JPS6361334B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to aromatic polyester carbonates having excellent Young's modulus. Conventionally, polyethylene terephthalate has excellent mechanical strength, heat resistance, and chemical resistance, and is therefore widely used as a material for fibers, films, plastics, and the like. However, polyethylene terephthalate fibers are still not sufficient for industrial applications, such as tire cords, which require high strength and Young's modulus. The invention of JP-A-50-43223 is an attempt to create a molded article of aromatic polyester having a high Young's modulus. Here, high Young's modulus fibers made of melt-spun copolyesters containing components such as p-oxybenzoic acid, hydroquinone, terephthalic acid, and isophthalic acid have been proposed, but such polyesters have extremely high melt viscosity; Conventional melt spinning is difficult. Therefore, by melt spinning a relatively low molecular weight copolyester and then heat treating the resulting fibers at high temperatures,
The molecules are cross-linked and chain-grown to obtain a high molecular weight, and the fibers are further stretched to produce a fiber with a high Young's modulus. In view of these points, the present inventors have conducted intensive studies and have developed an aromatic polyester that is easy to mold and has high strength and Young's modulus by introducing a specific aromatic dihydroxy compound and carbonic acid residue into the aromatic polyester. They discovered carbonate and arrived at the present invention. That is, the present invention

【formula】

Aromatic dihydroxy compound residue (B) mainly consisting of [Formula],

[expression] and/or

In an aromatic polyester carbonate which is composed of repeating structural units of [Formula] and (-CO-)(D), and in which all of the bonding modes of these structural units are ester bonds, the ratio of ester bonds to carbonate bonds is 18
24 and a flow temperature of 250 to 400°C. In the present invention, component (A) consists of p-oxybenzoic acid residues. Next, component (B) consists of aromatic dihydroxy compound residues. The aromatic dihydroxy compound includes dioxydiphenyl and/or its nuclear substituted derivatives (for example, halogen atoms such as chlorine atom, bromine atom, iodine atom, etc., lower alkyl groups such as methyl group, ethyl group, etc., methoxy group, ethoxy group) The main target is dioxydiphenyl derivatives in which at least one hydrogen atom of the benzene nucleus is substituted with an atom or group such as an alkoxy group, etc. Examples of such compounds include dioxydiphenyl, dioxydiphenyl chloride, dioxydiphenyl bromide, dioxydiphenyl iodide, methyldioxydiphenyl, methoxydioxydiphenyl, and the like. The aromatic dihydroxy compound of component (B) is a part of dioxydiphenyl (e.g., 50 mol% or less, preferably 80 mol% or less) and other aromatic dihydroxy compounds (e.g., resorcinol, hydroquinone, dioxynaphthalene, etc.). 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4
-hydroxyphenyl) cyclohexane and their nuclear substituted derivatives, etc.) or other diols such as aliphatic diols such as ethylene glycol, neopentyl glycol, etc., alicyclic diols such as cyclohexane dimethylol, cyclohexane diol, etc. You may substitute one species or two or more species. In the present invention, examples of compounds that provide aromatic dihydroxy compound residues, which are component (B), include dioxydiphenyl residues, as well as dioxydiphenyl, p-diacetoxybenzene, p-dibenzoyloxy Preferable examples include esters of aliphatic carboxylic acids such as benzene or aromatic carboxylic acids. Furthermore, component (C) consists of aromatic dicarboxylic acid residues, and examples of the aromatic dicarboxylic acid residues include residues of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and the like. In addition, component (D) is a carbonic acid residue. Compounds that provide this carbonic acid residue include diaryl carbonates such as diphenyl carbonate, halides such as phosgene, and the like. The ratio of ester bonds to carbonate bonds in the aromatic polyester carbonate of the present invention is preferably 18 to 24 from the viewpoint of the balance of physical properties of the polymer. The flow temperature of the aromatic polyester carbonate in the present invention represents the heat melt fluidity of the thermoplastic resin, and the lower the temperature, the higher the fluidity, and the lower the molecular weight of the resin.
