JP5135727B2 - Method for producing polyarylene sulfide composition - Google Patents

Description

  The present invention relates to a method for producing a polyarylene sulfide composition. More specifically, the present invention relates to a method for efficiently increasing the melt viscosity of a polyarylene sulfide composition and efficiently producing a polyarylene sulfide composition having improved molding processing characteristics such as injection molding, blow molding and pipe molding.

  Polyarylene sulfide (hereinafter referred to as PAS) typified by polyphenylene sulfide (hereinafter referred to as PPS) is an engineering plastic excellent in heat resistance, flame retardancy, chemical resistance and rigidity, and injection molding. It is widely used for electrical / electronic equipment members, automobile equipment members, precision machine members, etc. However, PAS has a problem that it is difficult to synthesize a polymer having a high molecular weight, and due to insufficient melt viscosity, molding such as injection molding, blow molding, and pipe molding is difficult.

  As a conventional method for solving this problem, a method in which PAS is treated with a gas containing oxygen at a high temperature to perform oxidative crosslinking (see, for example, Patent Document 1), a method in which the PAS is treated with an oxidizing agent or a radical generator. (For example, refer patent document 2) Or the method (for example, refer patent documents 3-6) etc. which raise melt viscosity by adding various alkoxysilane compounds are proposed.

Japanese Patent Publication No. 45-003368 JP 59-168032 A JP-A-63-251430 Japanese Patent Laid-Open No. 01-089208 Japanese Patent Laid-Open No. 01-146955 Japanese Patent Laid-Open No. 2006-45451

  However, the methods proposed in Patent Documents 1 and 2 are based on a radical crosslinking reaction involving oxygen, the reaction is difficult to control, and the equipment for processing is complicated. There was also a problem that the obtained PAS was markedly colored. Further, according to the methods proposed in Patent Documents 3 to 6, although it is possible to increase some melt viscosity by using a large amount of alkoxysilane compound, it is still not satisfactory in terms of molding processability. There wasn't.

  Thus, the present invention provides a method for efficiently increasing the melt viscosity of a PAS composition and efficiently producing a PAS composition having improved molding processing characteristics such as injection molding, blow molding, and pipe molding.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor, when producing a PAS composition with a melt-kneader, brings PAS into contact with a specific alkoxysilane compound under a specific condition. It has been found that the melt viscosity of the composition can be remarkably increased, and the present invention has been completed.

That is, the present invention includes a PAS, amino group, and an alkoxysilane compound having at least one functional group selected from the group consisting of an epoxy group and an isocyanate group, continuously fed independently to the melt kneader The present invention relates to a method for producing a PAS composition, characterized in that the temperature at the time of contact is lower than the boiling point of the alkoxysilane compound and then melt-kneading at a temperature equal to or higher than the melting point of polyarylene sulfide .

  Hereinafter, the present invention will be described in detail.

  As the PAS used in the present invention, any may be used as long as it belongs to a category called PAS, and among them, the obtained PAS composition is excellent in mechanical strength and molding processability. Therefore, a PAS having a melt viscosity of 50 to 3000 poise measured by a Koka flow tester using a die having a diameter of 1 mm and a length of 2 mm under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg is preferable, particularly 60 to 1500 poise. Are preferred.

  Further, the PAS preferably contains a p-phenylene sulfide unit represented by the following general formula (1) as a constituent unit in an amount of 70 mol% or more, particularly 90 mol% or more.

そして、他の構成成分としては、例えば
下記の一般式（２）に示されるｍ−フェニレンスルフィド単位、

And as another structural component, for example, m-phenylene sulfide unit represented by the following general formula (2),

一般式（３）に示されるｏ−フェニレンスルフィド単位、

O-phenylene sulfide unit represented by the general formula (3),

一般式（４）に示されるフェニレンスルフィドスルホン単位、

A phenylene sulfide sulfone unit represented by the general formula (4),

一般式（５）に示されるフェニレンスルフィドケトン単位、

A phenylene sulfide ketone unit represented by the general formula (5),

一般式（６）に示されるフェニレンスルフィドエーテル単位、

A phenylene sulfide ether unit represented by the general formula (6),

一般式（７）に示されるジフェニレンスルフィド単位、

A diphenylene sulfide unit represented by the general formula (7),

一般式（８）に示される置換基含有フェニレンスルフィド単位、

A substituent-containing phenylene sulfide unit represented by the general formula (8),

（ここで、ＲはＯＨ、ＮＨ_２、ＣＯＯＨ、ＣＨ_３を示し、ｎは１又は２を示す。）
一般式（９）に示される分岐構造含有フェニレンスルフィド単位、

(Here, R represents OH, NH ₂ , COOH, CH ₃ , and n represents 1 or 2)
A branched structure-containing phenylene sulfide unit represented by the general formula (9):

等を含有していてもよく、中でもＰＰＳが好ましい。

Etc., and PPS is particularly preferable.

  The PAS production method is not particularly limited. For example, the PAS can be produced by a method of reacting an alkali metal sulfide and a dihaloaromatic compound in a generally known polymerization solvent. Examples of the metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof, and these may be used in the form of hydrate. These alkali metal sulfides can be obtained by reacting an alkali metal hydrosulfide with an alkali metal base, but may be prepared in situ prior to addition of the dihaloaromatic compound into the polymerization system, You can use the one adjusted in. Examples of the dihaloaromatic compound include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 1-chloro-4-bromobenzene, 4,4'-dichlorodiphenyl sulfone, 4,4'-dichlorodiphenyl ether, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl, and the like. The charging ratio of the alkali metal sulfide and the dihaloaromatic compound is preferably in the range of alkali metal sulfide / dihaloaromatic compound (molar ratio) = 1 / 0.9 to 1.1.

  As the polymerization solvent, a polar solvent is preferable, and an organic amide which is aprotic and stable to alkali at high temperature is particularly preferable. Examples of the organic amide include N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoramide, N-methyl-ε-caprolactam, N-ethyl-2-pyrrolidone, and N-methyl-2-pyrrolidone. 1,3-dimethylimidazolidinone, dimethyl sulfoxide, sulfolane, tetramethylurea and mixtures thereof. Moreover, it is preferable to use this polymerization solvent in 150-3500 weight% with respect to the polymer produced | generated by superposition | polymerization, and it is preferable to use especially in the range used as 250-1500 weight%. The polymerization is preferably carried out at 200 to 300 ° C., particularly 220 to 280 ° C. for 0.5 to 30 hours, particularly 1 to 15 hours with stirring.

  Furthermore, even if the PAS is linear or is treated and crosslinked at high temperature in the presence of oxygen, a small amount of polyhalo compound higher than trihalo is added to introduce a slight cross-linked or branched structure. Even if it is, it may be a heat-treated in a non-oxidizing inert gas such as nitrogen, or may be a mixture of these structures. In particular, when a polyphenylene sulfide resin that has not been subjected to oxidative crosslinking treatment such as heat treatment in an oxygen atmosphere or heat treatment with addition of a peroxide or the like is used, a PAS composition with less coloring can be obtained. preferable.

  Further, the PAS may be one in which ions are reduced by performing a deionization process. As a method of deionization treatment, from a method of washing uncrosslinked PAS with high temperature water of 130 to 250 ° C., a method of washing with an organic solvent, a method of washing with an acid or an aqueous solution thereof, or washing with a combination thereof, It can be arbitrarily selected as desired.

  Examples of the alkoxysilane compound having one or more functional groups selected from the group consisting of an amino group, an epoxy group, an isocyanate group, and a ketimine group used in the present invention include γ-aminopropyltrimethoxysilane and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1 -Propaneamine, etc. Shishiran compounds can be used in the form of each alone or in combination.

  The alkoxysilane compound increases the melt viscosity of the PAS composition and improves molding processability such as injection molding, blow molding, and pipe molding. For this purpose, 0.05 to 3 parts by weight with respect to 100 parts by weight of PAS. It is preferable to use in the range of parts by weight.

  The melt kneader used in the present invention may be any device as long as it can melt and knead PAS, and examples thereof include a melt kneader mixer, a single screw extruder, and a twin screw extruder. Of these, it is preferable to use a single-screw extruder or a twin-screw extruder because the reaction efficiency of PAS and the alkoxysilane compound can be increased as a result of excellent melt-kneading efficiency.

  In the present invention, by continuously supplying PAS and the alkoxysilane compound independently to a melt kneader, the obtained PAS composition can efficiently increase the melt viscosity. Here, when a commonly used method such as dry blending PAS and the alkoxysilane compound in advance using a Henschel mixer or the like is performed, the reactivity of the alkoxysilane compound is significantly impaired, and high It becomes difficult to obtain a PAS composition having a melt viscosity.

  When the PAS continuously supplied to the melt-kneader and the alkoxysilane compound are in contact with each other, it is preferable that the alkoxysilane compound is not volatilized because of its excellent handleability and reactivity. The temperature condition is preferably less than the boiling point of the alkoxysilane compound, more preferably in the range of room temperature to 200 ° C, particularly preferably in the range of 100 ° C to 200 ° C.

  In addition, after the PAS and the alkoxysilane compound are in contact with each other, the PAS is preferably melted because of its excellent reactivity and productivity, and the temperature condition at that time is more preferably the melting point of the PAS or more. Is preferably in the range of melting point to melting point + 100 ° C., particularly in the range of melting point + 10 ° C. to melting point + 60 ° C.

  In the present invention, when continuously supplying PAS and the alkoxysilane compound independently to the melt-kneader, the supply port, vent port, etc. of the melt-kneader can be used.

  In the present invention, in order to obtain a PAS composition having more excellent mechanical strength, an inorganic filler can be further supplied as desired to produce a PAS composition. In that case, it is preferable to supply 0.01 to 450 parts by weight of an inorganic filler with respect to 100 parts by weight of PAS because a PAS composition excellent in balance between mechanical strength and moldability is obtained. It is particularly preferable to supply 10 to 250 parts by weight.

  As the inorganic filler, known fillers such as a fiber, a powder, and a plate are used. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel, Examples of the metal fibrous material include aluminum, titanium, copper, and brass. Particularly typical fibrous fillers are glass fiber and carbon fiber.

  Examples of the particulate filler include carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, iron oxide, titanium oxide, Metal oxide such as zinc oxide, aluminum, metal carbonate such as calcium carbonate and magnesium carbonate, metal sulfate such as calcium sulfate and barium sulfate, other silicon carbide, silicon nitride, boron nitride, various metal powders Etc.

  Examples of the plate-like filler include mica, glass flakes, various metal foils and the like.

  In the present invention, it is also possible to produce a PAS composition by using a small amount of other thermoplastic resins within a range not to impair the purpose. Here, the thermoplastic resin may be any thermoplastic resin that is stable at high temperatures. For example, an aromatic polyester composed of an aromatic dicarboxylic acid such as polyethylene terephthalate or polybutylene terephthalate and a diol or oxycarboxylic acid. Polyamide, polycarbonate, ABS, polyphenylene oxide, polyalkyl acrylate, polyacetal, polysulfone, polyether sulfone, polyether imide, polyether ketone, polyphenylene sulfide ketone, fluororesin and the like. These thermoplastic resins can also be used as a mixture of two or more.

  Furthermore, in the present invention, known substances added to general thermoplastic resins and thermosetting resins, that is, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, mold release agents, flame retardants, It is also possible to produce a PAS composition by appropriately using a flame retardant, a coloring agent such as a dye or a pigment, a lubricant, a nucleating agent, etc. according to the required performance.

  According to the present invention, it is possible to effectively remarkably increase the melt viscosity of a PAS composition, so that a PAS composition having improved molding processing characteristics such as injection molding, blow molding, pipe molding and the like is efficiently produced. It becomes possible.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these Examples. In addition, the melt viscosity described in an Example and a comparative example was measured in accordance with the following method.

~ Measurement of melt viscosity ~
Using a CFT-500 type flow tester manufactured by Shimadzu Corporation (dies: φ = 1.0 mm, L = 2.0 mm), the melt viscosity was measured at a load of 10 kgf after being held at 315 ° C. for 5 minutes.

Reference Example 1 (Synthesis of PPS)
An autoclave was charged with 100 l of N-methyl-2-pyrrolidone, 53.3 kg of 45% sodium hydrosulfide, and 35.9 kg of 48% sodium hydroxide, and 44.3 kg of water was distilled off while gradually raising the temperature to 200 ° C. Next, after cooling to 150 ° C., 55 l of N-methyl-2-pyrrolidone and 66.8 kg of p-dichlorobenzene were added, the temperature was raised to 225 ° C. and polymerized for 1 hour, and then the temperature was raised to 250 ° C. Polymerized for 2 hours. Further, 16.3 kg of water was added, and polymerization was carried out at 250 ° C. for 2 hours. After completion of the polymerization, the mixture was cooled to obtain a polymerization slurry.

  The polymerization slurry was recovered from the polymerization slurry by removing the polymerization solvent using a centrifugal sedimentation separator. Thereafter, the obtained polymerization cake was washed 5 times with warm water, then immersed in a hydrochloric acid aqueous solution adjusted to pH 3, and stirred at 25 ° C. for 30 minutes. Thereafter, washing was further carried out until the washing solution exceeded pH 6, followed by drying at 100 ° C. to obtain 31 kg of PPS.

  The melt viscosity of the obtained PPS (hereinafter referred to as PPS (1)) was 360 poise.

Example 1
PPS (1) is supplied from the supply port of a twin screw extruder (manufactured by Toshiba Machine Co., Ltd., (trade name) TEM-35-102B) having a melt-kneading zone set at 300 ° C., and 3-aminopropyltrimethoxysilane (boiling point; 215 ° C.) using a liquid feed pump (manufactured by Masterflex, (trade name) L / S 07524-50), 0.5 parts by weight with respect to 100 parts by weight of PPS (1) from the vent port closest to the supply port Was continuously fed to the twin screw extruder. At this time, the temperature of PPS (1) at the vent port was measured with a radiation thermometer (manufactured by Horiba, Ltd., (trade name) IT-550S), and it was 150 ° C.

  Then, PPS (1) and 3-aminopropyltrimethoxysilane were melt-kneaded and pelletized to obtain a PPS composition. The melt kneading time of PPS (1) and 3-aminopropyltrimethoxysilane was about 20 seconds.

  The melt viscosity of the obtained PPS composition is shown in Table 1.

  The melt viscosity of the obtained PPS composition was effectively remarkably enhanced, and had molding processing characteristics effective for injection molding, blow molding, pipe molding, and the like.

Examples 2-4
A PPS composition was obtained in the same manner as in Example 1, except that the amount shown in Table 1 was supplied instead of 0.5 part by weight of 3-aminopropyltrimethoxysilane per 100 parts by weight of PPS (1).

  The melt viscosity of the obtained PPS composition is shown in Table 1.

  The melt viscosity of the obtained PPS composition was effectively remarkably enhanced, and had molding processing characteristics effective for injection molding, blow molding, pipe molding, and the like.

Comparative Example 1
To 100 parts by weight of PPS (1), 0.5 part by weight of 3-aminopropyltrimethoxysilane was premixed for 15 minutes using a Henschel mixer. This mixture was supplied from a supply port of a twin-screw extruder (manufactured by Toshiba Machine, (trade name) TEM-35-102B) set at a kneading zone of 300 ° C., and melt-kneaded and pelletized to obtain a PPS composition.

  The melt viscosity of the obtained PPS composition is shown in Table 2.

  The melt viscosity of the obtained PPS composition was low.

Comparative Examples 2-4
A PPS composition was obtained in the same manner as in Comparative Example 1 except that the amount shown in Table 2 was supplied instead of 0.5 part by weight of 3-aminopropyltrimethoxysilane per 100 parts by weight of PPS (1).

  The melt viscosity of the obtained PPS composition is shown in Table 2.

  The melt viscosity of the obtained PPS composition was low.

Example 5
Except for supplying 0.5 parts by weight of 3-aminopropyltrimethoxysilane to 100 parts by weight of PPS (1), 0.75 parts by weight of 3-glycidoxypropyltrimethoxysilane (boiling point: 290 ° C.) was supplied. A PPS composition was obtained in the same manner as in Example 1.

  Table 3 shows the melt viscosity of the obtained PPS composition.

  The melt viscosity of the obtained PPS composition was effectively remarkably enhanced, and had molding processing characteristics effective for injection molding, blow molding, pipe molding, and the like.

Example 6
Except for supplying 0.5 parts by weight of 3-aminopropyltrimethoxysilane to 100 parts by weight of PPS (1), 0.75 parts by weight of 3-isosoanatopropyltriethoxysilane (boiling point: 250 ° C.) was supplied. A PPS composition was obtained in the same manner as in Example 1.

  Table 3 shows the melt viscosity of the obtained PPS composition.

  The melt viscosity of the obtained PPS composition was effectively remarkably enhanced, and had molding processing characteristics effective for injection molding, blow molding, pipe molding, and the like.

Example 7
Instead of 0.5 parts by weight of 3-aminopropyltrimethoxysilane per 100 parts by weight of PPS (1), N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine ( (Boiling point: 290 ° C.) A PPS composition was obtained in the same manner as in Example 1 except that 0.75 part by weight was supplied.

  Table 3 shows the melt viscosity of the obtained PPS composition.

  The melt viscosity of the obtained PPS composition was effectively remarkably enhanced, and had molding processing characteristics effective for injection molding, blow molding, pipe molding, and the like.

Claims (4)

A polyarylene sulfide, an amino group, an alkoxysilane compound having at least one functional group selected from the group consisting of an epoxy group and an isocyanate group, was continuously fed independently to the melt kneader, the polyarylene A method for producing a polyarylene sulfide composition, characterized in that the temperature at which the sulfide and the alkoxysilane compound contact each other is lower than the boiling point of the alkoxysilane compound, and then melt kneaded at a temperature equal to or higher than the melting point of the polyarylene sulfide. 0.05 to 3 parts by weight of an alkoxysilane compound having one or more functional groups selected from the group consisting of an amino group, an epoxy group and an isocyanate group is used with respect to 100 parts by weight of polyarylene sulfide. The manufacturing method of the polyarylene sulfide composition of Claim 1. Furthermore, an inorganic filler is supplied, The manufacturing method of the polyarylene sulfide composition of Claim 1 or 2 characterized by the above-mentioned. The method for producing a polyarylene sulfide composition according to any one of claims 1 to 3, wherein the melt kneader is a single screw extruder or a twin screw extruder.