JPH062869B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Field The present invention relates to a melt anisotropic polyester composition having excellent thermal and mechanical properties.

[Conventional technology]

In recent years, regardless of whether it is a fiber, film or molded product,
There is a strong demand for materials with excellent rigidity, heat resistance and chemical resistance. Polyesters have come to be widely accepted for general molded articles, but many polyesters are not suitable for applications requiring high strength because they have poor mechanical properties such as flexural modulus. In order to improve this mechanical physical property, a method of blending a reinforcing material such as calcium carbonate or glass fiber is known, but since the specific gravity of the material becomes large, the advantage of lightweight, which is a characteristic of plastics, is reduced. At the time of molding, wear of the molding machine is severe, and there are many practical problems. In recent years, liquid crystalline polyester has been attracting attention as a polyester that does not require a reinforcing material and is suitable for applications requiring high strength. It has been particularly noted that Journal of Polymer Science Polymer Chemistry Edition, Volume 14 (1976), page 2043 and Japanese Patent Publication No. 56-18016. J. This is after Jackson announced a thermal liquid crystal polymer consisting of polyethylene terephthalate and acetoxybenzoic acid.

Among them, Jackson said that this liquid crystal polymer has a rigidity of 5 times or more that of polyethylene terephthalate, a strength of 4 times or more, and
It was reported that it exerts impact strength of 5 times or more, showing a new possibility for high-performance resins.

However, the liquid crystalline copolyester has infusible particles (different polymer) in addition to the copolyester. In addition, when the relationship between the melt viscosity and the shear rate was investigated, the temperature dependence was so great that stable molding could not be performed, and the yarn obtained by extruding this polymer had such problems that the ultimate elongation was small. Have

These drawbacks have already been improved as shown in Japanese Patent Application No. 59-42270. However, the polymer produced by this method has a low melting point (Tm), and the composition of the obtained polymer is such that the raw materials used during polymerization are charged. Since it is determined by the ratio, when a polymer having a different composition is required, it has to be newly polymerized, which is disadvantageous in flexibility and economical efficiency.

[Object of the Invention]

The present inventors have arrived at the present invention as a result of intensive studies in view of such points.

That is, the present invention provides a resin composition which exhibits melt anisotropy and has excellent thermal and mechanical properties.

That is, this composition comprises (a) a dicarboxylic acid unit represented by the general formula (I) (In the formula, at least 60 mol% or more of R is a 1,4-phenylene group, and 40 mol% or less is a C _{6 to} C ₁₆ divalent aromatic hydrocarbon group other than a 1,4-phenylene group, C _4- C
₂₀ divalent alicyclic hydrocarbon groups or C _{1 to} C ₄₀ divalent aliphatic hydrocarbon groups are shown. However, the hydrogen atom of the benzene ring of the aromatic hydrocarbon group (including the 1,4-phenylene group) may be substituted with a halogen atom, a C ₁ -C ₄ alkyl group or an alkoxy group) General formula ( Glycol unit represented by II) —O—R′—O— (II) (wherein R ′ is a C _{1 to} C ₂₀ divalent aliphatic hydrocarbon group or a C _{4 to} C ₂₀ group). A divalent alicyclic hydrocarbon group) and a melt-moldable polyester comprising 2% by weight to 50%
% By weight and (b) polyester represented by the general formula (A) (In the formula, R ¹ represents a 1,4-phenylene group.
The hydrogen atom of the benzene ring of the 1,4-phenylene group may be substituted with a halogen atom, a C ₁ -C ₄ alkyl group or an alkoxy group. R ² is -CH ₂ CH ₂ - shows a. ) And an oxycarboxylic acid represented by the general formula (H) HO—R ³ —COOH (H) (wherein R ³ represents a 1,4-phenylene group.
The hydrogen atom of the benzene ring of the 1,4-phenylene group may be reacted with a halogen atom, which may be substituted with a C ₁ -C ₄ alkyl group or an alkoxy group) to form a copolymerized oligomer, and then acetyl group. A mixture of phenol and tetrachloroethane prepared by adding an agent to carry out an acetylation reaction and then performing a polycondensation reaction in a 1: 1 (weight ratio) mixture solution.
Logarithmic viscosity ηinh measured at 30 ° C at a concentration of 5 g / dl is 0.4d
50% by weight to 98% by weight of copolyester having a content of 1 / g or more
It consists of weight%.

