JP3453893B2 - Polyarylene sulfide composite material and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide composite material and a method for producing the same, and more particularly to a polyarylene sulfide composite material excellent in strength and elongation and excellent in toughness and a method for producing the same.

Polyarylene sulfide represented by polyphenylene sulfide (hereinafter abbreviated as PPS) (hereinafter P
(Abbreviated as AS) is drawing attention as an electric / electronic device member and an automobile device member by taking advantage of its excellent heat resistance and chemical resistance. Further, it can be molded into various molded parts, films, sheets, pipes, fibers and the like by injection molding, extrusion molding and the like, and is widely used in fields where heat resistance and chemical resistance are required.

[0003]

2. Description of the Related Art PAS is a polymer in which aromatic residues are bonded via a thioether bond, and a method for producing the same is disclosed in Japanese Examined Patent Publication No. 45-3368. However, since the PAS produced by such a method has a low molecular weight and is fragile, a method of linearly increasing the molecular weight by a polymerization reaction is disclosed in JP-B-52-12240. According to this method, although the toughness of PAS is improved to some extent, it has not yet reached a sufficiently satisfactory level.

It is also known to blend various elastomers with PAS for the purpose of improving the toughness of PAS.
No. 54757, JP-A-59-113055 and the like. However, in the PAS composition obtained by such a method, although the effect of improving the toughness is recognized, a large amount of elastomer is blended, so that the excellent heat resistance and chemical resistance originally possessed by PAS are deteriorated. Not only the flame retardance disappears, but also the strength is greatly reduced.

On the other hand, as a method of finely dispersing a metal in a polymer matrix, a method of heating a polymer containing a specific organometallic complex is disclosed in Japanese Patent Publication No. 61-38938. But according to our study
When this method is applied to the PAS system, the decomposition rate of the organometallic complex is remarkably high, probably because the melt processing conditions of the PAS are extremely severe, and as a result, a large number of coarse metal particles are produced, which is the object of the present invention. It turns out that the effect of doing is not obtained sufficiently.

[0006]

DISCLOSURE OF THE INVENTION The present invention has solved the drawbacks of the above-mentioned conventional techniques and has excellent strength and elongation while maintaining the excellent heat resistance, chemical resistance and flame retardancy inherent to PAS. A high toughness PAS composite material and a method for producing the same are provided.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that by dispersing a specific metal in polyarylene sulfide under specific conditions, excellent heat resistance, chemical resistance and flame retardancy inherent to PAS can be obtained. It has been found that a high toughness PAS composite material which is excellent in strength and elongation while maintaining the property is completed, and has completed the present invention.

That is, the present invention provides PASs 95-99.99.
% By weight and 0.01 to 5% by weight of at least one metal selected from Group VIII and Group Ib of the Periodic Table of Elements, the metal having an average particle size of 0.5 in the PAS matrix.
The present invention relates to a PAS composite material characterized by being uniformly dispersed in a size of ˜30 nm and a method for producing the same.

The present invention will be described in detail below.

The PAS composite material of the present invention has a periodic table V
It is characterized in that at least one kind of metal selected from Group III and Group Ib is uniformly dispersed in PAS with an average particle size of 0.5 to 30 nm. As used herein, the term “uniformly dispersed” means that the metal particles are at least 70%, preferably 9% of each other without agglomerating with each other.
It shows that 0% or more is dispersed independently.

In the present invention, the average particle size of the dispersed metal has an extremely large effect in achieving the effect sufficiently. When the average particle size of the metal is less than 0.5 nm, the metal particles are not sufficiently formed, and a high toughness PAS composite material excellent in strength and elongation cannot be obtained, which is not preferable. On the other hand, if it exceeds 30 nm, the surface area of the metal particles is reduced and PAS cannot be sufficiently restrained, so that a high toughness PAS composite material excellent in strength and elongation cannot be obtained, which is not preferable.

The PAS used in the present invention refers to a polymer in which aromatic residues are bonded via a thioether bond, and mainly refers to a polymer composed of repeating units represented by the following general formulas (I) to (VI). It is a thing.

[0013]

[Chemical 1]

[0014]

[Chemical 2]

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

[0018]

[Chemical 6]

(Where Y is -R, -OR, -OM, -C
_{OOR, -COOM, -NR 2, -CONR} 2 or -CN
(R is hydrogen, an alkyl group having 1 to 24 carbon atoms or 6 carbon atoms.
To 24 cycloalkyl groups, aryl groups and aralkyl groups, and M is an alkali metal. ), X is -CO-,
^{-CONR 1 -, - O -,} - S -, - SO -, - SO
^{_{2 -, - CR 2 R 3}} - or ^{-SiR 2 R 3 - (R 1} , R 2 and R ³ are each hydrogen, an alkyl group or a cycloalkyl group having 6 to 24 carbon atoms having 1 to 24 carbon atoms, aryl Group, an aralkyl group), a is an integer of 0-4, and b is 0-2.
Is an integer, c is an integer from 0 to 4, d is an integer from 0 to 3, and e is 0.
~ 3, f is an integer from 0 to 3, g is an integer from 0 to 5, h
Represents an integer of 0 to 4, i represents an integer of 0 to 4, j represents an integer of 0 to 4, k represents an integer of 0 to 4, and n represents an integer of 1 to 3. ) PAS used in the present invention includes repeating units (I) to
The polymer may contain (VI) alone or may contain a plurality of repeating units. When it contains a plurality of repeating units, it may be a random copolymer or a block copolymer. Absent. Further, even if the PAS used in the present invention is linear, it may have a branched or crosslinked structure such as PAS obtained by copolymerizing a polyhaloaromatic compound containing three or more halogens or by heat curing in air. You may have it. Some examples of such PAS include Japanese Patent Publication No. 45-3368 and Japanese Patent Publication No. 52-122.
No. 40, PPS, Indian Journal of Chemistry, 21 , 501
(1982) polyphenylene sulfide ketone, polyphenylene sulfide sulfone as disclosed in JP-B-53-25880,
Polybiphenylene sulfide as disclosed in JP-B-45-3368, polyphenylene sulfide amide as disclosed in JP-A-63-83135, and as disclosed in JP-A-1-263118. Examples thereof include polycyanophenylene sulfide.

The PAS used in the present invention preferably has a weight average molecular weight of 10,000 to 1,000,000 because the toughness improving effect aimed at by the present invention is easily obtained and the melt processability is excellent. Used. The weight average molecular weight here is measured by using a gel permeation chromatograph (hereinafter abbreviated as GPC). For example, in the case of PPS, 1-chloronaphthalene is used as a solvent, and the weight average molecular weight is measured at 210 ° C. The weight average molecular weight can be determined.

On the other hand, the metal which is another constituent of the present invention is at least one kind of metal selected from Group VIII and Group Ib of the Periodic Table of the Elements, for example, iron, cobalt, nickel, ruthenium, rhodium and palladium. , Osmium, iridium, platinum, copper, silver, gold and the like. These metals can be used alone or in the form of an alloy or a mixture of two or more kinds.

The metal content in the composite material of the present invention is preferably 0.01 to 5% by weight based on the total weight of the composite material. If the metal content is less than 0.01% by weight, the amount of metal is too small, so that sufficient PAS restraint cannot be achieved, and the effect of the present invention is difficult to obtain. On the other hand, when the metal content exceeds 5% by weight, not only is the metal dispersed insufficiently, but also the melt viscosity becomes extremely high, which adversely affects the moldability, which is not preferable.

The PAS composite material of the present invention has a PAS 95-
99.99% by weight, and VIII and I of the periodic table of the elements
At least one kind of metal selected from group b 0.01 to 5
A PAS composite material characterized in that the metal is uniformly dispersed in a PAS matrix with an average particle size of 0.5 to 30 nm, and a method for obtaining such a composite material is provided. If so, any method may be used for the PA of the present invention.
You may use as a manufacturing method of S composite material.

And in the present invention, the preferred PAS
As a method for manufacturing the composite material, there can be mentioned a manufacturing method characterized by including at least two steps of the following (1) and (2).

(1) General formula (a), MmXn (a) (wherein M is a metal of Group VIII and Ib of the Periodic Table of the Elements, and X is a halogen ion, a sulfate ion, a nitrate ion, a phosphate ion, a carboxyl group, 0.02 to 10% by weight of at least one kind of metal salt represented by at least one kind of ion selected from acid ion and sulfonate ion, m is 1 or 2, and n is an integer of 1 to 4). Is dissolved in a solvent, and polyarylene sulfide 90 to 99.98 wt%
After mixing with, removing the solvent.

(2) A solid solution or a mixture of polyarylene sulfide and a metal salt is added at 300 ° C to 400 ° C.
Heating, and applying a shear rate of 10 to 500 sec ^-1 to melt-knead to reduce the metal salt to a metal and uniformly finely disperse the metal in the polyarylene sulfide.

The step (1) is a step of preparing a solid solution or a uniform mixture of the metal salt represented by the general formula (a) and PAS.

The metal salt represented by the general formula (a) is a precursor for producing a metal of Group VIII and Group Ib of the Periodic Table of Elements by being reduced in the step (2) described later, for example, iron chloride, Iron nitrate, iron sulfate, cobalt bromide, cobalt chloride, cobalt naphthenate, cobalt nitrate, cobalt stearate, cobalt acetate, cobalt sulfate, nickel acetate, nickel bromide, nickel chloride, nickel 2-ethylhexanoate, nickel formate, Nickel nitrate, nickel sulfate, ruthenium chloride, rhodium acetate, rhodium chloride, rhodium nitrate, palladium acetate, palladium chloride, palladium nitrate, palladium sulfate, iridium chloride, platinum chloride, copper acetate, copper bromide, copper chloride, copper citrate, Copper fluoride,
Copper formate, copper iodide, copper naphthenate, copper nitrate, copper 4-cyclohexylbutyrate, copper oleate, copper gluconate, copper oxalate, copper sulfate, copper phthalate, copper terephthalate, copper diphosphate, phosphoric acid Examples thereof include copper, silver acetate, silver bromide, silver chloride, silver iodide, silver lactate, silver nitrate, silver sulfate, silver toluenesulfonate and silver trifluoromethanesulfonate. These metal salts can be used in the form of one kind or a mixture of two or more kinds.

The mixing ratio of the metal salt and PAS in this step is such that the mixing ratio of the metal and PAS in the obtained PAS composite material is PAS95 with respect to 0.01 to 5% by weight of the metal.
~ 99.99% by weight, the metal salt 0.02
The PAS is preferably 90 to 99.98% by weight with respect to 10% by weight.

The solvent for dissolving the metal salt is sufficient as long as it has sufficient solubility in the metal salt, and is not particularly limited. And, for example, water, methanol, ethanol, propanol, ethylene glycol, glycerin,
Acetone, ethyl ether, tetrahydrofuran, dioxane, methylene chloride, chloroform, pyridine, ethyl acetate, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1-chloronaphthalene and the like can be mentioned. These solvents may be used alone or as a mixed solvent of two or more kinds. Further, as a method of mixing the metal salt solution and PAS, there are a method of mixing the metal salt solution and solid PAS, a method of mixing the solution in which PAS is dissolved in a solvent and the metal salt solution in a liquid state, and the like. Used.

Regarding the method for removing the solvent from the mixture containing these solvents, the usual operation, that is, the solvent removal under heating and / or reduced pressure conditions can be adopted. However, the heating at this time is preferably performed in a temperature range in which decomposition of the metal salt does not proceed so much.

Next, the step (2) will be described. In this step, a solid solution or a uniform mixture of the metal salt and PAS obtained in the step (1) is heated and melt-kneaded under a specific condition to obtain a PAS composite in which metal particles are uniformly finely dispersed in a PAS matrix. This is a process of manufacturing a material.

