JP3230257B2 - Curing method of polyphenylene sulfide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing PPS having improved impact resistance and tensile elongation at break.

[0002]

2. Description of the Related Art PPS is known as a high-performance engineering plastic having excellent chemical resistance, heat resistance and flame retardancy.

[0003] PPS is conventionally produced by a method based on Japanese Patent Publication No. 45-3368 and the like. However, the resulting polymer has a low molecular weight and thus does not have sufficient strength. Even manufacturing is known to be difficult. Therefore, a method of increasing the molecular weight by oxidatively crosslinking a low molecular weight product of a synthesized polymer in air at a temperature equal to or lower than its melting point to increase the strength of a molded product and improve molding processability has been carried out. Polymers having a high molecular weight obtained by this method are used industrially.

[0004] However, the high molecular weight polymer obtained by the oxidative crosslinking has a serious drawback of poor toughness, that is, low tensile elongation at break and low tensile strength. Therefore, many improvements in the polymerization process have been proposed to improve such disadvantages. For example, JP-A-50-8469
In JP-A-8, an alkali metal carboxylate is added as a polymerization catalyst. However, this production method requires not only a special polymerization catalyst but also a high cost such as a polymer purification step for removing the polymerization catalyst is required for PPS without a solvent suitable for dissolving at 200 ° C. or lower. Is a problem.

In Japanese Patent Application Laid-Open No. 62-197422, PPS before oxidative crosslinking having a melt flow rate below a certain value is oxidatively cross-linked until the melt flow rate becomes below a certain value, and the melt before and after oxidative crosslinking is melted. A method for producing PPS that is oxidatively crosslinked so that the ratio of the flow rate values falls within a certain range has been proposed. However, this is intended to prevent the occurrence of weld cracks, and is insufficient for improving toughness and impact resistance.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a conventional PPS
The object of the present invention is to improve the brittleness, which has been known as a drawback, and to provide a PPS excellent in impact resistance and tensile elongation at break.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have studied the zero shear viscosity before and after oxidative crosslinking, impact resistance and tensile elongation at break. It is surprising that the mechanical properties of PPS, especially the tensile elongation at break, are significantly increased at a certain zero shear viscosity before oxidative crosslinking, even if the zero shear viscosity after oxidative crosslinking is equivalent. Have been found to be non-destructive in the Izod impact test, and have reached the present invention.

That is, in the present invention, PPS having a zero shear viscosity (hereinafter abbreviated as η0 ′) before oxidative crosslinking of 800 or more has a zero shear viscosity (hereinafter abbreviated as η0) of 50,000 after oxidative crosslinking.
P is characterized by performing oxidative crosslinking until reaching
The present invention relates to a method for curing PS.

Hereinafter, the present invention will be described in detail.

The term "zero shear viscosity" in the present invention refers to a melt viscosity at a low shear rate at which a molten polymer exhibits Newtonian flow, and is a cone plate type rotational viscometer, for example, Weisenberg Greo manufactured by Sangamo, UK. It can be measured using a goniometer R20 or the like.

In the present invention, a cone plate type Weisenberg Grego goniometer is used, under a nitrogen atmosphere, at a steady flow rate of 0.01 to 100 (seconds- ¹ ) in a shear rate range of 300 to 300.
The measurement was performed in the temperature range of
(ML Williams-RE Landel-
J. D. The zero shear viscosity was determined by superimposing at 300 ° C. using the Ferry formula.

The PPS before oxidative crosslinking used in the present invention has the general formula

[0013]

Embedded image It consists of a repeating unit shown by this.

Then, the PPS is η0 ′ ≧ 800,
Preferably, it has η0 ′ of η0 ′ ≧ 1000, and there is no particular limitation as long as it can be obtained by a known method. However, when η0 ′ <800, the effects of improving the impact resistance and tensile elongation at break according to the present invention are not exhibited, which is not preferable.

As a specific method for producing such PPS,
For example, (1) a reaction between a halogen-substituted aromatic compound and an alkali sulfide (US Pat. No. 2,513,188;
No. 4-27671 and Japanese Patent Publication No. 45-3368), (2) a binding reaction of thiophenols in the presence of an alkali catalyst or a copper salt (US Pat. No. 327416)
No. 5 and British Patent No. 1160660).
(3) Bonding reaction of an aromatic compound with sulfur chloride in the presence of a Lewis acid catalyst (Japanese Patent Publication No. 46-27255 and Belgian Patent No. 29437).

In particular, Japanese Patent Publication No. Sho 52-1 meets the object of the present invention.
No. 2240, JP-B-54-8719, JP-B-53-25588, JP-B-57-334,
JP-A-55-43139, U.S. Pat.
No. 0, U.S. Pat. No. 4,324,886, preferably obtained by a method for producing high molecular weight PPS.

In the present invention, the oxidative crosslinking is carried out by controlling the temperature and time during the oxidative crosslinking of the PPS of the limited η0 ′ obtained by the above-mentioned production method or the like until η0 ≧ 50000, preferably η0 ≧ 70000. . Η0 is 5
If it is less than 0000, the effect of the present invention is reduced, which is not preferable.

Such oxidative crosslinking can be carried out using various known methods. For example, ribbon blender,
Oxidative crosslinking using a fluidized bed, an oven, or a container rotary mixer can be mentioned. Among them, a method using a ribbon blender is preferable, and the method is carried out in the form of powder of PPS in oxygen, ozone, or a gas containing these.

The temperature at which the oxidative crosslinking is carried out is 200 ° C. or higher and lower than the melting point.
It is not less than 270 ° C and not less than ℃. If the temperature is lower than 200 ° C., the curing speed is slow and not practical, and if it is higher than the melting point, fusion of PPS particles may occur.

The PPS produced according to the present invention includes:
Thermoplastic elastomers such as ethylene-propylene-ethylidene norbornene copolymer (EPDM rubber), ethylene-propylene copolymer (EP rubber), ethylene-butene-1 copolymer, and styrene are within the scope of the present invention. -It is also possible to add a butadiene block copolymer, a styrene-based block copolymer elastomer, an amide-based elastomer, an ester-based elastomer, a urethane-based elastomer or the like, or a rubbery polymer such as a conjugated diene rubber or an acrylic rubber. Furthermore, polyesters such as polyethylene, polystyrene, polybutene, polymethylstyrene, polyvinyl acetate, polyvinyl chloride, polyacrylate, polymethacrylate, polyacrylonitrile, polyethylene terephthalate, polybutylene terephthalate, and polyarylate, nylon 6, nylon 66, nylon 46, nylon 1
2, nylon 11, polyamide such as amorphous nylon, aromatic nylon, polyurethane, polyacetal, polycarbonate, polyphenylene ether, polysulfone,
Homopolymers such as polyether sulfone, polyallyl sulfone, polyphenylene sulfide sulfone, PPS, polyether ketone, polyether ether ketone, polyphenylene sulfide ketone, polyimide, polyamide imide, silicone resin, phenoxy resin, fluororesin, epoxy resin, random It is also possible to add thermoplastic resins and thermosetting resins such as polymers or blocks, graft copolymers and mixtures thereof.

If necessary, glass fibers, carbon fibers, ceramic fibers such as alumina fibers, aramid fibers,
Reinforcing filler such as wholly aromatic polyester fiber, metal fiber, potassium titanate whisker, silicon carbide whisker, calcium carbonate, mica, talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite , Zeolite, nepheline sinite, attapulgite, wollastonite,
Ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide,
Magnesium oxide, iron oxide, molybdenum disulfide, graphite,
Inorganic fillers such as gypsum, glass beads, glass powder, glass balloon, quartz, quartz glass, and organic and inorganic pigments can also be blended.

As the glass fiber, for example, a fiber length of 1.5
Chopped strands having a fiber diameter of 3 to 20 μm, a milled fiber having a fiber length of 30 to 500 μm, and a fiber diameter of 3 to 20 μm, glass flakes and glass powder of 325 mesh or less can be mentioned.

Also, a plasticizer such as an aromatic hydroxy derivative, a release agent, a silane or titanate coupling agent, a lubricant, a heat stabilizer, a weather resistance stabilizer, a crystal nucleating agent, a foaming agent, a rust inhibitor, For the purpose of controlling the degree of crosslinking of ion trapping agents, flame retardants, flame retardant assistants, antioxidants, ultraviolet absorbers, hindered amine light stabilizers, coloring agents and PPS, metal salts of thiophosphinic acid as crosslinking accelerators, If necessary, a dialkyltin dicarboxylate, aminotriazole or the like as a crosslinking inhibitor may be added.

The PPS produced according to the present invention can be pelletized by various known methods by adding the above-mentioned components. For example, a hot melt kneading method using a single screw extruder, a twin screw extruder, a kneader, a Brabender or the like is most preferable.
The kneading temperature at this time is not particularly limited, but can be arbitrarily selected usually from 200 to 400 ° C.

[0025]

EXAMPLES The present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

REFERENCE EXAMPLE 1 (Synthesis of PPS) In a 530-liter reactor equipped with a stirrer, a dehydration tower and a jacket, 110-liter of N-methylpyrrolidone and sodium sulfide (purity: Na ₂
S60.2% by weight) was charged with 61.1 kg and heated with a jacket under stirring until the internal temperature reached about 200 ° C.
Distillation was performed through a dehydration tower. At this time, 13.5 liters of an extract consisting mainly of water was distilled off. Then p
68.7 kg of dichlorobenzene and 48 liters of N-methylpyrrolidone were added, the temperature was raised to 225 ° C. over 2 hours, reacted at 225 ° C. for 2 hours, and then raised to 250 ° C. over 30 minutes. The reaction was further performed at 250 ° C. for 3 hours.

After the completion of the reaction, the reaction mixture was transferred to a solvent recovery device equipped with a stirrer, a jacket and a vacuum line. At this time, 30 liters of N-methylpyrrolidone was added.
Subsequently, by heating under reduced pressure, 210 liters of a distillate mainly composed of N-methylpyrrolidone was distilled off.

Subsequently, 200 liters of water was added to form a water slurry, which was heated and stirred at 80 ° C. for 15 minutes, and then centrifuged to collect a polymer.

Further, the polymer was returned to the solvent recovery unit, 200 liters of water was added, and the mixture was heated and stirred at 100 ° C. for 30 minutes. After cooling, the polymer powder was recovered by a centrifuge. This operation was repeated twice.

The obtained polymer was transferred to a ribbon blender with a jacket and dried. Η0 ′ of the polymer thus obtained was 745, which was
I.

Reference Example 2 Instead of 68.7 kg of p-dichlorobenzene in Reference Example 1, 69.0 kg of P-dichlorobenzene was used.
Reference Example 1 except that the reaction time at 250 ° C. was 4 hours
Was synthesized in the same manner as described above. Η0 ′ of the polymer thus obtained was 1170, which was
And

Examples 1 to 5, Comparative Examples 1 to 7 15 kg of the PPS obtained in Reference Examples 1 and 2 was charged into a ribbon blender having an internal capacity of 110 liters, and the rotation speed was 60 rpm.
m, and air was blown in at a rate of 10 l / min.
Oxidative crosslinking was carried out at 5 ° C. for various times.

Table 1 shows η0 ′, η0, and oxidative crosslinking time.

The PPS obtained in this manner is
Using a co-rotating twin-screw extruder set at 340 ° C., the mixture was melt-kneaded at a screw rotation speed of 200 rpm, and the extruded strand was pelletized. The pellets obtained here were supplied to a screw in-line type injection molding machine set at 270 to 330 ° C., and a test piece for a tensile test and a test piece for an Izod impact test were injection-molded at a mold temperature of 135 ° C. Using these test pieces, a tensile test (AST
MD-638), Izod impact test (ASTMD-2)
56) was performed. Table 1 shows the results.

[0035]

[Table 1] FIG. 1 shows the tensile elongation at break plotted against zero shear viscosity to visually show the effect of the present invention.

[0036]

The PPS produced by the present invention is excellent in impact resistance and tensile elongation at break. Therefore, printed wiring boards, electronic component sealing materials, various connector components, heat-resistant paints can be obtained by various conventionally known methods. It can be molded into molded articles of various shapes such as thin molded articles, fibers, sheets, films, tubes, etc., and processing methods such as injection molding, extrusion molding, blow molding, foam molding, etc. are possible. It is suitably used for blow molding. As a specific field of application, it can be widely used as a molding material having excellent heat resistance, flame retardancy and moldability in the field of industrial materials such as automobiles, electricity, electronics, and machinery.

[Brief description of the drawings]

FIG. 1 shows PP obtained by Examples of the present invention and Comparative Examples
It is a figure which shows the relationship between zero shear viscosity of S and tensile elongation at break.

Claims (1)

(57) [Claims] 1. Zero shear viscosity at 300 ° C. (unit: POI)
SE) having a poly (p-phenylene sulfide) of 800 or more before oxidative crosslinking (however, after completion of polymerization, under an inert atmosphere,
Processed at a temperature of 230-265 ° C, 800 POISE
The above melt viscosity (diameter 0.
300 ° C, 20 mm using a 5 mm, 2 mm long die
(Measured at 0 (sec) ^-1 ) except for the substantially linear polyphenylene sulfide resin . 3) after oxidative crosslinking
Poly zero shear viscosity at 00 ° C. is characterized by performing oxidative crosslinking to reach 50,000 (p- phenylene
(Lens sulfide) curing method.