[Structure of Invention]

The present invention will be described in more detail. As the melt-moldable polyester of the component (a), generally, the general formula (E)
Raw material polyester represented by (In the formulae, R and R ′ are the same as the general formulas (I) and (I
The same meanings as R and R'in I) are used. However, in order to produce such a raw material polyester (E), the carboxylic acid HOOCRCOOH represented by the general formula (F). And its esters are used. Examples of carboxylic acids are terephthalic acid, methoxyterephthalic acid, ethoxyterephthalic acid, fluoroterephthalic acid, chloroterephthalic acid, methylterephthalic acid, isophthalic acid, phthalic acid,
Methoxyisophthalic acid, diphenylmethane 4,4'-dicarboxylic acid, diphenylmethane 3,3'-dicarboxylic acid, diphenyl ether 4,4'-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, naphthalene-2,6
-Dicarboxylic acid, naphthalene 1,5 dicarboxylic acid, naphthalene 1,4 dicarboxylic acid, adipic acid, sebacic acid,
Azelaic acid, suberic acid, dodecanedicarboxylic acid, 3
-Methyl azelaic acid, glutaric acid, succinic acid, cyclohexane 1,4 dicarboxylic acid, cyclohexane 1,3
Examples thereof include dicarboxylic acid and cyclopentane 1,3 dicarboxylic acid. These may be mixed and used, and any of those represented by the general formula (F) can be used.

Further, specific examples of the diol HOR'OH represented by the general formula (G) used for producing (E) ... (G) include ethylene glycol, 1,3-propanediol, and 1,2-propane. Propanediol, 1,3 butanediol, 1,4-butanediol, neopentyl glycol, 1,6 hexanediol, 1,12-dodecasin diol, cyclohexane 1,4 diol, cyclohexane 1,3 diol, cyclohexane 1,2 -Diol, cyclopentane 1,3-diol and the like can be mentioned, but they may be used in combination, and any of those represented by the general formula (G) can be used.

As the polyester represented by the formula (E) used in the present invention, any of those represented by the general formula (E) can be used, but polyethylene terephthalate and polybutylene terephthalate are preferred because of their easy availability, and particularly polyethylene terephthalate Is preferred.

The copolyester (b) can be produced by subjecting a polyester and an oxycarboxylic acid to a catalytic reaction to form a copolymer oligomer, followed by acetylation and polymerization, and further deacetic acid.

To describe the production method in more detail, the raw material polyester represented by the general formula (A) (Wherein R ¹ and R ² have the same meanings as described above) and an oxycarboxylic acid represented by the general formula (H): HO—R ³ COOH (H) (wherein R ³ has the same meaning as described above). Meaning) After contacting and heating at 150 to 350 ° C. under normal pressure to form a copolymerized oligomer, acetylating agent is added for acetylation and polymerization, and deacetic acid is further removed under reduced pressure and under vacuum. , By completing the reaction. It is also possible to share a diol and a dicarboxylic acid (the above-mentioned (G) and (F) are similarly exemplified) when the raw material polyesters (A) and (H) are brought into contact with each other.

Examples of the oxy acid represented by the general formula (H) include parahydroxybenzoic acid.

The amount of oxycarboxylic acid used is (H) / {raw material polyester + (H)}, (H) / {raw material polyester + dicarboxylic acid + (H)}, (H) / {raw material polyester + diol + (H)} Or (H) / {raw material polyester + dicarboxylic acid + diol + (H)} 30 to 80 mol%
Is. Acetic anhydride is used as a typical acetylating agent, but the acetylating agent is not limited thereto. If necessary, a transesterification catalyst, an acetylation catalyst and a polymerization catalyst may be used.

Further, the copolymerized polyester (b) may be introduced with a small amount of the copolymerization component according to various purposes.

The structure of the component (b) copolymerized polyester produced in this manner is described in, for example, Japanese Patent Application No.
A unit as described in 42270.

That is, the general formula (J) (In the formula, R ¹ has the same meaning as in the general formula (A)) Glycol unit represented by the general formula (B) —O—R ² —O— (B) (In the formula, R ² is the above. An oxycarboxylic acid unit represented by the general formula (A) and the general formula (C) (Wherein R ³ is as defined in the above general formula (H)), but a part of the oxycarboxylic acid unit (C) is bonded to a part of the glycol unit (B) by an ether bond to give a general formula ( D) And the content of the dicarboxylic acid unit (J) is 10 to 40 mol%, and the oxycarboxylic acid unit is based on the total amount of the dicarboxylic acid unit (J) and the oxycarboxylic acid unit (C). The ratio (C) / {(J) + (C)} of (C) is 30 to 80.
Mol%, and the ratio (C) / {(B) + (C)} of oxycarboxylic acid unit (C) to the total amount of glycol unit (B) and oxycarboxylic acid unit (C) is 30 to 80.
Mol%, the ratio of the unit (D) to the glycol unit (B) is 3 to 50 mol%, and in the relationship between the melting point Tm measured by the differential scanning calorimeter (DSC) and the composition, (C) / { When (B) + (C)} changes from 65 mol% to 35 mol%, Tm changes by 15 ° C. or more, in a 1: 1 (weight ratio) mixture of phenol and tetrachloroethane. The logarithmic viscosity ηinh measured at 30 ° C. at a concentration of 0.5 g / dl is 0.4 dl / g or more.

The composition ratio of component (a) and component (b) is such that (a) is 2 to 50% by weight, (b)
Is 98 to 50% by weight, and preferably (a) is 2 to 20.
% By weight, and (b) is 98 to 80% by weight. When the amount of the component (b) is less than this range, the obtained resin does not exhibit melt anisotropy and is inferior in strength.

Generally, when polymers are melt-mixed with each other, if the compatibility is poor, phase separation occurs and the physical properties are remarkably deteriorated. However, the present invention has an advantage in that the polyesters are melt-mixed with each other so that the transesterification reaction easily occurs and sufficient compatibility is obtained. Further, since this transesterification reaction is carried out in a short time, a special melt-mixing device is not required and, for example, a normal extruder can be used.

In the manufacture of the composition of the present invention, each component is usually supplied in the form of pellets or powder. Each component is weighed separately and physically mixed in a suitable device such as a ball mill. The mixture is then dried at about 160 ° C. in vacuum for 12 hours. The purpose of the drying process is to remove water from the mixture to prevent degradation of the polymer.

〔Example〕

The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

In the examples, the logarithmic viscosity was measured at 30 ° C. at a concentration of 0.5% using a mixed solvent of tetrachloroethane / phenol = 1/1 (weight ratio). The melt mixing of the polymers was carried out using a J5S type extruder (Dalmagee type screw) manufactured by Japan Steel Works, Ltd. The melt fiberization of the polymer composition was performed using a capillary rheometer manufactured by Intesco Co., Ltd. with a nozzle having a diameter of 1.0 mm and a length of 10 mm and a taper of 45 ° at a shear rate of 10 ³ / sec. Tensile test is UTM- manufactured by Toyo Baldwin Co., Ltd.
Using IIIL type, pulling speed 10mm / min, check space 20cm
It was done in. The liquid crystallinity was judged by the presence or absence of optical anisotropy in the molten state. The equipment was equipped with a heat stage manufactured by Zeus. A "Nikon modified microscope" POH type was used. The value of SONICKUMOJIURA for the fiber is Dynamo MOKUJI RASTER PPM-5R (ASTM F of Toyo Seiki Co., Ltd.).
89-68). The composition ratio (oxyacid unit / terephthalic acid unit) was measured using proton N.
Measured by MR, Tm is measured by Perkin-Elmer DSC
-It was done by a type II machine.

Examples 1 to 5 Polyethylene terephthalate oligomer (ηinh 0.10dl
/ G) 38.4 g to p-hydroxybenzoic acid 41.4 g
And 0.024 g of stannous acetate were charged into a polymerization tube equipped with a stirrer and purged with nitrogen three times, and then the polymerization tube was placed in an oil bath at 240 ° C. and stirred under a nitrogen stream for 1 hour. Next, 36.72 g of acetic anhydride was added and stirred for 1 hour and 30 minutes. While distilling out acetic acid and unreacted acetic anhydride, the bath temperature was then raised to 275 ° C., and the pressure was reduced to 10 Torr. The pressure in the polymerization tube was returned to normal pressure with nitrogen, 0.044 g of zinc acetate dihydrate was added, and the mixture was stirred under a vacuum of 0.2 Torr for 6 hours to complete the polymerization. The polymer (Z) has a logarithmic viscosity of 0.70 dl
/ G, and showed optical anisotropy in the range of 170 to> 350 ° C. This polymer was dried under reduced pressure with polyethylene terephthalate (ηinh 0.64 dl / g) at 160 ° C. for 12 hours, mixed at a predetermined ratio, and melt-extruded with an extruder. The nozzle temperature of the extruder was 280 ° C.
The obtained resin composition was further dried under reduced pressure at 160 ° C. for 12 hours, and fiberized by a capillary rheometer. Table 1 shows the physical properties of the obtained fiber.

Comparative Example 1 Polyethylene terephthalate oligomer (ηinh 0.01dl
/ G) 64.8 g of p-hydroxybenzoic acid 56.9 g and stannous acetate 0.037 g were charged into a polymerization tube equipped with a stirrer and purged with nitrogen three times, and then the polymerization tube was placed in an oil bath at 240 ° C. The mixture was stirred under a nitrogen stream for 1 hour. Then acetic anhydride 52.
6 g was added and stirred for 1 hour and 30 minutes. While distilling out acetic acid and unreacted acetic anhydride, the bath temperature was then raised to 275 ° C., and the pressure was reduced to 10 Torr. The pressure in the polymerization tube was returned to normal pressure with nitrogen, and 0.067 g of zinc acetate dihydrate was added.
Polymerization was completed by stirring under Torr vacuum for 6 hours. The logarithmic viscosity of the produced polymer is 0.55 dl / g and is 190 to> 35.
It exhibited optical anisotropy in the range of 0 ° C. 160 polymer
It was dried under reduced pressure at 12 ° C. for 12 hours, fiberized in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table-1.

Comparative Example 2 Polyethylene terephthalate oligomer (ηinh 0.10dl
/ G) 72.0 g of p-hydroxybenzoic acid 51.8 g and stannous acetate 0.037 g were charged into a polymerization tube equipped with a stirrer, and after purging with nitrogen three times, the polymerization tube was placed in an oil bath at 248 ° C. and nitrogen. The mixture was stirred under an air stream for 1 hour. Next, 47.9 g of acetic anhydride was added and stirred for 1 hour and 30 minutes. After distilling off acetic acid and unreacted acetic anhydride, the bath temperature was raised to 283 ° C. and then 1
The pressure was reduced to 0 Torr. The pressure in the polymerization tube was returned to normal pressure with nitrogen, and 0.068 g of zinc acetate dihydrate was added.
Polymerization was completed by stirring under vacuum of rr for 6 hours. The logarithmic viscosity of the produced polymer is 0.71 dl / g and is 200 to> 350 ° C.
The optical anisotropy was shown in the range. Polymer at 160 ℃, 1
After drying under reduced pressure for 2 hours, fiberization was performed in the same manner as in Example 1 and physical properties were measured. The results are shown in Table-1.

Comparative Example 3 Polyethylene terephthalate oligomer (ηinh 0.10dl
/ G) 72.0 g of p-hydroxybenzoic acid 51.8 g and stannous acetate 0.037 g were charged into a polymerization tube equipped with a stirrer and purged with nitrogen three times, and then the polymerization tube was placed in an oil bath at 240 ° C. and nitrogen. The mixture was stirred under an air stream for 1 hour. Next, acetic anhydride 47.9g
Was added and stirred for 1 hour and 30 minutes. While distilling off acetic acid and unreacted acetic anhydride, the bath temperature was then raised to 275 ° C., and the pressure was reduced to 10 Torr. The pressure in the polymerization tube was returned to normal pressure with nitrogen, and 0.068 g of zinc acetate dihydrate was added.
Polymerization was completed by stirring under vacuum of rr for 6 hours. The produced polymer had an inherent viscosity of 0.61 and exhibited optical anisotropy in the range of 200 to> 350 ° C. Polymer at 160 ℃, 12
It was dried under reduced pressure for a period of time and fiberized in the same manner as in Example 1 to measure the physical properties. The results are shown in Table-1.

[Effects of the Invention] As described above, the resin composition of the present invention exhibits melt anisotropy and exhibits excellent thermal and mechanical properties.

Claims (1)

[Claims] 1. A dicarboxylic acid unit represented by the general formula (I): (In the formula, at least 60 mol% or more of R is a 1,4-phenylene group, and 40 mol% or less is a C _{6 to} C ₁₆ divalent aromatic hydrocarbon group other than a 1,4-phenylene group, C _4- C
₂₀ divalent alicyclic hydrocarbon groups or C _{1 to} C ₄₀ divalent aliphatic hydrocarbon groups are shown. However, the hydrogen atom of the benzene ring of the aromatic hydrocarbon group (including the 1,4-phenylene group) may be substituted with a halogen atom, a C ₁ -C ₄ alkyl group or an alkoxy group) General formula ( Glycol unit represented by II) -OR'-O -... (II) (In the formula, R'is a C _{1 to} C ₂₀ divalent aliphatic hydrocarbon group or a C _{4 to} C ₂₀ A divalent alicyclic hydrocarbon group) and a melt-moldable polyester comprising 2% by weight to 50%
% By weight and (b) polyester represented by the general formula (A) (In the formula, R ¹ represents a 1,4-phenylene group.
The hydrogen atom of the benzene ring of the 1,4-phenylene group may be substituted with a halogen atom, a C ₁ -C ₄ alkyl group or an alkoxy group. R ² is -CH ₂ CH ₂ - shows a. ) And an oxycarboxylic acid represented by the general formula (H) HO—R ³ —COOH ... (H) (In the formula, R ³ represents a 1,4-phenylene group.
The hydrogen atom of the benzene ring of the 1,4-phenylene group may be reacted with a halogen atom, which may be substituted with a C ₁ -C ₄ alkyl group or an alkoxy group) to form a copolymerized oligomer, and then acetyl group. A mixture of phenol and tetrachloroethane prepared by adding an agent to carry out an acetylation reaction and then performing a polycondensation reaction in a 1: 1 (weight ratio) mixture solution.
Logarithmic viscosity ηinh measured at 30 ° C at a concentration of 5 g / dl is 0.4d
50% by weight to 98% by weight of copolyester having a content of 1 / g or more
A resin composition exhibiting melt anisotropy, which is composed of wt%.