JP3511271B2 - Method for producing polyarylene sulfide copolymer and composition containing copolymer obtained by the method - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polyarylene sulfide (PAS) copolymer and a composition containing the copolymer obtained by the method. More specifically, the present invention relates to a method for efficiently producing a polyarylene sulfide copolymer that is suitably used for various electric and electronic equipment parts and automobile equipment parts, and a composition containing the copolymer obtained by the production method.

[0002]

2. Description of the Related Art In recent years, polyarylene sulfide has excellent heat resistance, mechanical properties, chemical resistance, etc.
As described above, it has been widely used in various electric and electronic equipment parts, automobile equipment parts and the like. However, since polyarylene sulfide has a slow crystallization rate at the time of molding, there is a problem that sufficient crystallization does not occur in a mold at low temperature, resulting in deformation of the product, deterioration of heat resistance, and poor surface appearance. In order to eliminate such inconvenience, those to which a carboxylic acid ester has been added (JP-A-62-23048) and those to which a phosphoric acid ester has been added (JP-A-62-230850, JP-A-1-225660). JP-A-3-91563), alkyl mercaptan and inorganic filler added (JP-A 5-140451), monoepoxy compound added (JP-A 64-65171) and mercaptosilane. With addition of
No. 2-52958) and the like are disclosed.

[0003]

However, in both cases, a relatively low molecular weight substance having poor heat resistance is mixed as an additive such as a plasticizer by an extruder, and therefore unreacted substances are volatilized as vaporized gas during kneading. The effect is not sufficient, or it decomposes as a decomposed gas at the time of molding the product, and the molding surface and the mold are contaminated, resulting in deterioration of physical properties. Epoxy compounds are the most effective as a surface treatment material for glass fibers (GF) for PAS, etc., but this epoxy compound reacts with unreacted materials of alkyl mercaptan and inorganic filler, so that wetting of resins such as GF It has been a factor that hinders the deterioration of the physical properties and deteriorates the physical properties. In addition, a compound in which an aminated PAS is reacted with an acid anhydride (Japanese Patent Laid-Open No. 4-372624) is disclosed, but it is an acid anhydride having no alkyl chain and has no effect of promoting crystallization. . Furthermore P
Although a method of reacting an AS cyclic compound with an amino group-containing ring-opening polymerization catalyst has also been proposed, it is a method of introducing an amino group into a low molecular weight PAS cyclic compound, which is a high molecular weight PA.
It was not intended to use S or control the crystallization rate. The present invention has been made in view of the above-described problems, and an alkyl group (chain) is introduced into polyarylene sulfide (PAS) so that P having a high crystallization rate during molding can be obtained.
It is possible to obtain an AS copolymer, and to improve the reaction rate in the alkyl group (chain) introduction reaction and increase the amount of alkyl group (chain) introduced.
An object is to provide a method for producing an S copolymer. Further, even when using a low temperature mold at the time of molding, PAS excellent in physical properties and surface appearance and having a small amount of gas generation
It is an object to provide a composition containing a copolymer.

[0004]

To achieve the above object, according to the present invention, polyarylene sulfide (A) is used.
And a reactive compound (B) having a functional group are reacted with each other, in the method for producing a polyarylene sulfide copolymer, a polyarylene sulfide (A) and a reactive compound (B) having a functional group represented by the following formula (I ) Or an epoxy compound (B1) represented by the following formula (II) and a Lewis base (C) are reacted in an aprotic organic solvent (D),
Provided is a method for producing a polyarylene sulfide copolymer, which comprises introducing an alkyl group into the polyarylene sulfide (A). ^{R 1 -R 2 -X ... (I} ) ( wherein, ^{R 1} represents an alkyl group, an alkyloxy group, alkyl
Rcarbonyloxy group, R ² is a divalent hydrocarbon or o
Luganosiloxane and X each represent an epoxy group . )

[Chemical 2]

As a preferred embodiment, the mixing ratio of the polyarylene sulfide (A) at the time of reaction is 10 with respect to 1 liter of the aprotic organic solvent (D).
0 to 1,000 g, the epoxy compound (B1)
Of the polyarylene sulfide (A) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyarylene sulfide (A), and the mixing ratio of the Lewis base (C) is polyarylene sulfide. (A) 0.0001 to 1 wt% relative to 100 parts by weight of the polyarylene sulfide copolymer is provided.