The heating temperature used in this step is preferably 300 to 400 ° C., particularly 320 to 3 ° C., because the reduction of the metal salt proceeds sufficiently and there is no risk of PAS decomposition.
80 ° C. is preferred. Further, the shear rate during melt-kneading is 10 because metal aggregation does not occur and fine dispersion is achieved, and there is no risk of PAS deterioration and main chain scission due to heat generation by shearing.
It is preferably ˜500 sec ⁻¹ .

The melt-kneading time under the above conditions can be freely selected within the range where the reduction reaction of the metal salt proceeds sufficiently, and usually about 3 to 15 minutes is sufficient.

By kneading under the above conditions,
At least 50% or more of the metal salt as a metal precursor is reduced to a metal, and the high toughness PAS composite material of the present invention excellent in strength and elongation can be obtained.

As the production apparatus used in the step (2), a usual melt blending apparatus can be used, and for example, a batch type melt kneading apparatus, a single screw extruder or a twin screw extruder is preferably used.

The composite material of the present invention can be molded into various molded articles, films, sheets, fibers, pipes and the like by injection molding, extrusion molding, compression molding, etc., if desired, but glass fiber, carbon, etc. Fiber, ceramic fiber such as alumina fiber, aramid fiber, wholly aromatic polyester fiber,
Metal fiber, reinforcing filler such as potassium titanate whiskers, calcium carbonate, mica, talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nepheline sinite, attapulgite, w Rastonite, sepiolite, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon, quartz It is also possible to mix an inorganic filler such as quartz glass, an organic pigment or an inorganic pigment.

Further, a releasing agent such as wax, a silane-based or titanate-based coupling agent, a lubricant, a heat resistance stabilizer, a weather resistance stabilizer, a crystal nucleating agent, a foaming agent, a rust preventive agent, an ion trap agent, a flame retardant agent. A flame retardant auxiliary agent may be added if necessary.

Further, if necessary, a thermoplastic elastomer such as olefin type, styrene type, urethane type, ester type, fluorine type, amide type, acrylic type, polybutadiene, polyisoprene, polychloroprene, polybutene, styrene-butadiene rubber or Rubber components such as hydrogenated products, acrylonitrile-butadiene rubber, ethylene-propylene copolymer, ethylene-propylene-ethylidene norbornene copolymer, or polyethylene, polypropylene, polystyrene, poly α-methylstyrene, polyvinyl acetate, polychlorinated Vinyl, polyacrylic acid ester, polymethacrylic acid ester, polyacrylonitrile, polyamide such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, nylon 46, polyethylene terephthalate Over DOO, polybutylene terephthalate, polyesters such as polyarylates, polyurethanes, polyacetals, polycarbonates, polyphenylene oxide, polysulfone, polyether sulfone,
Homopolymers such as polyallylsulfone, polyetherketone, polyetheretherketone, polyimide, polyamideimide, silicone resin, phenoxy resin, fluororesin, melt-processable liquid crystal polymer forming an anisotropic melt phase, random, block It is also possible to use a mixture of one or more graft copolymers.

[0040]

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

Synthesis Example 1 (Production of PPS) Internal volume 53 equipped with stirrer, dehydration tower and jacket
In a 0 liter reactor, 110 liters of N-methylpyrrolidone and sodium sulfide (purity: Na ₂ S 60.2% by weight) 61.1
Then, kg was charged, heated with a jacket under stirring, and dehydrated through a dehydration tower until the internal temperature reached about 200 ° C.
At this time, 13.5 l of a distillate mainly consisting of water was distilled off. Then, 68.0 kg of p-dichlorobenzene, N
-Methylpyrrolidone 48l was added and over 2 hours 22
After heating up to 5 ° C and reacting at 225 ° C for 2 hours, 3
The temperature was raised to 250 ° C over 0 minutes, and the reaction was further performed at 250 ° C for 3 hours. At this time, the pressure rose to 10.5 kg / cm ² .

After the reaction was completed, the reaction mixture was transferred to a solvent collector equipped with a stirrer, a jacket and a decompression line. At this time, 30 l of N-methylpyrrolidone was added. Subsequently, it was heated under reduced pressure to distill off 200 l of a distillate mainly composed of N-methylpyrrolidone. Next, water 200
1 was added to make a water slurry, and the mixture 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 l of water was added, the mixture was heated and stirred at 180 ° C. for 30 minutes, and after cooling, the polymer powder was recovered by a centrifuge.
This operation was repeated twice.

The obtained polymer (PPS) was transferred to a ribbon blender with a jacket and dried. This PPS
Was partially sampled and the weight average molecular weight was measured to be 41,000. After the completion of sampling, the temperature was raised to 265 ° C. while flowing air with stirring at a flow rate of 400 l / hour, and a curing treatment was performed for 2 hours. The weight average molecular weight after the completion of curing was 52,000. PP obtained in this way
Hereinafter, S is abbreviated as PPS-I.

Synthesis Example 2 (Production of PPS Modified with Carboxylic Acid) Synthesis was carried out except that 67.3 kg of p-dichlorobenzene and 0.88 kg of 2,4-dichlorobenzoic acid were used instead of 68.0 kg of p-dichlorobenzene. Carboxylic acid-modified PPS was produced in the same manner as in Example 1. The weight average molecular weight of the obtained polymer was 37,000. When this PPS was cured at 265 ° C. for 1 hour as in Synthesis Example 1, the weight average molecular weight increased to 46,000. The PPS thus obtained is hereinafter abbreviated as PPS-II.

Example 1 0.32 g of silver nitrate (manufactured by Wako Pure Chemical Industries, special grade reagent) was dissolved in 100 ml of a mixed solvent of methanol / H ₂ 0 = 1: 1 to prepare a uniform solution, and the PPS obtained in Synthesis Example 1 was prepared. -I 100g
After mixing the solution with
A homogeneous mixture of PS-I and silver nitrate was obtained. This mixture was melt-kneaded with a lab mixer (manufactured by Toyo Seiki Co., Ltd., trade name Labo Plastomill) for 10 minutes under the conditions of 340 ° C. and a shear rate of 100 sec ⁻¹ . After crushing the sample after kneading, use a small injection molding machine (Matsushita Electric Co., Ltd., trade name Panajection) to perform injection molding under the conditions of a cylinder temperature of 330 ° C and a mold temperature of 120 ° C to prepare a test piece. , ASTM D
According to 638, tensile strength and tensile breaking elongation were measured.

The results are shown in Table 1. The tensile strength and the tensile elongation at break are 880 kg / cm ² and 15.0%, respectively, which shows that both the strength and the elongation are superior to those of PPS alone.

When the X-ray diffraction (JEOL, trade name JPX-11PA) of the test piece was measured, it was 2θ.
Diffraction peaks were observed around = 38 ° and 44.2 °, and it was confirmed that silver particles in a metallic state were precipitated in this sample. From this, it is presumed that the added silver nitrate was thermally decomposed and reduced in the process of melt-kneading with PPS to become a zero-valent silver metal.

On the other hand, in order to confirm the dispersed state of silver, a transmission electron microscope (made by JEOL, trade name JEM-2000F
X) was used for observation. As a result, the silver particles become PPS
It was confirmed that the particles were dispersed uniformly in the matrix with an average particle size of 15 nm.

Examples 2 to 14 PPS obtained in the synthesis example and various metal salts shown in Table 1 were mixed in the same manner as in Example 1, and kneaded and molded in the same manner as in Example 1 to obtain tensile strength, The tensile breaking elongation was measured.
The results are summarized in Table 1, and it can be seen that the strength and elongation are superior to those of PPS alone. In addition, when the dispersed state of the metal was observed with a transmission electron microscope, it was found that the metal particles were extremely finely dispersed with an average particle size of 5 to 20 nm.

Comparative Examples 1 and 2 Only the PPS obtained in the synthesis example was kneaded by the same operation as in Example 1 and the same evaluation was performed. The results are shown in Table 2, and it can be seen that both the strength and the elongation are smaller than those of the examples when the metal salt is not added.

Comparative Example 3 Instead of silver nitrate, an organometallic complex palladium (I
I) Acetylacetonate was used, and this was dissolved in chloroform, mixed by the same operation as in Example 1, and after removing the solvent, kneaded, and the same evaluation was carried out. The results are shown in Table 2. When an organometallic complex is used, the decomposition of the complex rapidly progresses under these conditions, which may cause coarsening of the particle size of the dispersed metal, resulting in
The effect of improving elongation was slight.

Comparative Example 4 Palladium (II) chloride (Wako Pure Chemical Industries, special grade reagent)
After 33 g and 100 g of PPS-I were uniformly blended in a powder state, they were kneaded by the same operation as in Example 1 and evaluated in the same manner. The results are shown in Table 2. Palladium chloride was not finely dispersed by simply mixing it with PPS in a powder state, and the effect of improving strength and elongation was slight.

Comparative Example 5 Copper (II) chloride dihydrate (Wako Pure Chemical Industries, special grade reagent)
After 54 g of powder was uniformly blended with 100 g of PPS-I, kneading was performed in the same manner as in Example 1 and the same evaluation was performed. The results are shown in Table 2, but fine mixing of copper was not achieved simply by mixing copper chloride with PPS in the powder state.
The effects of improving strength and elongation were also slight.

Comparative Example 6 Except that 0.54 g of copper (II) chloride dihydrate was used in place of silver nitrate and no kneading operation was performed.
Mixing with PPS was carried out in the same manner as in Example 1. The obtained PPS / copper chloride mixture was treated with a press molding machine at 30
Press molding was performed at 0 ° C. to prepare a test piece, and the same evaluation as in Example 1 was performed. The results are shown in Table 2, and it is understood that when the molding is performed without performing the kneading operation, the dispersion of the copper particles becomes insufficient and the effect of improving the strength and the elongation is small.

Comparative Example 7 A PPS / silver nitrate mixture was prepared in the same manner as in Example 1 except that the kneading operation was not performed, and the resulting mixture was press-molded in the same manner as in Comparative Example 6. As a test piece, the same evaluation as in Example 1 was performed. The results are shown in Table 2, and it can be seen that when the molding is performed without performing the kneading operation, the dispersion of the silver particles becomes insufficient and the effect of improving the strength and the elongation is small.

Comparative Example 8 Palladium (II) chloride was used instead of 0.32 g of silver nitrate.
Mixing and kneading were carried out in the same manner as in Example 1 except that 13.2 g (manufactured by Wako Pure Chemical Industries, special grade reagent) was used, and an attempt was made to mold a test piece by injection molding. It could not be molded high. As described above, it is understood that when the content of metal exceeds the range of the present invention, the moldability is significantly adversely affected.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

As is clear from the above description, the PAS composite material of the present invention has improved brittleness, which was a drawback of conventional PAS, and has also achieved high strength. It is extremely useful in that it enables not only applications in the fields of electric / electronic parts and automobile parts that have been made, but also as non-reinforced PAS whose use has been limited in performance.

Claims (2)

(57) [Claims] 1. Polyarylene sulfide 95-99.9.
9 wt% and 0.01 to 5 wt% of at least one metal selected from Group VIII and Ib of the Periodic Table of Elements, the metal having a mean particle size of 0.5 to 30 nm in the polyarylene sulfide matrix. A polyarylene sulfide composite material characterized by being uniformly dispersed in size. 2. At least the following two steps: (1) General formula (a), MmXn (a) (wherein M is a metal of Group VIII and Ib of the Periodic Table of the Elements, X is a halogen ion, a sulfate ion, At least one kind of ion selected from nitrate ion, phosphate ion, carboxylate ion, and sulfonate ion, m is 1 or 2, and n is an integer of 1 to 4). Dissolve 0.02 to 10% by weight of a salt in a solvent to obtain polyarylene sulfide 90 to 99.98% by weight.
After mixing with, removing the solvent. (2) heating the solid solution or mixture of polyarylene sulfide and metal salt to 300 ° C to 400 ° C, and
A step of applying a shear rate of 0 to 500 sec ^-1 and melt-kneading to reduce the metal salt to a metal and uniformly finely disperse the metal in the polyarylene sulfide. A method for producing a polyarylene sulfide composite material, which comprises: