JPH0446300B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a thermoplastic polyester composition that is well-balanced in mechanical properties, particularly impact resistance, mechanical properties at high temperatures, flame retardance, molded product appearance, heat resistance, and moldability. Thermoplastic polyesters, represented by polyethylene terephthalate, are used in a wide range of fields due to their excellent properties, but their crystallization rate is slow and their moldability and impact resistance are poor.
It is used only by modifying it by adding a fibrous reinforcing agent such as glass fiber or a granular reinforcing agent such as talc. However, polyethylene terephthalate molded products obtained by blending so-called reinforcing agents have a significantly inferior appearance, including surface gloss, and their moldability, impact resistance, heat resistance, and flame retardance are still insufficient. , further improvements are desired. On the other hand, poly(1,4-phenylene sulfide)
Resin itself has excellent flame retardancy and heat resistance, and molding materials reinforced with reinforcing agents such as glass fiber are being used as metal substitutes in fields such as automobile parts and electronics-related parts. It is attracting attention as a material that has the potential to grow into large engineering plastics. However, unreinforced poly(1,4-phenylene sulfide) resin has poor extrusion stability and moldability, and the resulting molded products are black and have poor appearance, as well as poor mechanical performance, including impact resistance. In reality, it is not yet used as a molding material because of its insufficient physical properties. Therefore, the present inventors continued to study with the aim of improving this problem, and as a result, polyethylene-1, polyethylene-1,
2-bis(2-chlorophenoxy)ethane-4,
By blending specific amounts of 4'-dicarboxylate and poly(1,4-phenylene sulfide),
A thermoplastic polyester composition that not only has excellent mechanical properties, especially impact resistance, high-temperature properties, flame retardance, molded product appearance, and heat resistance, but also has good extrusion stability and desirable moldability. The present invention has been achieved based on the discovery that the present invention can be obtained. That is, the present invention uses poly(1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate in an amount of 5 to 95 parts by weight).
The present invention provides a thermoplastic polyester composition containing 95 to 5 parts by weight of 4-phenylene sulfide. Even if polyethylene terephthalate, for example, is used in place of polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate in the present invention, it is not possible to achieve the object of the present invention. That is, the polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate of the present invention itself has flame retardant properties, and has better mechanical properties, heat resistance, and moldability than polyethylene terephthalate. The melting point of poly(1,4-phenylene sulfide) is 273℃, which is quite good.
The melting point of polyethylene terephthalate is 255℃, which is similar to that of poly(1,4-phenylene sulfide), indicating good compatibility and some kind of intermolecular reaction. There is a considerable difference). Polyethylene-1,2-bis(2-chlorophenoxy) in the polyester composition of the present invention
The proportion of ethane-4,4'-dicarboxylate is 5
~95% by weight is essential. If it is less than 5% by weight, the extrusion stability, impact strength, moldability, and appearance of the molded product are poor, and if it is more than 95% by weight, the impact strength is low. The method for producing polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate used in the present invention includes 1,2-
Bis(2-chlorophenoxy)ethane-4,4'-
Direct polymerization from dicarboxylic acids and ethylene glycol or transesterification from esters of dicarboxylic acids (eg dimethyl ester) and ethylene glycol are common. The direct polymerization method uses 220% without a catalyst or in the presence of titanium, tin compounds, etc.
This is a method in which an esterification reaction is performed at ~270°C, followed by a polycondensation reaction at 220~300°C under high vacuum in the presence of compounds such as antimony, lead, germanium, titanium, etc. In addition, the transesterification method can be used for calcium, magnesium, zinc, manganese, cobalt,
This is a method in which a transesterification reaction is carried out at 130 to 260°C in the presence of a lithium compound, etc., followed by a polycondensation reaction at 220 to 300°C under high vacuum in the presence of a compound such as antimony, lead, germanium, or titanium. Specific examples of these compounds include tetrabutyl titanate, monobutyltin oxide, dibutyltin oxide, antimony trioxide, lead dioxide, germanium dioxide, calcium acetate, magnesium acetate, zinc acetate, manganese acetate, cobalt acetate,
Examples include lithium acetate. In addition, the amount of these catalysts added to the polymer
It is 0.001 to 1% by weight, and preferably 0.03 to 0.3% by weight in the case of a transesterification reaction catalyst. To prevent undesirable coloring during this polycondensation reaction, phosphorus compounds such as phosphoric acid, phosphoric esters (such as trimethyl phosphate), phosphorous acid, and phosphorous esters (such as trimethyl phosphite) may be added. You can also do it. Furthermore, in addition to the above-mentioned dicarboxylic acid or its ester and the above-mentioned ethylene glycol in the present invention, a small proportion of other compounds having ester-forming ability can also be copolymerized. For example, succinic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid,
4,4-diphenyldicarboxylic acid, hexahydroterephthalic acid, 1,2-bis(phenoxy)ethane-4,4'dicarboxylic acid, 1,2-bis(2,6
-dichlorophenoxy)ethane-4,4'-dicarboxylic acid, 1(chlorophenoxy)-2(phenoxy)
Dicarboxylic acids such as ethane-4,4'-dicarboxylic acid and/or their ester-forming derivatives and polyethylene glycol, polypropylene glycol, hexamethylene glycol, 1,4
-Cyclohexane-dimethanol, diethylene glycol, neopentyl glycol, bis(β-
Dioxy compounds such as hydroxyethoxy)bisphenol A, oxycarboxylic acids such as p-(β-oxyethoxy)benzoic acid and/or ester-forming derivatives thereof, and the like are used, but 1-(2-chlorophenoxy) is particularly preferred. -2(phenoxy)ethane-4,4'-dicarboxylic acid and/or its ester-forming derivative. The intrinsic viscosity of the thus obtained polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate is preferably from 0.3 to 1.2, more preferably from 0.4 to 1.0. In addition, the poly(1,4-phenylene sulfide) resin used in the present invention has the general formula