Further, the aprotic organic solvent (D)
Is N-methyl-2-pyrrolidone, and a method for producing a polyarylene sulfide copolymer is provided.

Furthermore, the polyarylene sulfide copolymer is characterized by comprising 100 parts by weight of the polyarylene sulfide copolymer obtained by the above-mentioned production method and 0 to 400 parts by weight of the inorganic or organic filler (E). A composition containing is provided.

The method for producing the polyarylene sulfide copolymer of the present invention and the composition containing the copolymer obtained by the method will be specifically described below. 1. Method for producing polyarylene sulfide copolymer (1) Reaction component In the present invention, polyarylene sulfide (A)
With an epoxy compound (B1) and a Lewis base (C) in an aprotic organic solvent (D) to give PAS
An alkyl group is introduced into (A). ( A) Polyarylene sulfide (A) The polyarylene sulfide (PA used in the present invention
S) (A) is a polymer containing a repeating unit represented by the structural formula -Ar-S- (where Ar is an arylene group) in an amount of 70 mol% or more.
I)

[0009]

[Chemical 3]

(In the formula, R ³ is a substituent selected from an alkyl group having 6 or less carbon atoms, an alkoxy group, a phenyl group, a carboxyl group, a cyano group, an amino group and a halogen atom, and m is an integer of 0-4. In addition, n is an average degree of polymerization and is in the range of 1.3 to 30), and is a polyphenylene sulfide having a repeating unit represented by 70 mol% or more. Above all, α-chloronaphthalene solution (concentration 0.4 g
/ Dl), the inherent viscosity at 206 ° C. is 0.1 to 0.5
(Dl / g), preferably 0.13 to 0.4 (dl / g
g), more preferably 0.15 to 0.35 (dl /
Those in the range of g) are suitable. PAS is generally known to have a substantially linear molecular structure having no branched or crosslinked structure and a structure having a branched or crosslinked structure depending on the production method. Is also effective. The preferred PAS used in the present invention has a repeating unit of 70% by mole or more of paraphenylene sulfide units, more preferably 80% by mole.
It is a homopolymer or copolymer containing the above. If this repeating unit is less than 70 mol%, the original crystallinity, which is a characteristic of a crystalline polymer, tends to be low, and sufficient mechanical properties may not be obtained, which is not preferable. Examples of the copolymerization structural unit include a metaphenylene sulfide unit, an orthophenylene sulfide unit, a p, p'-diphenylene ketone sulfide unit, a p, p'-diphenylene sulfone sulfide unit, a p, p'-biphenylene sulfide unit, and a p. , P′-diphenylene ether sulfide unit, 2,6-naphthalene sulfide unit and the like. As the polyarylene sulfide of the present invention, in addition to the above-mentioned substantially linear polymer, a branched or crosslinked polyarylene sulfide obtained by polymerizing a small amount of a monomer having three or more functional groups as a part of the monomer is also used. It is possible to use a blended polymer prepared by blending the above linear polymer with the above-mentioned linear polymer. Further, as PAS as the component (A) used in the present invention, a polymer having a relatively low molecular weight linear polymer whose melt viscosity is increased by oxidative crosslinking or thermal crosslinking to improve molding processability can also be used.

(B) Epoxy compound (B1 ) As the epoxy compound (B1) used in the present invention,
Examples thereof include those represented by the above formula (I) or formula (II). That is, in ^{R 1 -R 2 -X ... (I} ) ( wherein, ^{R 1} represents an alkyl group, an alkyloxy group, alkyl
Rcarbonyloxy group, R ² is a divalent hydrocarbon or o
Luganosiloxane and X each represent an epoxy group . )

[Chemical 4] Such an epoxy compound (B1) has an epoxy group of 1
It is a monoepoxy compound (B1-1) having only one.

Monoe used for the component (B1) of the present invention
The epoxy compound (B1-1) has one epoxy group in the molecule.
It is a compound having only one.

Examples of such compounds include various glycidyl esters, glycidyl ethers, and 1,2-
Examples thereof include alkylene oxides. As specific examples, various alkyl glycidyl ethers such as bromo glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, cyclopentyl glycidyl ether, hexyl glycidyl ether, cyclohexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, no Nanyl glycidyl ether, decanyl glycidyl ether, dodecanyl glycidyl ether,
Tridecanyl glycidyl ether, tetradecanyl glycidyl ether, pentadecanyl glycidyl ether,
Alkyl polyethylenoxy glycidyl ether, alkyl glycidyl ether having 16 to 50 carbon atoms, glycerol glycidyl ether, glycerol glycidyl ether and their double bond inclusions, aryl glycidyl ethers such as phenyl glycidyl ether, biphenyl glycidyl ether, naphthyl glycidyl ether , Methylphenyl glycidyl ether, ethyl phenyl glycidyl ether, propyl phenyl glycidyl ether, butyl phenyl glycidyl ether, propenyl phenyl glycidyl ether, C5-20 alkyl group-substituted phenyl glycidyl ether, chloro-substituted phenyl glycidyl ether, bromo-substituted glycidyl ether, Glycidyl esters such as acrylic acid glycidyl ester, Aryl glycidyl esters having 7 to 30 carbon atoms such as glycidyl esters of saturated and unsaturated fatty acids having 2 to 50 carbon atoms such as glycidyl acrylate, coconut oil glycidyl ester, soybean oil glycidyl ester, and benzoic acid glycidyl ester , And its alkyl, halogen-substituted products, glycidyl ester represented by the following formula,

[0014]

[Chemical 5]

(Wherein R represents a linear or branched alkylene group having 1 to 10 carbon atoms), glycidyl phthalimide,
Substitution of alkylene oxides such as cyclohexane oxide, and their aryl groups having 1 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, phenoxy groups, halogen groups, nitro groups, etc. You can raise your body. These monoepoxy compounds (B1-1) may be used as a mixture of two or three or more.

[0016]

[0017]

(C) Lewis Base (C) The Lewis base (C) used in the present invention is not particularly limited, but a tertiary amine compound is preferable because of its excellent electron donating property. Examples of such a tertiary amine compound include the compound shown in Chemical formula 3 below, dimethylbenzylamine, 1,8-diazabicyclo (5,4,0) undecane (DBU), and pyridine.
Examples of other Lewis bases (C) include tris (dimethylaminomethyl) phenol, ammonium chloride, caustic soda, triphenylphosphine, and aqueous ammonia.

[0019]

[Chemical 6]

This Lewis base (C) improves the reaction rate in the alkyl group introduction reaction of the present invention,
At the same time, it acts as a catalyst for increasing the introduction amount of the alkyl group (chain).

(D) Aprotic organic solvent (D) The aprotic organic solvent (E) used in the present invention is generally an aprotic polar organic compound (eg, amide compound, lactam compound, urea compound). , Organic sulfur compounds, cyclic organic phosphorus compounds, etc.) can be preferably used as a single solvent or as a mixed solvent.

Among these aprotic polar organic compounds, examples of the amide compound include N, N-
Dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dipropylacetamide, N,
Examples thereof include N-dimethylbenzoic acid amide.

Examples of the lactam compound include caprolactam, N-methylcaprolactam, N
-N-alkylcaprolactams such as -ethylcaprolactam, N-isopropylcaprolactam, N-isobutylcaprolactam, N-normalpropylcaprolactam, N-normalbutylcaprolactam, N-cyclohexylcaprolactam, N-methyl-2-pyrrolidone (NMP), N -Ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-normal propyl-2-pyrrolidone, N-normal butyl-2-pyrrolidone, N-cyclohexyl-
2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-
Methyl-3,4,5-trimethyl-2-pyrrolidone, N
-Methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-
6-methyl-2-piperidone, N-methyl-3-ethyl-2-piperidone and the like can be mentioned.

Examples of the urea compound include tetramethylurea, N, N'-dimethylethyleneurea, N, N'-dimethylpropyleneurea and the like.

Further, as the organic sulfur compound,
For example, dimethyl sulfoxide, diethyl sulfoxide, diphenyl sulfone, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, and the like as the cyclic organic phosphorus compound. Examples thereof include 1-methyl-1-oxophosphorane, 1-normalpropyl-1-oxophosphorane, 1-phenyl-1-oxophosphorane and the like.

These various aprotic polar organic compounds may be used alone or in combination of two or more,
Furthermore, it can be used as the aprotic organic solvent by mixing with other solvent components which do not hinder the purpose of the present invention.

Of the above various aprotic organic solvents, N-alkylcaprolactam and N- are preferred.
Alkylpyrrolidone, particularly preferred is N-methyl-2-pyrrolidone.

(2) Blending Ratio of Introducing Alkyl Group into PAS (A) The blending ratio in the reaction of introducing an alkyl group into PAS (A) in the present invention will be described below.

(I) PAS (A) 1 liter for 1 liter of the aprotic organic solvent (D).
It is preferable that the amount is from 00 to 1,000 g. If it is less than 100 g, the productivity will decrease, and if it exceeds 1,000 g, the reaction will be insufficient.

(Ii) Epoxy compound (B1) The amount is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, and most preferably 0.5 to 10 parts by weight based on 100 parts by weight of PAS. Parts by weight. 0.
If it is less than 1 part by weight, the intended effect cannot be obtained,
If it exceeds 20 parts by weight, the crystallinity is lowered and the heat resistance is lowered, so that the molecular weight is lowered.

(Iii) Lewis base (C) 0.0001 based on 100 parts by weight of the PAS (A).
It is preferable to be set to 1% by weight. 0.0001% by weight
If it is less than the above range, the reactivity is not improved by the addition, and if it exceeds 1% by weight, the reactivity is deteriorated.

Reaction conditions (i) The reaction temperature is preferably 30 to 300 ° C, more preferably 200 to 300 ° C. If the temperature is lower than 30 ° C, the reaction becomes insufficient, and 3
When the temperature exceeds 00 ° C, a side reaction occurs.

(Ii) Reaction time is preferably 10 minutes to 25 hours, more preferably 30 minutes to 3 hours. If it is less than 10 minutes, the reaction becomes insufficient, and 2
If it exceeds 5 hours, the productivity will decrease and side reactions will occur.

(Iii) Reaction pressure There is no particular limitation, and normal pressure may be used.

Post-treatment In the present invention, the post-treatment is not particularly limited, and the alkyl group (chain) is subjected to usual filtration, washing with water, an organic solvent (acetone, alcohol, etc.), and drying.
It is possible to obtain PAS (A) into which is introduced.

2. Composition filler containing PAS copolymer (F) The inorganic or organic filler (E) used in the composition containing the PAS copolymer of the present invention has mechanical properties, heat resistance, and dimensional stability. A fibrous, powdery, or plate-like filler is used depending on the purpose such as obtaining a molded product having excellent properties such as (deformation resistance, warpage) and electrical properties. The fibrous filler includes glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum, titanium,
Inorganic fibrous substances such as metallic fibrous substances such as copper and brass can be mentioned. Particularly typical fibrous filler is glass fiber or carbon fiber. In addition, high-melting point organic fibrous substances such as aromatic polyamide, fluororesin, and acrylic resin can also be used. On the other hand, as the granular filler, carbon black, fused or crystalline silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth,
Silica salts such as wollastonite, metal oxides such as iron oxide, titanium oxide, zinc oxide, alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metals such as calcium sulfate, barium sulfate. Other examples include sulfates, silicon carbide, boron nitride, and various metal powders. Examples of the plate-shaped filler include mica, glass flakes, various metal foils, and the like. These inorganic fillers can be used alone or in combination of two or more.
The combined use of fibrous fillers, in particular glass fibers or carbon fibers and granular and / or plate-like fillers is particularly advantageous in terms of mechanical strength and dimensional accuracy,
It is a preferable combination in terms of having electrical properties and the like. When using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary. If this example is shown, an epoxy compound, an isocyanate compound,
It is a functional compound such as a silane compound and a titanate compound. These compounds may be used by subjecting the filler to a surface treatment or a converging treatment in advance, or may be added at the same time when the material is prepared. The amount of filler used is the same as the PAS
(A) 400 parts by weight or less per 100 parts by weight, preferably 10 to 300 parts by weight. The lower limit is not particularly limited, but if it is less than 10 parts by weight, mechanical strength and rigidity may be poor depending on the use of the molded product. Also, 40
If it exceeds 0 parts by weight, molding work becomes difficult and
The mechanical properties of the molded product deteriorate.

Other Thermoplastic Resins In the composition of the present invention, as the base polymer, other thermoplastic resins may be supplementarily used in a small amount in addition to PAS (A) within a range not impairing the purpose. Is. Any other thermoplastic resin may be used as long as it is a thermoplastic resin that is stable at high temperatures.
For example, an aromatic polyester resin composed of an aromatic dicarboxylic acid such as polyethylene terephthalate or polybutylene terephthalate and a diol or an oxycarboxylic acid, nylon 6, nylon 6-6, nylon 6-10,
Polyamide resins such as nylon 12 and nylon 46, olefin resins containing ethylene, propylene and butene as a main component, polystyrene, polystyrene-acrylonitrile, styrene resins such as ABS, polycarbonate,
Polyphenylenoxide, polyalkyl acrylate, polyacetal, polysulfone, polyether sulfone,
Examples thereof include polyetherimide, polyetherketone, and fluororesin. Further, these thermoplastic resins may be used as a mixture of two or more kinds.

Additives In the composition of the present invention, known additives generally added to thermoplastic resins, that is, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, dyes and pigments, etc. Colorants,
Lubricants, mold release agents, etc. can be appropriately added depending on the required performance.

[0039]

EXAMPLES The present invention will be described in more detail below with reference to examples. The following Examples 1 to 19 and Comparative Examples 1 to
In 8, the preparation of PAS and the method of manufacturing and evaluating samples were performed as follows. <Preparation of PAS> PAS1 A hydrous sodium sulfide (Na ₂ S) was added to a polymerization tank equipped with a stirrer.
5H ₂ O) 883 mol, LiCl 830 mol, N
Dehydration treatment was carried out for 1 hour while adding MP 510 liters and keeping the temperature at 145 ° C. under reduced pressure. Then, the reaction system was cooled to 45 ° C., 857 mol of DCB (p-dichlorobenzene) was added, and polymerization was carried out at 260 ° C. for 3 hours. 5 times with hot water, 1
It was washed once with 70 ° C. NMP and three times with water, and dried at 185 ° C. to obtain a linear PAS1. The obtained PAS1 had an inherent viscosity of 0.23.

PAS2 (aminated PAS) Hydrous sodium sulfide (Na ₂ S) was added to a polymerization tank equipped with a stirrer.
5H ₂ O) 840 mol, LiCl 833 mol and NM
P510 liter was added and dehydration treatment was carried out for 1 hour while maintaining the temperature at 145 ° C. under reduced pressure. Then, after cooling the reaction system to 45 ° C., 840 mol of DCB and 41.5 mol of DCA were added and 240
Polymerization was carried out at ℃ for 5 hours. The contents were washed 5 times with hot water, once with 170 ° C. NMP, 3 times with water and dried at 185 ° C. to obtain aminated PAS2. The obtained PAS2 has an inherent viscosity of 0.
22 (dl / g) and the amount of amino groups was 1.0 mol%. The following were used as the monoepoxy compound. ME1: Cardanol epoxy compound (trade name: Epicard, manufactured by Shima Trading Co., Ltd.), and its structural formula is shown below.

[0041]

[Chemical 7]

ME2: n-butyl glycidyl ether (trade name: BGE manufactured by Yuka Shell Co., Ltd.), and its structural formula is shown below.

[0043]

[Chemical 8]

ME3: C12-C13 mixed alcohol type glycidyl ether (trade name: Y manufactured by Yuka Shell Co., Ltd.
ED-111) and its structural formula are shown below.

[0045]

[Chemical 9]

ME4: (trade name of Rikaresin EB manufactured by Shin Nippon Rika Co., Ltd.) and its structural formula are shown below.

[0047]

[Chemical 10]

The following were used as the polyepoxy compound. DE1: Ethylene, polyethylene glycol diglycidyl ether (product name: Denacol EX-861, manufactured by Nagase Chemical Industry Co., Ltd.) DE2: Polytetramethylene glycol diglycidyl ether (product name: Nagase Chemical Industry Co., Ltd .: Denacol EX
-992)

As the plasticizer, PL1: trimellitic acid isodecyl ester (C10 manufactured by Asahi Denka Co., Ltd.)
As an inorganic filler, GF (manufactured by Asahi Fiber Glass: JAFT591) or calcium carbonate (manufactured by Shiraishi Calcium: P-30) was used.

<Sample Production and Evaluation Method> (Kneading) After dry blending with a twin screw extruder at a compounding ratio described below,
The resin of the copolymer was melt mixed at a temperature of 300 ° C. to prepare pellets. (Physical property evaluation) The pellets obtained above were made into a test piece at a resin temperature of 300 ° C. for neat, a mold temperature of 135 ° C. at 100 ° C. for a composition containing a filler, and a Izod strength (ASTM). Bending strength (ASTM D7)
90) and surface gloss (JIS K7105). (Gas Generation Amount) A gas generation amount was calculated by measuring the weight reduction rate of the obtained PAS copolymer and the pellet containing the composition containing the PAS copolymer, which was left at 320 ° C. for 30 minutes, using TGA. (Crystallization rate) The obtained PAS copolymer and a pellet of the composition containing the same were pressed at 320 ° C. and then rapidly cooled with ice water to obtain an amorphous film, which was then held at 50 ° C. for 1 minute in DSC. 32
The low temperature crystallization temperature and the melting crystallization temperature obtained by measuring the temperature pattern of 20 ° C./min to 0 ° C., holding at 320 ° C. for 5 minutes and then decreasing to 50 ° C. at 20 ° C./min. Evaluated. The low temperature crystallization temperature refers to the crystallization temperature that appears after the glass transition temperature when the temperature is raised, and the melt crystallization temperature refers to the crystallization temperature that appears when the temperature is lowered after melting once at 320 ° C. When the crystallization speed is high, the low temperature crystallization temperature is low and the melt crystallization temperature is high.

[ Reference Example 1 ] PAS1 was added to 1 liter of SUS autoclave with 50 parts.
g, NMP (250 ml), ME1 (2.5 g) and pyridine (0.02 g) were added, reacted at 260 ° C. for 60 minutes, filtered off, washed twice with acetone and twice with water, and depressurized at 120 ° C. It was dried under to obtain a PAS copolymer.

[0052] In Comparative Example 1 Reference Example 1, except that no addition of ME1 and pyridine Follow the same procedure as in Reference Example 1 to obtain a PAS copolymer.

[Comparative Example 2] In Comparative Example 1 , except that pyridine was not added.
The same operation as in Reference Example 1 was performed to obtain a PAS copolymer.

[Comparative Example 3] 25 g of ME1 was dry blended with 500 g of PAS1 and melted and kneaded at 290 ° C in an extruder to obtain a mixture.

[0055] In Example 1 Reference Example 1, except for using ME2 in place of ME1 perform the same operation as in Reference Example 1 to obtain a PAS copolymer.

[0056] In Example 2 Reference Example 1, except for using ME3 in place of ME1 perform the same operation as in Reference Example 1 to obtain a PAS copolymer.

[0057] In Example 3 Reference Example 1, except for using ME4 instead of ME1 perform the same operation as in Reference Example 1 to obtain a PAS copolymer.

[0058] In Reference Example 2 Reference Example 1, except for using DE1 in place of ME1 perform the same operation as in Reference Example 1 to obtain a PAS copolymer.

[0059] In Reference Example 3 Reference Example 1, except for using DE2 in place of ME1 perform the same operation as in Reference Example 1 to obtain a PAS copolymer.

[0060] In Reference Example 4 Reference Example 1, except for using PAS2 instead of PAS1 perform the same operation as in Reference Example 1 to obtain a PAS copolymer.

