JPH0428748B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition comprising a modified polyphenylene ether and a polyamide. In recent years, in the plastics industry, with the diversification of uses, there has been a demand for high added value through composite resins. For this reason, polymer alloying is becoming popular. Polymer alloys are made by combining existing polymers to take advantage of the properties of each component polymer and to compensate for their weaknesses.
This product was born from the technical idea of responding to diversifying applications that cannot be met with existing polymers alone. For combinations of polymers with very good compatibility, alloying is performed to improve moldability and other modifications, but for combinations of polymers with significantly different compatibility, even the production of molded products is difficult. Even if a molded product is obtained, its mechanical properties, especially impact strength, bending strength, etc., are far inferior to the properties of the molded product obtained from each component alone, and it is brittle and completely unusable. Ta. Polymer alloying only becomes meaningful by taking advantage of their mutually distinct characteristics, and for this reason, how to successfully create combinations of poorly compatible polymers on an industrial scale will become increasingly important in the future. . Polyphenylene ether has excellent, well-balanced properties across the board, including mechanical properties, electrical properties, flame retardance, heat resistance, and water resistance, and has good moldability, making it widely used as an engineering plastic. As is well known, it is used for this purpose. However, like general-purpose plastics such as ABS resin, polyphenylene ether has a very large drawback of swelling or dissolving in common organic solvents such as acetone, toluene, and halogenated hydrocarbons. There were limits to its application to areas that often come into contact with solvents. On the other hand, polyamide is one of the few engineering plastics that have excellent organic solvent resistance. However, polyamide has drawbacks such as nylon 6, a typical resin, having a high moisture absorption rate as seen in nylon 66, poor water resistance, poor dimensional stability, and low heat distortion temperature. As described above, since polyphenylene ether and polyamide have very different properties, it is expected that a polymer alloy obtained by combining them will have new properties that complement the properties of both. Japanese Patent Publication No. 45-997 proposes a resin composition consisting of polyphenylene ether and polyamide for the purpose of improving the fluidity of polyphenylene ether, but the compatibility of both components is extremely poor. In particular, the mechanical properties such as bending strength and impact strength were significantly reduced, and the molded products were only extremely brittle. As a result of intensive studies on polymer alloys of polyphenylene ether and polyamide, the present inventors found that a resin composition consisting of a specific modified polyphenylene ether and polyamide has the impact resistance required for engineering plastics. The present invention was achieved by discovering the fact that the resin composition sufficiently satisfies the performance level of polyamide, and the fact that such a resin composition has the excellent solvent resistance of polyamide and the excellent dimensional stability and heat resistance of polyphenylene ether. It is something. That is, the present invention relates to (A) general formula (However, R ₁ and R ₂ represent an alkyl group having 1 to 4 carbon atoms or a halogen atom, and n is 60 to 300
It is. ) A 1,2-substituted olefin having a carboxyl group or an acid anhydride structure of 0.3% by weight or more in the presence of a radical generator of 0.1% by weight or more based on the polyphenylene ether. 100 parts by weight of polyphenylene ether having a carboxyl group and/or carboxylic anhydride structure obtained by reacting the compounds as part of the substituents, and (B) 10 parts by weight to 1000 parts by weight of polyamide.
It is a resin composition consisting of parts by weight. Preferred specific examples of the polyphenylene ether represented by the above general formula used in the preparation of component (A) constituting the resin composition of the present invention include poly(2,6
-dimethylphenylene-1,4-ether), poly(2-methyl-6-ethylphenylene-1,4)
-ether), poly(2,6-diethylphenylene-1,4-ether), poly(2-methyl-6
-n-propylphenylene-1,4-ether),
poly(2-ethyl-6-chlorophenylene-1,
4-ether), poly(2-ethyl-6-chlorophenylene-1,4-ether), and the like. Preferred specific examples of the 1,2-substituted olefin compound having a carboxyl group or acid anhydride structure used in the preparation of component (A) include maleic anhydride, hymic anhydride, itaconic anhydride, glutaconic anhydride, and citraconic anhydride. acid, aconitic anhydride, 5-norbornene-2-methyl-2-carboxylic acid, phthalic acid and the like. The amount of the 1,2-substituted olefin compound having a carboxyl group or an acid anhydride structure is 0.3% by weight or more, preferably from 0.5 to 4% by weight, based on the polyphenylene ether. If the amount is less than 0.8% by weight, no improvement in mechanical properties such as impact strength or bending strength will be observed in the resulting resin composition of the modified product and polyamide. In addition, the radical generator used in the preparation of component (A) includes known organic peroxides and diazo compounds, and preferred specific examples include benzoyl peroxide, dicumyl peroxide, di-tert-
Examples include butyl peroxide, tert-butylcumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and azobisisobutyronitrile. The amount of the radical generator used is 0.1% by weight or more, preferably in the range of 0.3% to 5% by weight, based on the polyphenylene ether. If the amount is less than 0.1% by weight, no improvement in performance, particularly in impact strength, will be observed in the resulting resin composition of the modified product and polyamide. The following methods can be used to prepare component (A). [1] Add a radical generator and a 1,2-substituted olefin compound having a carboxyl group or carboxylic acid anhydride structure to a solution containing polyphenylene ether, and heat at a temperature of 60°C to 150°C for several tens of minutes to several hours. , stirring method, [2] In a system substantially free of solvent, at 220°C to 370°C
The time ranges from 20 seconds to 30 minutes, preferably 40 °C.
A method of melting and kneading each component for seconds to five minutes. Method [1] is preferably adopted when existing reaction equipment and purification equipment are available, but method [2] can be modified with light equipment such as a general-purpose twin screw extruder. There are advantages such as there is no need for a solvent removal step or a polymer purification step, and changes can be made in a short time. Examples of the polyamide of component (B) constituting the resin composition of the present invention include polyamides obtained from aliphatic, aromatic or alicyclic dicarboxylic acids and diamines, polyamides obtained from aminocarboxylic acids and cyclic lactams, etc. Preferred specific examples include nylon 6, nylon 12, nylon 66, nylon 6/10 copolymer, nylon 6/66
Examples include copolymers. In the resin composition of the present invention, the content ratio of component (A) and component (B) is 10 to 1000 parts by weight, preferably 30 parts by weight, to 100 parts by weight of component (A).
The amount is 500 parts by weight, and is appropriately selected depending on the intended use. By appropriately selecting the type and content of each component (A) and (B) of the resin composition of the present invention, organic solvent resistance, water resistance, dimensional stability, heat distortion temperature, and mechanical properties can be improved. Various adjustments can be made within a preferred range. Mixing of the two components for producing the resin composition of the present invention may be carried out by any known method. For example, you can mix the granules or powder of each component in a V-type blender, Henschel mixer, super mixer, kneader, etc., and then mold this directly.
The mixture may be melt-mixed using an extruder, kneader, intensive mixer, etc. to form chips, which may then be molded.
In any case, an appropriate method may be adopted depending on the composition ratio of the resin composition and the desired shape and properties of the product. Other polymers can be added to the resin composition of the present invention in order to improve the fluidity of the resin, molded products, and impact resistance. In particular, styrene resins, olefin resins, polyphenylene ether copolymer resins, or polymerizable monomer compounds may be coexisting during the production of modified polyphenylene ethers, and resin compositions with polyamides may also be used. It may be added during product manufacturing. The resin composition of the present invention may contain additives such as dyes, pigments, fillers, flame retardants, light stabilizers, antioxidants, and plasticizers, and may also contain glass fibers,
It can also be reinforced by adding fibrous fillers such as carbon fibers. The resin composition of the present invention is useful as an engineering plastic;
It can be formed into a sheet and is used for automotive parts (radiator tanks, fuse boxes, etc.)
A wide range of applications, including electrical parts (connectors, switches, etc.), housings (calculators, copiers, camera parts, watch parts, etc.), and separation membranes (reverse osmosis membranes, ultrafiltration membranes, gas separation membranes, etc.) used for. Hereinafter, the present invention will be explained in more detail with reference to Examples. Reference example 1 Intrinsic viscosity measured at 25℃ using chloroform
After dry blending 1 kg of 0.91 dl/g poly(2,6-dimethylphenylene-1,4-ether) powder, 20 g of maleic anhydride, and 10 g of dicumyl peroxide at room temperature, the screw diameter was 29 mm. ,
Using a co-rotating vented twin-screw extruder with L/D = 25, the mixture was melt-kneaded at a cylinder temperature of 300°C and screw rotation speed of 150 rpm, extruded with a residence time of 50 seconds, and passed through a cooling bath. Turned into pellets. 5 g of this pellet was collected, pulverized into fine powder using a pulverizer, and heated and refluxed in a Soxhlet extractor using 100 ml of ethanol for 48 hours. Then 110℃
A sample was obtained by drying under reduced pressure for 5 hours. The presence of a -CO ₂ - structure derived from the reaction with maleic anhydride in this sample was detected in the Fourier-integrated infrared absorption spectrum.
This was confirmed by analyzing the absorption peak at 1600 to 1800 cm ^-1 . Reference Example 2 1 kg of the same poly(2,6-dimethylphenylene-1,4-ether) powder used in Reference Example 1
and 20 g of maleic anhydride were dry blended, and then treated under the same modification conditions as in Reference Example 1 in the absence of a radical generator. 5g from the pellets obtained
was collected and purified in the same manner as in Reference Example 1 using a Soxhlet extractor, and then analyzed by infrared absorption spectrum in the same manner as in Reference Example ₁ .
No absorption peak originating from was observed. Reference Example 3 1 kg of the same poly(2,6-dimethylphenylene-1,4-ether) powder used in Reference Example 1
and 10 g of dicumyl peroxide were dry blended and treated under the same modification conditions as in Reference Example 1 to obtain pellets. Example 1, Comparative Examples 1 to 3 The pellets obtained in Reference Examples 1 to 3 were mixed with nylon 6 and then molded, and the physical properties of the molded products were measured and compared. Relative viscosity for nylon 6
Pellets of 2.6 (measured with 96% sulfuric acid at 25°C and 1% concentration) were used. That is, 100 parts by weight of the pellets of modified reference example 1 and 100 parts by weight of nylon 6 pellets were dry-blended and then dried under reduced pressure at 105°C for 24 hours. After drying, the mixture was melt-kneaded using a vented twin-screw extruder with a screw diameter of 29 mm and L/D=25 at a cylinder temperature of 275° C. and a screw rotation speed of 150 rpm to obtain pellets. After drying the pellets under reduced pressure at 105° C. for 24 hours, molded pieces with a thickness of 1/8 inch were obtained at 270° C. using an injection molding machine with a screw diameter of 25 mm according to a conventional method (Example 1). For comparison, the pellets of Reference Examples 2 and 3 and the above nylon 6 pellets were mixed at the same mixing ratio as in Example 1, and then molded pieces were obtained under the same melt-kneading and molding conditions as in Example 1 (Comparative Example). 2,3). Furthermore, the same unmodified poly(2,6-dimethylphenylene-1,4-ether) pellets used in Reference Example 1 and nylon 6 pellets were mixed at the same mixing ratio as in Example 1. A molded piece was obtained under the same melt-kneading and molding conditions as in Example 1 (Comparative Example 3). Table 1 shows the physical properties of each molded piece. As is clear from the comparison between Examples and Comparative Examples, the resin compositions of the present invention were found to have significantly improved impact resistance and bending strength.

[Table] Reference example 4 Intrinsic viscosity measured at 25℃ using chloroform
500 parts by weight of poly(2,6-dimethylphenylene-1,4-ether) pellets of 0.93 dl/g;
Polystyrene (Topolex 55 manufactured by Mitsui Toatsu Co., Ltd.)
0) 400 parts by weight, 15 parts by weight of maleic anhydride,
After dry blending with 10 parts by weight of di-tert-butyl peroxide, the screw diameter was 43 mm, L/D=
Using a co-rotating vented twin screw extruder with cylinder temperature of 270℃ and screw rotation speed.
The mixture was melt-kneaded at 150 rpm and extruded with an average residence time of 3 minutes to obtain pellets. Examples 2 to 4, Comparative Examples 4 to 6 Nylon 6 (relative viscosity 2.65, 96% sulfuric acid at 25°C, 1%
Measured by concentration. ) pellets, 200 parts by weight each,
After dry blending at a ratio of 100 parts by weight and 50 parts by weight, the mixtures were dried under reduced pressure at 105°C for 24 hours. After drying, use the same vented twin-screw extruder as used in Reference Example 4 to heat the cylinder at a temperature of 260°C and a screw rotation speed.
After melt mixing at 150 rpm, pellets were obtained. Next, the pellets were dried under reduced pressure at 105°C for 24 hours, and then molded at 270°C using a regular injection molding machine.
A molded product with a thickness of 1/8 inch was obtained. For comparison, poly(2,6-dimethylphenylene-1,4-
After dry blending 500 parts by weight of ether), 400 parts by weight of polystyrene used in Reference Example 4, and 200 parts by weight, 100 parts by weight, and 50 parts by weight of the above-mentioned nylon 6, drying was carried out in the same manner as in Examples 2 to 4. Pellets were obtained under melt extrusion conditions, and then molded products were obtained. Table 2 shows the results of measuring the performance of the obtained molded product.
Shown below.

[Table] Compared to the Examples, all of the Comparative Examples had "sink marks" and flow marks on the surface of the molded products, and the molded products had poor appearance. Furthermore, the molded product of the comparative example was brittle and easily broke. In contrast, the molded products of Examples had good appearance and significantly improved mechanical properties. By adjusting the composition ratio, the molded product of the example has the excellent organic solvent resistance of polyamide,
It has the water resistance of polyphenylene ether and has an improved low heat distortion temperature of polyamide. Table 3 shows the thermal properties and chemical properties.

【table】

[Table] Reference Example 5 1.5 kg of ethylbenzene and poly(2,6-dimethylphenylene-
1,4-ether) 2.0Kg and maleic anhydride 40
After replacing with _N2 , the internal temperature of the reaction vessel was raised from room temperature to 130°C with stirring, and then di-tert-
20 g of butyl peroxide was charged, and the polymerization reaction was continued for 2 hours while maintaining the temperature between 135 and 145°C. Next, the reaction product was taken out, and the solvent ethylbenzene was removed using a vacuum dryer to obtain a modified product. Infrared absorption spectrum analysis of the obtained modified product revealed that the content of maleic anhydride units was 1.96%. Example 5, Comparative Example 7 300 parts by weight of the modified product obtained in Reference Example 5 and 700 parts by weight of pellets of nylon 66 (relative viscosity 2.4, measured with 96% sulfuric acid at 25°C and 1% concentration) were dried. After blending, the mixture was dried under reduced pressure at 105°C overnight. After drying,
Using a vented twin-screw extruder similar to that used in Example 1, the cylinder temperature was 270°C and the screw rotation speed was
Pellets were obtained by melt-kneading at 150 rpm.
After drying this pellet under reduced pressure at 105℃ for 24 hours,
An injection molded product with a thickness of 1/8 inch was obtained at a molding temperature of 270°C. For comparison, the same unmodified poly(2,6-dimethylphenylene-1,4-ether) used in Reference Example 5 and the above nylon 66 were mixed at the same mixing ratio as in Example 5. A molded article was obtained under the same molding conditions as in Example 5, and its performance was measured. The results are shown in Table-4. As is clear from Table 4, the molded product of Comparative Example 7, which does not contain maleic anhydride units, has low impact strength and breaks easily, whereas the molded product of Example maintains good mechanical properties. Ta.

【table】

Claims (1)

[Claims] 1 (A) General formula (However, R ₁ and R ₂ represent an alkyl group having 1 to 4 carbon atoms or a halogen atom, and n is 60 to 300
It is. ) A 1,2-substituted olefin having a carboxyl group or an acid anhydride structure of 0.3% by weight or more in the presence of a radical generator of 0.1% by weight or more based on the polyphenylene ether. 100 parts by weight of polyphenylene ether having a carboxyl group and/or carboxylic anhydride structure obtained by reacting the compounds as part of the substituents, and (B) 10 parts by weight to 1000 parts by weight of polyamide.
A resin composition consisting of parts by weight.