JPH069820B2 - Method for producing resin composition containing polyphenylene ether and polyamide - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a resin composition, particularly a resin composition containing polyphenylene ether and pariamide.

Conventional technology and problems to be solved by the invention A resin composition obtained by compatibilizing a polyphenylene ether and a polyamide is known to have excellent impact resistance, heat resistance, and solvent resistance, and is widely used. Has been. In recent years, it has attracted attention as a material particularly suitable for outer panels for automobiles.

Many techniques for compatibilizing polyphenylene ether and polyamide have been proposed in the past. These are, for example, by adding a compound having a specific functional group such as maleic anhydride or linseed oil, or modifying the end group of the polymer.

However, the production of the resin composition is carried out using a conventional extruder (see FIGS. 1 and 2). That is, all the composition components are introduced at once from a single raw material supply port (A ₁ , A ₂ ). For this reason, the removal (deaeration) of the gaseous substances generated during the melt-kneading is not sufficient, and it is difficult to achieve fine dispersion of the composition components. Second
As shown in the figure, there is an extruder equipped with a degassing vent (B ₁ ), but this degassing vent is only for degassing water (steam) contained in a small amount in the composition components, It is completely inadequate for removing gaseous substances generated during kneading.

Therefore, depending on the conventional method, a polyphenylene ether having an excellent appearance without occurrence of silver streaks and the like, and physical properties, in particular, excellent fluidity and impact resistance at low temperatures required as a material for outer panels of automobiles. It has been difficult to produce a resin composition containing a polyamide and a polyamide.

Therefore, an object of the present invention is to provide a method for producing a resin composition containing a polyphenylene ether and a polyamide, which is also suitable as a material for an outer panel of an automobile and has particularly excellent appearance, fluidity and impact resistance at low temperature. Is.

Means for Solving the Problems In the present invention, a composition component (first component) that generates a large amount of a gaseous substance during melt-kneading and another composition component (second component) are introduced from separate raw material supply ports. If the gaseous substance generated by the melt-kneading of the first component is forcibly degassed before the introduction of the second component, the gaseous substance can be efficiently treated without being hindered by the second component. It is based on the finding that degassing and fine dispersion of the composition components are achieved.

That is, the present invention is a method for producing a resin composition containing a polyphenylene ether, a polyamide and a compatibilizer using an extruder, wherein the extruder is provided on the upstream side with respect to the flow direction of the raw material. It has a raw material supply port, a second raw material supply port provided on the downstream side, and a vacuum vent provided between the first and second raw material supply ports. The method is characterized in that a composition component containing a polyphenylene ether and a compatibilizer is introduced from one raw material supply port, and a polyamide is introduced from a second raw material supply port.

The extruder used in the present invention (see FIG. 3) has a first raw material supply port (A ₃ ), a vacuum vent (B ₂ ) and a second raw material supply port (A ₄ ) in the flow direction of the raw material. They are provided in this order. Polyphenylene ether, a compatibilizer, a rubbery polymer, and optionally a styrene polymer are introduced from the first raw material supply port (A ₃ ), and only polyamide is introduced from the second raw material supply port. Thus, the polyphenylene ether and compatibilizer will effectively react or be mixed before being mixed with the polyamide.
Furthermore, the rubber-like polymer and styrene-based polymer introduced at the same time can be uniformly finely dispersed in polyphenylene ether.

The temperature between the first raw material supply port (A ₃ ) and the second raw material supply port (A ₄ ) is preferably maintained in the range of 270 to 370 ° C. When the temperature is lower than 270 ° C, the opposite of the polyphenylene ether and the compatibilizer and the degassing of the gaseous substance are insufficient, and it becomes difficult to uniformly finely disperse the composition components such as the rubber-like polymer, When the temperature is higher than 370 ° C, thermal decomposition of the mixed components occurs, which is not preferable.

A vacuum vent (B ₂ ) provided between the first raw material supply port (A ₃ ) and the second raw material supply port (A ₄ ) forces the gaseous substance generated at the temperature during mixing under reduced pressure. To remove. Decompression degree of vacuum vent is preferably 50 cm
Hg or more, more preferably about 60 cm Hg or more (about absolute pressure
16 cmHg or less). This makes it possible to prevent the occurrence of silver streaks, which impairs the appearance of the molded product, and has a favorable effect on the improvement of various physical properties.

Vacuum Vent _{(B 2)} and the first raw material supply port _{(A 3)} and the length of the second raw material supply port and _{(A 4) (1} and ₂₎ is not particularly critical. However, when the vacuum vent and the raw material supply port are too close to each other, the raw material component of the powder introduced from the raw material supply port may be sucked into the vacuum vent, so a device for preventing this, for example, melt sealing. A screw design for etc. is required. Therefore, the vacuum vent is located downstream of the portion in which the raw material components introduced from the first raw material supply port are completely melted and in the flow direction of the raw material components, and the raw material components introduced from the second raw material supply port. It is preferable to be provided on the upstream side of the second raw material supply port to the extent that air is not sucked.

A vent hole may be further provided between the first raw material supply port and the vacuum vent to degas the raw material, and particularly to remove water contained in the raw material.

The polyamide is independently introduced from the second raw material supply port (A ₄ ), flows toward the die (C ₃ ) while being uniformly mixed with the raw material components from the first raw material supply port (A ₃ ), and the final polyphenylene ether is obtained. A resin composition containing and a polyamide is obtained.

At this time, the temperature between the second raw material supply port (A ₄ ) and the die (C ₃ ) is preferably maintained in the range of 220 to 320 ° C. When the temperature is lower than 220 ° C, the mutual reaction between the composition components is insufficient and sufficient compatibility cannot be obtained. On the other hand, the temperature is 320
When the temperature is higher than ° C, thermal decomposition of the composition components occurs, which is not preferable.

Preferred specific examples of the polyphenylene ether used in the present invention include, for example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2 -Methyl-6-ethyl-1,
4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-) 1,4-phenylene) ether, and the like.

Preferred specific examples of the polyamide used in the present invention include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyundecane amide (nylon 11). ), Polydodecanamide (nylon 1
2) and copolymers and mixtures of these polyamides.

The compatibilizing agent used in the present invention is not particularly limited, and any compatibilizing agent used in the prior art can be used. These include compounds with specific functional groups such as citric acid, maleic anhydride, linseed oil, liquid polybutadiene and the like.

The resin composition produced by applying the method of the present invention preferably contains a rubber-like polymer. Specific examples of the rubber-like polymer used in the present invention include, for example, natural rubber, butadiene polymer, butadiene-styrene copolymer and hydrogenated products thereof (random copolymer, block copolymer, graft copolymer, etc. All are included.), Isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer, isobutylene-isoprene copolymer, acrylic ester polymer, ethylene-propylene copolymer. Examples thereof include polymers, ethylene-propylene-diene copolymers, thiochol rubbers, polysulfide rubbers, polyurethane rubbers, polyether rubbers (eg polypropylene oxide), epichlorohydrin rubbers and the like.

Moreover, the resin composition to which the method of the present invention is applied may optionally contain a styrene polymer. Examples of the styrene-based polymer used in the present invention include homopolymers of styrene or a derivative thereof and natural polymers such as polybutadiene, polyisoprene, butyl rubber, EPDM, ethylene-propylene copolymer, natural rubber and epichlorohydrin. Alternatively, a styrene polymer mixed with or modified with a synthetic elastomer substance, and further a styrene-containing copolymer, for example, a styrene-acrylonitrile copolymer (SAN), a styrene-maleic anhydride copolymer, a styrene-acrylonitrile. -Butadiene copolymer (ABS) may be mentioned. Preferred styrene-based polymers for the present invention include homopolystyrene and rubber-reinforced polystyrene.

The resin composition produced by applying the method of the present invention preferably contains the above components in the following amounts.

Polyphenylene ether 10 to 70 parts by weight Polyamide 30 to 70 〃 Rubber-like polymer 1 to 30 〃 Compatibilizer 0.01 to 10 〃 Styrene-based polymer 0 to 30 〃 The present invention will be described in more detail with reference to the following examples.

Examples 1 to 4 The distance from the first raw material supply port to the vacuum vent ( ₁ ) 960 mm, the distance from the vacuum vent to the second raw material supply port ( ₂ ) 340 mm, and the distance from the second raw material supply port to the die 1100 mm. Using a twin screw extruder with a screw diameter of 53 mm and a screw length of 2340 mm (L / D = 44),
Melt-kneading extrusion of the composition components shown in Table 1 was performed under the following conditions to obtain pellets. At this time, the polyamide was introduced from the second raw material supply port, and the other components were introduced from the first raw material supply port.

Vacuum vent Decompression degree: 60cmHg Barrel setting temperature: From the first material supply port to the second material supply port 360 ℃ From the second material supply port to the die 280 ℃ Screw speed: 330rpm Extrusion speed: 80kg / hour After drying the obtained pellets at 120 ° C. for 4 hours, a test piece was prepared by injection molding at 280 ° C.

Using the pellets and test pieces thus obtained,
The properties of the resin composition were tested. The test results are shown in Table 1.

Comparative Example 1 Pellets and test pieces were prepared in the same manner as in Examples 1 to 4 except that all the composition components including polyamide were introduced from the first raw material supply port, and the properties of the resin composition were tested.

The test results are shown in Table 1.

In comparison between Example 4 and Comparative Example 1, in Example 4, the properties, particularly the results of the -40 ° C. high-speed impact test, are dramatically improved, and the degree of improvement in appearance is also remarkable.

Example 5 and Comparative Example 2 The pellets obtained in Example 4 were dried at 120 ° C for 4 hours. The pellets are placed in the barrel of an injection molding machine at 20 ° C at 20 ° C.
After being retained for a minute, a rectangular plate of 150 × 150 × 3 mm was prepared by injection molding.

On the other hand, a square plate having the same size was prepared in the same manner as above except that a twin-screw extruder having no vacuum vent was used, and the two square plates were visually compared.

The results are shown in Table 2.

[Brief description of drawings]

1 and 2 are schematic diagrams showing a conventional extruder, and FIG. 3 is a schematic diagram showing an extruder used in the method of the present invention. A _1, A 2 _... feed inlet B 1 _... degassing vent A 3 _... first raw material supply port A 4 _... second raw material supply port B 2 _... vacuum vent _{C 1, C 2, C 3} ... die l 1 _... first 1 Distance from raw material supply port to vacuum vent l ₂ ... Distance from vacuum vent to second raw material supply port

Claims (8)

[Claims] 1. A polyphenylene ether using an extruder,
In the method for producing a resin composition containing a polyamide and a compatibilizer, the extruder, with respect to the flow direction of the raw material,
It has a first raw material supply port provided on the upstream side, a second raw material supply port provided on the downstream side, and a vacuum vent provided between the first and second raw material supply ports. A method comprising introducing a composition component containing a polyphenylene ether and a compatibilizing agent from the first raw material supply port and introducing a polyamide from the second raw material supply port while degassing under reduced pressure. 2. The temperature from the first raw material supply port to the second raw material supply port and the temperature from the second raw material supply port to the die are respectively
The method of claim 1 which is maintained at 270-370 ° C and 220-320 ° C. 3. The method according to claim 1 or 2, wherein the degree of vacuum of the vacuum vent is 50 cmHg or more. 4. The vacuum vent is introduced from a second raw material supply port downstream of a portion where the raw material components introduced from the first raw material supply port are completely melted in the flow direction of the raw material. 4. The method according to any one of claims 1 to 3, which is provided upstream of the second raw material supply port to the extent that the raw material components are not sucked.
The method of any one of paragraphs. 5. The method according to any one of claims 1 to 4, wherein a composition component containing polyphenylene ether, a compatibilizer and a rubber-like polymer is introduced from the first raw material supply port. 6. A composition ingredient containing 10 to 70 parts by weight of polyphenylene ether, 0.01 to 10 parts by weight of a compatibilizer, and 1 to 30 parts by weight of a rubber-like polymer is introduced from a first material supply port to supply a second material. A method according to any one of claims 1 to 4, wherein 30 to 70 parts by weight of polyamide are introduced by mouth. 7. The polyphenylene ether is poly (2,
6-dimethyl-1,4-phenylene) ether,
The compatibilizer is citric acid, and the rubbery polymer is styrene-butadiene copolymer (SBS), hydrogenated styrene-butadiene copolymer (SEBS) and styrene-ethylene-propylene copolymer (SEP). 7. The method of claim 6 which is at least one copolymer selected from the group consisting of), and said polyamide is nylon 6 or nylon 66. 8. The method according to claim 6, wherein the composition component introduced from the first raw material supply port also contains 30 parts by weight or less of polystyrene and / or rubber-reinforced polystyrene.