It is a polymer whose main constituent unit is a repeating unit of [Formula], and may contain a small amount of divalent aromatic residue other than 1,4-phenylene. Specific examples thereof include:

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc. (X is F, C1, Br or CH ₃ , m is 1-3)
can be mentioned. Among them, typical polyarylene sulfide resin has the general formula

It is a polyphenylene sulfide represented by the formula: For example, one commercially available from Phillips Petroleum Company of the United States under the trade name "Ryton" can be used. This poly(1,4-phenylene sulfide) resin has a molecular weight of 10,000 or more, particularly 20,000 to 50,000, and a melting point of 270 to 290°C. The above-mentioned "Ryton" usually has a molecular weight of 20,000 or less, but a high molecular weight polyphenylene sulfide having a molecular weight of 20,000 or more can be easily obtained, for example, by the method described in Japanese Patent Publication No. 12240/1983. The resin composition of the present invention may contain conventional additives such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, etc., to the extent that they do not impair the purpose of the present invention.
fillers, fibrous or granular reinforcing agents, coloring agents,
Flame retardants, flame retardant aids, antistatic agents, crystallization promoters, other thermoplastic or thermosetting resins, etc. can be further blended. There are no particular limitations on the means for preparing the resin composition of the present invention, but it is possible to A typical method is to melt and knead the material in an extruder at high temperature and then pelletize it. The melt kneading temperature is 280~
320℃ is preferable, and below 280℃ polyethylene-
1,2-bis(2-chlorophenoxy)ethane-
4,4'-dicarboxylate and poly(1,4
- Phenylene sulfide) resin will not be sufficiently melted, and if the temperature exceeds 320°C, it will lead to crosslinking reaction or thermal decomposition reaction, so care must be taken. The resin composition of the present invention thus obtained can be easily molded by conventional methods such as injection molding and extrusion molding, and the resulting molded products and films exhibit excellent performance as described above. The effects of the present invention will be further explained below with reference to Examples. Example 1 Polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate (intrinsic viscosity 0.53) and poly(1,4-phenylene sulfur) having different molecular weights shown in Table 2. id)
Dry blend (A to C) in the proportions shown in Table 1,
After melt-mixing using a screw extruder set at 290 to 310°C, the mixture was extruded into guts and pelletized using a strand cutter. As a measure of extrusion stability during gut extrusion, the ratio of pelletizable guts to the total guts was evaluated. Each pellet was then placed in a 5 oz screw in-line injection molding machine set at 290-300°C.
Izotsu impact test piece under the condition of mold temperature 140℃,
A dumbbell test piece and a test piece for measuring heat distortion temperature were molded. At the time of molding dumbbell test pieces, the lower limit pressure for molding, which is a measure of moldability, was measured, and the mold releasability, degree of burrs, and appearance of the molded product (surface gloss) were evaluated. Izot impact strength, flexural modulus and thermal deformation temperature of each of the obtained test pieces were measured according to the following standards, and the izod impact strength and flexural modulus were measured at a temperature of 25°C. Izot impact strength: ASTM D-256 Flexural modulus: ASTM D-790 Heat distortion temperature: ASTM D-648 (18.6 Kg/cm ² ) These evaluation results and measurement results are also shown in Table 1.

[Table] As is clear from Table 1, the polyester composition of the present invention has good extrusion stability, high Izot impact strength, high flexural modulus, and good surface gloss and moldability of molded products. . It was also found that it had good flame retardancy. In contrast, poly(1,4-phenylene sulfide) or polyethylene-1,2-bis(2
If the amount of -chlorophenoxy)ethane-4,4'-dicarboxylate is less than 5% by weight, the impact strength will be low, and the surface gloss and moldability of the molded product will be poor. Furthermore, when polyethylene terephthalate (intrinsic viscosity 0.64) is used instead of polyethylene-1,2-bis-2(chlorophenoxy)ethane-4,4'-dicarboxylate, the extrusion stability is insufficient, resulting in poor impact strength and thermal deformation. It can be seen that the temperature is low and the moldability is insufficient. It was also found that the flame retardant performance was poor.

Claims (1)

[Claims] 1 Contains 95 to 5 parts by weight of poly(1,4-phenylene sulfide) to 5 to 95 parts by weight of polyethylene-1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate A thermoplastic polyester composition characterized by: