invention measured at 250 to 450 ° C., for example, a temperature 30 ° C. higher than the softening point (Ts) at 100 sec ⁻¹ , is 10 ² to 10 ⁶ boise, preferably 2 × 10 ² to 10 ⁵ boise. Is the range.

The melting point (Tm) and glass transition temperature (Tg) of the aromatic polyesters of the present invention are usually not detected by Differential Scanning Calorimetry (DSC) and therefore the aromatic polyester is substantially amorphous and thermomechanical. Narizer (TMA)
The softening point (Ts) measured in (4) is preferably in the range of 250 to 400 ° C.

The aromatic polyester of the present invention can be produced by the following method. That is, a low-boiling compound produced by reacting the oxycarboxylic acid ester molding derivative, the aromatic dicarboxylic acid or its ester molding derivative and the ester-forming derivative of the aromatic diol under melting conditions and reduced pressure conditions at high temperature. Aromatic polyester can be produced by distilling out of the reaction system. For example, the acetic acid ester of the oxycarboxylic acid, the bisacetic acid ester of the aromatic dicarboxylic acid and the aromatic diol are usually added at a temperature of 200 to 450 ° C., preferably 250 to 400 ° C. under a normal pressure to a pressure of 0.1 mmHg. The aromatic polyester of the present invention can be produced by a method of carrying out a polycondensation reaction by distilling off the acetic acid produced by the reaction. Further, the phenol ester of the oxycarboxylic acid, the bisphenol ester of the aromatic dicarboxylic acid and the aromatic diol are usually added at a temperature of 200 to 450 ° C., preferably 250 to 400 ° C. under a normal pressure to a pressure of 0.1 mmHg. The aromatic polyester of the present invention can also be produced by a method of carrying out a polycondensation reaction by distilling off the phenol produced by the reaction by reacting. Although a catalyst may not be used in the polycondensation reaction, examples of the catalyst that can be used in the polycondensation reaction include aluminum acetate, calcium acetate, magnesium acetate, potassium acetate, sodium acetate, potassium phosphate, sodium sulfate, acetic acid. copper,
Examples thereof include antimony oxide, tetrabutoxy titanium, tin acetate and the like. The proportion used is usually 0.0001 to 1% by weight, preferably 0.001 based on the polycondensation raw material.
To 0.1% by weight.

The aromatic polyester of the present invention can be used for various heat resistant molding applications. For example, in addition to the fact that a molded body can be manufactured by ordinary injection molding and extrusion molding, it can be molded into a fibrous shape by a melt spinning method which is usually performed with polyethylene terephthalate or the like.

(Effects of the Invention) The aromatic polyester of the present invention is excellent in heat resistance, flexural rigidity and mechanical strength such as tensile strength and impact strength, excellent in high temperature hydrolysis resistance, and further excellent in melt moldability. Therefore, it can be used in the field of heat-resistant molded articles and fibers.

〔Example〕

The aromatic polyester of the present invention will be specifically described with reference to examples.

The performance of the aromatic copolyester was evaluated according to the following method.

Tm, Tg: Perkin Elmer differential scanning calorimeter (DSCII
Type), synthetic polyester as it is about 10mg
To raise the temperature from 50 ° C to 400 ° C at a rate of 20 ° C / min, then decrease the temperature to 50 ° C at 40 ° C / min, and again to 400 ° C.
The temperature was raised at 0 ° C / min. Tm adopts the endothermic peak value at the 1st and 2nd temperature rise, and Tg is the value at the 2nd temperature rise (first inflection point)
It was adopted.

Ts: Using a 942 type thermomechanical analyzer (TMA) manufactured by Dupont Co., a press sheet with a thickness of 1 mm, a quartz glass needle (diameter 25 mil) at a temperature rising rate of 20 ° C / min and a load of 50 g.
The point where the needle was inserted by 0.1 mm was defined as Ts.

Heat distortion temperature (HDT): Measured according to ASTM D 648 (load 18.6 Kg / cm ² ).

Melt viscosity: Measured at a shear rate of 100 sec ^-1 using a Shimadzu-made capillary rheometer.

Storage elastic modulus (E '): Using Vibron-DDV-III from Toyo Baldwin
It was measured at 23 ° C. and 110 Hz.

Example 1 A polyester composed of 80 mol% of p-oxybenzoic acid unit, 10 mol% of 4,4'-dihydroxydiphenyl ether unit and 10 mol% of 4,4'-dicarboxydiphenyl ether unit was synthesized as follows. In a 500 ml reactor, p-acetoxybenzoic acid 144 g (0.8 mol), 4,4'-diacetoxydiphenyl ether 28.6 g (0.1 mol) and 4,4'-dicarboxydiphenyl ether 25.8 g (0.1 mol) It was placed,
Acetic acid was distilled off at 275 ° C. for 2 hours with stirring, then heated to 330 ° C. for 2 hours, cooled to room temperature, and the internal solution was pulverized to a size of 1 mm or less. Put this crushed material into the reactor and
Heat treatment at 1 mmHg for 1 hour each at 0 and 270 ℃, then 3
Heat treatment was performed at 00 ° C. for 24 hours at 1 mmHg.

No Tm or Tg of the polyester was detected. 342 ℃, 1
At 00 sec ^-1 , the melt viscosity was 1400 poise. When a press sheet was prepared at 350 ° C. and TMA, HDT, and vibron were measured, Ts was 312 ° C., HDT was 235 ° C., and E ′ at 23 ° C. was 3.8 GPa.

Example 2 A polyester composed of 80 mol% of p-oxybenzoic acid unit, 10 mol% of 3,4'-dihydroxydiphenyl ether unit and 10 mol% of 3,4'-dicarboxydiphenyl ether unit was synthesized as follows. In a 500 ml reactor, p-acetoxybenzoic acid 144 g (0.8 mol), 3,4'-diacetoxydiphenyl ether 28.6 g (0.1 mol), 3,4'-dicarboxydiphenyl ether 25.8 g (0.1 mol) , Acetic acid was distilled off for 2 hours at 275 ° C. under stirring, then 330 hours for 2 hours.
After the temperature was raised to ℃, it was cooled to room temperature and the internal solution was pulverized to a size of 1 mm or less. Put this crushed material into the reactor, 250, 270
Heat treatment at 1mmHg for 1 hour each at ℃, then at 300 ℃
Heat treatment was performed at 1 mmHg for 24 hours.

No Tm or Tg of the polyester was detected. 333 ° C, 1
The melt viscosity at 00 sec ^-1 was 1600 poise. Press sheets were made at 350 ℃ and TMA, HDT and vibron were measured. Ts was 303 ℃, HDT was 238 ℃, and E'at 23 ℃ was 4.3 GPa.
It was.

Comparative Example 1 A polyester comprising 40 mol% of p-oxybenzoic acid unit, 30 mol% of 4,4'-dihydroxydiphenyl ether unit and 30 mol% of 4,4'-dicarboxydiphenyl ether unit was synthesized as follows. In a 500 ml reactor, 72 g (0.4 mol) of p-acetoxybenzoic acid, 85.8 g (0.3 mol) of 4,4′-diacetoxydiphenyl ether, 77.5 g (0.3 mol) of 4,4′-dicarboxydiphenyl ether. , And distill acetic acid at 275 ° C for 2 hours with stirring, and then at 2 hours at 330 ° C.
After the temperature was raised to room temperature, it was cooled to room temperature and the internal solution was pulverized to a size of 1 mm or less. The crushed material was put into a reactor and the temperature was 1 at 250 ° C.
Heat treatment was carried out for 1 hour at 1 mmHg and then at 270 ° C. for 24 hours at 1 mmHg.

Tm of the polyester was not detected, but Tg was 136 ° C
It was. The melt viscosity at 159 ° C. and 100 sec ⁻¹ was 10 ⁶ poise or more. Create press sheet at 350 ℃, TMA, HD
When T and vibron were measured, Ts was 129 ° C and HDT was 116.
E'at 2.5 ° C and 23 ° C was 2.5 GPa.

Example 3 A polyester composed of 80 mol% of p-oxybenzoic acid unit, 10 mol% of 2,6-dihydroxynaphthalene unit and 10 mol% of 4,4'-dicarboxydiphenyl ether unit was synthesized as follows. In a 500 ml reactor, 144 g (0.8 mol) of p-acetoxybenzoic acid, 24 of 2,6-diacetoxynaphthalene.
After adding 4g (0.1mol) and 4,4'-dicarboxydiphenyl ether 25.8g (0.1mol), distill acetic acid at 275 ° C for 2 hours with stirring and then heating to 330 ° C for 2 hours. After cooling to room temperature, the internal solution was crushed to a size of 1 mm or less. This pulverized product was placed in a reactor and heat-treated at 1 mmHg at 250, 270, 290, 310, and 330 ° C. for 1 hour each, and then at 350 ° C. for 10 hours at 1 mmHg.

No Tm or Tg of the polyester was detected. 402 ° C, 1
The melt viscosity at 00 sec ^-1 was 1800 poise. A press sheet was prepared at 400 ℃, and TMA, HDT, and vibron were measured. Ts was 372 ℃, HDT was 316 ℃, and E'at 23 ℃ was 5.2 GPa.
It was.

Example 4 A polyester comprising 70 mol% of p-oxybenzoic acid unit, 15 mol% of 2,6-dihydroxynaphthalene unit and 15 mol% of 4,4'-dicarboxydiphenyl ether unit was synthesized as follows. In a 500 ml reactor, 126 g (0.7 mol) of p-acetoxybenzoic acid, 36 of 2,6-diacetoxynaphthalene.
After adding 6 g (0.15 mol) and 4,4'-dicarboxydiphenyl ether 38.7 g (0.15 mol), distilling acetic acid at 275 ° C for 2 hours with stirring, and then heating to 330 ° C for 2 hours After cooling to room temperature, the internal solution was crushed to a size of 1 mm or less. This crushed material was put into a reactor, heat-treated at 1 mmHg at 250, 270, 290 and 310 ° C for 1 hour each, and then at 330 ° C for 24 hours 1m.
It heat-processed by mHg.

No Tm or Tg of the polyester was detected. 371 ° C, 1
The melt viscosity at 00 sec ^-1 was 1400 poise. Press sheets were prepared at 400 ℃ and TMA, HDT and vibron were measured. Ts was 341 ℃, HDT was 283 ℃, and E'at 23 ℃ was 4.9 GPa.
It was.

Example 5 A polyester consisting of 60 mol% of p-oxybenzoic acid unit, 20 mol% of 2,6-dihydroxynaphthalene unit and 20 mol% of 4,4'-dicarboxydiphenyl ether unit was synthesized as follows. In a 500 ml reactor, p-acetoxybenzoic acid 108 g (0.6 mol), 2,6-diacetoxynaphthalene 48.
After adding 8g (0.2mol) and 4,4'-dicarboxydiphenyl ether 25.8g (0.1mol), distill acetic acid at 275 ° C for 2 hours with stirring, and then raise the temperature to 330 ° C in 2 hours. After cooling to room temperature, the internal solution was crushed to a size of 1 mm or less. Put this crushed material into the reactor and use 1 at 250, 270, and 290 ℃ respectively.
Heat treatment at 1mmHg for 1 hour, then at 310 ℃ for 24 hours at 1mmHg
Heat treated in.

No Tm or Tg of the polyester was detected. 342 ℃, 1
At 00 sec ^-1 , the melt viscosity was 1500 poise. When a press sheet was prepared at 350 ° C. and TMA, HDT, and vibron were measured, Ts was 312 ° C., HDT was 223 ° C., and E ′ at 23 ° C. was 4.6 GPa.

Example 6 A polyester composed of 70 mol% of p-oxybenzoic acid unit, 15 mol% of 2,6-dihydroxynaphthalene unit and 15 mol% of 3,4'-dicarboxydiphenyl ether unit was synthesized as follows. In a 500 ml reactor, 126 g (0.7 mol) of p-acetoxybenzoic acid, 36 of 2,6-diacetoxynaphthalene.
After adding 6g (0.15mol) and 3,4'-dicarboxydiphenyl ether 38.7g (0.15mol), distill acetic acid at 275 ° C for 2 hours with stirring and then heating to 330 ° C for 2 hours. After cooling to room temperature, the internal solution was crushed to a size of 1 mm or less. The crushed material was put into a reactor, heat-treated at 250, 270, 290, and 310 ° C for 1 hour, 1 mmHg, and then at 330 ° C for 10 hours.
Heat treatment was performed at 1 mmHg.

No Tm or Tg of the polyester was detected. 354 ° C, 1
At 00 sec ^-1 , the melt viscosity was 1600 poise. When a press sheet was prepared at 360 ° C and TMA, HDT, and vibron were measured, Ts was 324 ° C, HDT was 263 ° C, and E'at 23 ° C was 4.6 GPa.

Comparative Example 2 A polyester composed of 40 mol% of p-oxybenzoic acid unit, 30 mol% of 2,6-dihydroxynaphthalene unit and 30 mol% of 4,4'-dicarboxydiphenyl ether unit was synthesized as follows. In a 500 ml reactor, p-acetoxybenzoic acid 72 g (0.4 mol), 2,6-diacetoxynaphthalene 73.2
g (0.3mol), 4,4'-dicarboxydiphenyl ether
Add 77.4 g (0.3 mol), distill acetic acid at 275 ° C for 2 hours with stirring, then raise the temperature to 330 ° C in 2 hours, cool to room temperature, and crush the internal solution to a size of 1 mm or less. did. The pulverized product was placed in a reactor and heat-treated at 250 mm, 270 and 290 ° C. for 1 hour at 1 mmHg, and then at 310 ° C. for 24 hours at 1 mmHg.

Tm of the polyester was not detected, but Tg was 132 ° C
It was. The melt viscosity at 301 ° C. and 100 sec ⁻¹ was 5600 poise. Create a press sheet at 350 ℃, TMA, HDT,
When Vibron was measured, Ts was 281 ° C and HDT was 156
The E'at 23 ° C and 23 ° C was 4.6 GPa.

Claims (1)

[Claims] 1. A fragrance comprising (A) a paraoxybenzoic acid component unit as a main component and an oxybenzoic acid component unit in a range of 50 to 90 mol%, and (B) a dihydroxynaphthalene component unit or a dihydroxydiphenyl ether component unit as a main component. An oxybenzoic acid component unit, wherein the group diol component unit is in the range of 5 to 25 mol%, and the aromatic dicarboxylic acid component unit (C) having a dicarboxydiphenyl ether component unit as the main component is in the range of 5 to 25 mol%. (A), the aromatic diol component unit (B) and the aromatic dicarboxylic acid component unit (C) are randomly arranged, and are substantially amorphous, and measured by a thermomechanical analyzer (TMA). softening point (Ts) is to have 250 to 450 ° C., and 250 to 450 ° C., to 10 ² no melt viscosity measured at 100 sec ^-1 10 ⁶ Poi Melt-moldable aromatic polyester, characterized in that in the range of.