The flow temperature was measured using a capillary rheometer (Flow Tester, CFT-500 model, manufactured by Shimadzu Corporation), and the sample resin heated and melted at a heating rate of 4°C/min was subjected to a load of 100 kg/ ^cm2 . It is expressed as the temperature at which the viscosity of the molten resin shows 48,000 poise when extruded from the original nozzle (inner diameter 1 mm, length 10 mm). The flow temperature of the aromatic polyester carbonate of the present invention is 250-400°C, preferably 270-350°C. If the flow temperature is less than 250℃, it is unfavorable because the physical properties of the molded product, especially heat resistance and Young's modulus, are insufficient.If it exceeds 400℃, it is not preferable because the flowability during molding is not good. do not have. Such polyester carbonate can be produced by any known method. For example, a polyester carbonate consisting of a p-oxybenzoic acid residue as the (A) component, a dioxydiphenyl residue as the (B) component, an isophthalic acid residue as the (C) component, and a carbonic acid residue as the (D) component is as follows. It can be manufactured by methods (1), (2), etc. (1) p-oxybenzoic acid and/or phenyl p-oxybenzoate and/or p-acetoxybenzoic acid and dihydroxyphenyl and/or diacetoxydiphenyl and isophthalic acid and/or diphenyl isophthalate and diphenyl carbonate; The reaction is carried out in a melt reaction (and, if necessary, a solid phase reaction) or in an inert solvent. (2) React p-oxybenzoic acid chloride, dioxydiphenyl, isophthalic acid chloride, and phosgene under alkaline melting. The reaction temperature is preferably 180°C or higher, more preferably 200°C or higher, particularly 250°C or higher and 400°C or lower. Any pressure can be used as the reaction pressure, but
It is preferable to reduce the pressure as the reaction progresses. A molded article made of the polyester carbonate of the present invention can be obtained by melt-molding the polyester carbonate thus obtained at a temperature above the melting point of the polymer and below the decomposition temperature, for example, from 240 to 400°C. For example, in the case of fibers,
This polymer is melted and extruded at, for example, 240 to 400°C, and the draft rate is 5 to 500 and the winding speed is 10 to 500.
It can be obtained by winding at m/min. Note that this fiber has a sufficiently high Young's modulus compared to polyethylene terephthalate fiber, etc., even without necessarily being subjected to stretching or heat treatment. Furthermore, this fiber can be drawn and heat treated to further increase its strength and Young's modulus. In the case of heat treatment, it is preferable to conduct the treatment at a temperature in the range of 180 to 400° C. under reduced pressure or while flowing gas for a period of several tens of seconds to 24 hours. This fiber can be advantageously used for tire cords, rubber reinforcing materials, fillers, and other heat-resistant industrial materials. Further, a film made of the polyester carbonate of the present invention can be obtained by melt-extruding this polymer at 240 to 400°C and then winding it up on a drum. A conventionally known device can be used as the film forming machine. Draft during extrusion is 1-10
Preferably it is 1-5. The film extruded onto the drum may be left to cool at room temperature, or may be rapidly cooled in water. The obtained film has sufficient Young's modulus and strength as compared to polyethylene terephthalate even as it is, but the strength and Young's modulus can be further increased by stretching and heat treatment in the same manner as the above-mentioned fibers. This film can be advantageously used as an industrial material. The present invention will be described below with reference to Examples, but the present invention is not limited to the Examples. Example 1 In a three-necked flask equipped with a stirrer, a nitrogen gas inlet, and a distillation outlet, p-oxybenzoic acid was added.
33.12g (0.24mol), 4,4'-dihydroxydiphenyl 20.46g (0.11mol), isophthalic acid 14.94g
(0.09 mol), diphenyl carbonate 98.44 g
(0.46 mol) and heated to 280°C over 5 hours while slowly blowing nitrogen. Next, while blowing nitrogen vigorously, the reaction temperature was increased to 320℃.
The temperature was raised to 100, and the mixture was reacted for 3 hours, and the carbon dioxide and phenol distilled out were removed, and the mixture was taken out in a molten state. The obtained polymer was ground to 0.5 mm or less and treated in a solid phase at 190°C for 5 hours, 220°C for 3 hours, and 250°C for 3 hours in nitrogen. The yield of the obtained polymer was 61.2g, which was less than the theoretical yield.
This corresponded to 99.5%. The theoretical yield in this case is
p-oxybenzoic acid residue, isophthalic acid residue,
It was determined from the 4,4'-dihydroxydiphenyl residue and the carbonate group remaining in the polymer. Diphenyl carbonate is consumed in an equimolar amount with the carboxyl group,
It was assumed that a 1/2 molar amount of reaction would occur for one phenolic hydroxyl group, which is larger than the carboxyl group. The obtained polymer could not be dissolved in chloroform, tetrahydrofuran, or m-cresol, and its molecular weight could not be determined.
The flow temperature as a guideline was 310°C. This polymer is spun using a melt spinning machine at a spinning temperature of
The yarn was spun at 350°C from a spinneret with a diameter of 0.3 mm and wound at a speed of 150 m/min. The Young's modulus of the obtained fiber is
The weight was 4900Kg/mm ² , the strength was 97Kg/mm ² , and the elongation was 2.1%. The surface reflection infrared absorption spectrum of the extruded sheet was measured with the die removed, and the ratio of ester bonds to carbonate bonds was determined from the intensity ratio of 1720 cm ^-1 (ester group) and 1750 cm ^-1 (carbonate group). The molar ratio was 24. In addition, the molar ratio is 21 when calculated from the amount of preparation. Example 2 3312 g (24.0 mol) of paraoxybenzoic acid, 4,4'-
Dihydroxydiphenyl 1488g (8.0mol), diphenyl isophthalate 1908g (6.0mol), diphenyl carbonate 6000g (28mol) and tin acetate
After charging 3.5 g and thoroughly replacing the inside of the system with nitrogen gas, the system was heated to 250° C. while slowly flowing nitrogen gas. The pressure inside the system was gradually reduced to an absolute pressure of 0.5 mmHg over about 30 minutes, and then the reaction temperature was raised to 300°C, and the reaction was continued for an additional 30 minutes. The obtained polymer was made into powder and heated at 280°C while flowing nitrogen gas.
Solid state polymerization was carried out at 300°C for 6 hours and then at 300°C for 3 hours. The yield of the obtained polymer was 5117 g, which was 98.4% of the theoretical yield. The obtained polymer could not be dissolved in the solvent shown in Example 1, and its molecular weight could not be determined, but as a guide, the flow temperature was 310°C. The resulting polymer was extruded at 350° C. through a die with slits with a gap of 0.3 mm onto a drum rotating at a speed of 10 m/min. The thickness of this film is approx.
100μm, Young's modulus in the mechanical axis direction (MD),
Strength and elongation are 1000Kg/ ^mm2 and 35Kg/mm2, respectively.
mm ² and 4.7%. Furthermore, this film can be stored in air at a temperature of 200℃.
Even after heating and holding for 2000 hours, almost no decrease in strength was observed. Furthermore, when the obtained film was heat-treated at 280°C for 4 hours under a reduced pressure of 0.3 mmHg, the Young's modulus, strength, and elongation in the mechanical axis direction (MD) of the film were 1300 Kg/mm ² and 43 Kg/mm ² , respectively. , which had improved to 3.1%. The ratio of ester bonds to carbonate bonds was determined to be 19 from the surface reflection infrared absorption spectrum of the film in the same manner as in Example 1. In addition, calculation from the amount of preparation gives 18, which is a good approximation. Example 3 In the same manner as in Example 1, p-oxybenzoic acid
33.12 g (0.24 mol), 22.32 g (0.12 mol) of 4,4'-dihydroxydiphenyl, 20.74 g (0.096 mol) of 2,6-dicarboxynaphthalene, and 102.72 g (0.48 mol) of diphenyl carbonate were charged and reacted. Ta. The yield of the obtained polymer was 66.7g, which was less than the theoretical yield.
It was 96.6%. This polymer could not be dissolved in the solvent shown in Example 1, and its molecular weight could not be determined, but the flow temperature as a guideline was 322°C. This polymer was melt-spun at a spinning temperature of 360°C in the same manner as in Example 1. The Young's modulus, strength, and elongation of the obtained fibers were 3300 Kg/mm ² and 89, respectively.
Kg/mm ² and 2.8%. The ratio of ester bonds to carbonate bonds was 19 as determined from the surface reflection infrared absorption spectrum of the sheet-like product extruded with the die removed. Calculation from the amount of preparation gives 18, which is a good approximation.

Claims (1)

[Claims] 1 [Formula] An aromatic dihydroxy compound residue (B) mainly consisting of [Formula],
[Formula] and/or [Formula] and (-CO-)(D) are the repeating structural units of the aromatic polyester carbonate, and all of the bonding modes of these structural units are ester bonds. Ratio to carbonate bond is 18
24 and a flow temperature of 250 to 400°C.