[0061] In Example 4 Reference Example 4, except for using ME2 in place of ME1 perform the same operation as in Reference Example 4, to obtain a PAS copolymer.

[0062] In Reference Example 5 Reference Example 4, except for using DE1 in place of ME1 perform the same operation as in Reference Example 4, to obtain a PAS copolymer. The above results are shown in Table 1.

[0063]

[Table 1]

From the above, the crystallization rate of Comparative Example 3 and Examples 1 to 4 was faster than that of Comparative Example 1, and Tcc
And Tmc are increased. However, in the kneading by the extruder of Comparative Example 3, there was little reaction, and gas (unreacted M
A large amount of E1) came out, and the environment was deteriorated and moldability was poor. Further, in Comparative Example 2, Tc is higher than that in Reference Example 1.
It was found that the degree of decrease in c and the increase in Tmc were small and the reaction rate was low. Furthermore, aminated PPS (PAS
In Reference Example 4 and Example 4 using 2), since the reactivity of the epoxy is increased as compared with PAS1, the introduction efficiency of the epoxy compound is good, and the decrease of Tcc and Tmc of Reference Example 1 are improved. The degree of rise has increased.

Comparative Example 5 67 parts by weight of GF was added to 100 parts by weight of PAS1, and the mixture was kneaded at 320 ° C. to prepare pellets and test pieces. The mechanical properties, gas amount, crystallization rate, and surface appearance of this test piece were examined.

Comparative Example 6 67% by weight of the mixture obtained in Comparative Example 3, 100 parts by weight.
GF of weight part was added, and it kneaded at 320 degreeC, the pellet was produced, and the test piece was produced. Mechanical properties of this test piece,
The amount of gas, the crystallization rate, and the surface appearance were examined.

[Comparative Example 7] 100 parts by weight of GF, based on 100 parts by weight of PAS1,
100 parts by weight of calcium carbonate was added, and the mixture was kneaded at 320 ° C. to prepare pellets and test pieces. The mechanical properties, gas amount, crystallization rate, and surface appearance of this test piece were examined.

[Comparative Example 8] 10 parts by weight of the mixture obtained in Comparative Example 3, 100 parts by weight.
0 parts by weight of GF and 100 parts by weight of calcium carbonate were added, and the mixture was kneaded at 320 ° C. to prepare pellets and test pieces. The mechanical properties, gas amount, crystallization rate, and surface appearance of this test piece were examined.

Reference Example 6 67 parts by weight of GF was added to 100 parts by weight of the PAS copolymer obtained in Reference Example 1 , and the mixture was kneaded at 320 ° C. to prepare pellets and test pieces. The mechanical properties, gas amount, crystallization rate, and surface appearance of this test piece were examined.

Example 5 67 parts by weight of GF was added to 100 parts by weight of the PAS copolymer obtained in Example 1 and kneaded at 320 ° C. to prepare pellets and test pieces. The mechanical properties, gas amount, crystallization rate, and surface appearance of this test piece were examined.

Reference Example 7 67 parts by weight of GF was added to 100 parts by weight of the PAS copolymer obtained in Reference Example 2 and kneaded at 320 ° C. to prepare pellets and test pieces. The mechanical properties, gas amount, crystallization rate, and surface appearance of this test piece were examined.

Reference Example 8 67 parts by weight of GF was added to 100 parts by weight of the PAS copolymer obtained in Reference Example 4 , and the mixture was kneaded at 320 ° C. to prepare pellets and test pieces. The mechanical properties, gas amount, crystallization rate, and surface appearance of this test piece were examined.

Reference Example 9 67 parts by weight of GF was added to 100 parts by weight of the PAS copolymer obtained in Reference Example 5 , and the mixture was kneaded at 320 ° C. to prepare pellets and test pieces. The mechanical properties, gas amount, crystallization rate, and surface appearance of this test piece were examined.

[ Reference Example 10 ] 100 parts by weight of GF and 100 parts by weight of calcium carbonate were added to 100 parts by weight of the PAS copolymer obtained in Reference Example 1 , and the mixture was kneaded at 320 ° C to prepare pellets. Then, a test piece was prepared. The mechanical properties, gas amount, crystallization rate, and surface appearance of this test piece were examined.

[ Reference Example 11 ] 100 parts by weight of GF and 100 parts by weight of calcium carbonate were added to 100 parts by weight of the PAS copolymer obtained in Reference Example 2 and kneaded at 320 ° C to prepare pellets. Then, a test piece was prepared. The mechanical properties, gas amount, crystallization rate, and surface appearance of this test piece were examined.

[ Reference Example 12 ] 100 parts by weight of GF and 100 parts by weight of calcium carbonate were added to 100 parts by weight of the PAS copolymer obtained in Reference Example 4 , and the mixture was kneaded at 320 ° C to prepare pellets. Then, a test piece was prepared. The mechanical properties, gas amount, crystallization rate, and surface appearance of this test piece were examined.

Reference Example 13 To 100 parts by weight of the PAS copolymer obtained in Reference Example 5 , 100 parts by weight of GF and 100 parts by weight of calcium carbonate were added and kneaded at 320 ° C. to obtain pellets. A test piece was prepared. About this test piece, mechanical properties, gas amount,
The crystal acceleration and surface appearance were examined. The above results are shown in Table 2.

[0078]

[Table 2]

From the above, the following was found. Compared with Comparative Example 5, the epoxy compound mixed in the extruder as in Comparative Example 6 had a mold temperature of 100 ° C. as compared with the mold temperature of 135 ° C.
The surface gloss of the molded product at 70 ° C. is 70 units as compared with 52.3 in Comparative Example 5, which improves the surface appearance. However, a large amount of gas is generated, and as a result, the physical properties are greatly reduced. Compared with this, as in Examples 7 to 11 , the PAS
The resin which is reacted with has a surface gloss equal to or higher than that of a mixture obtained by blending an epoxy compound with an extruder even when molding at a mold temperature of 100 ° C., and does not deteriorate physical properties.

[0080]

As described above, according to the present invention, P
By introducing an alkyl group (chain) into AS, it is possible to obtain a PAS copolymer having a high crystallization rate during molding. In addition, in the alkyl group (chain) introduction reaction, it is possible to improve the reaction rate and increase the introduction amount of the alkyl group (chain). Furthermore, a composition containing a PAS copolymer which is excellent in physical properties and surface appearance and has a small amount of gas generation can be obtained even when a low temperature mold is used during molding.

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Claims (4)

(57) [Claims] 1. A method for producing a polyarylene sulfide copolymer, which comprises reacting a polyarylene sulfide (A) with a reactive compound (B) having a functional group, which comprises the polyarylene sulfide (A) and a functional group. As the reactive compound (B), the following formula (I) or the following formula (I
The epoxy compound (B1) shown in I) and the Lewis base (C) are reacted in an aprotic organic solvent (D),
A method for producing a polyarylene sulfide copolymer, which comprises introducing an alkyl group into the polyarylene sulfide (A). ^{R 1 -R 2 -X ... (I} ) ( wherein, ^{R 1} represents an alkyl group, an alkyloxy group, alkyl
Rcarbonyloxy group, R ² is a divalent hydrocarbon or o
Luganosiloxane and X each represent an epoxy group . ) [Chemical 1] 2. The mixing ratio of the polyarylene sulfide (A) at the time of reaction is such that the aprotic organic solvent (D).
It is 100 to 1,000 g per 1 liter, and the mixing ratio of the epoxy compound (B1) at the time of reaction is 100 parts by weight of the polyarylene sulfide (A).
0.1 to 20 parts by weight, and the mixing ratio of the Lewis base (C) at the time of reaction is 0.0001 to 1% by weight based on 100 parts by weight of the polyarylene sulfide (A). The method for producing a polyarylene sulfide copolymer according to claim 1, which is characterized in that. 3. The aprotic organic solvent (D) is N
-Methyl-2-pyrrolidone, The method for producing a polyarylene sulfide copolymer according to claim 1 or 2, wherein 4. 100 parts by weight of a polyarylene sulfide copolymer obtained by the production method according to claim 1, and 0 to 4 inorganic or organic fillers (E).
100 parts by weight of the polyarylene sulfide copolymer.