JP3019105B2 - Method for producing polyarylene sulfide copolymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a polyarylene sulfide copolymer, and more particularly to a method for producing a polyarylene sulfide copolymer having a remarkably high crystallization rate. It is about.

Polyarylene sulfide has attracted attention as a member of electric and electronic devices and a member of an automobile device by utilizing its excellent heat resistance and chemical resistance.

Further, it can be molded into various molded parts, films, sheets, fibers, and the like by injection molding, extrusion molding, and the like, and is widely used in fields requiring heat resistance and chemical resistance.

[Prior Art] As disclosed in Japanese Patent Publication No. 45-3368, polyarylene sulfide is prepared by reacting a dihalo aromatic compound with an alkali metal sulfide such as sodium sulfide in a polar aprotic solvent such as N-methylpyrrolidone. Is obtained by reacting

However, polyarylene sulfide obtained by this method, particularly poly (p-phenylene sulfide) (hereinafter abbreviated as PPS), which is crystalline, has a relatively high glass transition temperature (Tg) of about 90 ° C. and a high crystallization rate. Therefore, when trying to obtain a molded product by injection molding, the mold temperature should be 130 to 1
Unless set to 50 ° C, a product with excellent heat resistance and dimensional stability could not be obtained. This is a major problem of PPS in the molding process compared to the fact that other general-purpose engineering plastics such as nylon and polybutylene terephthalate can be molded at a mold temperature of 100 ° C or less. I have.

In order to solve this problem, an oligomeric ester having a maximum weight average molecular weight of 6000 is added to PPS having a melt viscosity of at least 50 poise (JP-A-62-45654), and a monomeric carboxylic acid ester is added. (Japanese Unexamined Patent Publication No. Sho 62-230848), adding another thioether (Japanese Unexamined Patent Publication No. Sho 62-230849), and adding a specific aromatic phosphate ester (Japanese Unexamined Patent Publication No. Sho 62-230850). Kaihei 1-
No. 225660) is known. However, in any of the methods, the heat resistance of the additive is poor, so that an evaporating gas or a decomposition gas is generated during the molding process, or the low molecular weight additive migrates to the surface of the molded product, and the additive contaminates the surface of the molded product. And so on.

[Problems to be Solved by the Invention] The present invention provides a method for producing a polyarylene sulfide copolymer having a remarkably high crystallization rate based on the above items.

Means for Solving the Problems The present inventors have found that a polyarylene sulfide copolymer obtained by reacting a polyarylene sulfide having a hydroxyl group with a specific halogenated aliphatic hydrocarbon has the above-mentioned conventional problems. The present inventors have found that the crystallization rate has been improved, the crystallization rate has been remarkably increased, and sufficient crystallization can be achieved even when a low-temperature mold is used.

That is, the present invention, in a polar organic solvent, the reaction temperature 90 ~ 270 ° C ...
Wherein a polyarylene sulfide having a hydroxyl group is reacted with a halogenated aliphatic hydrocarbon by the following general formula (A) or (B): (R is an alkyl group having 1 to 50 carbon atoms, 1 is an integer of 2 or more,
m: n = 0.95: 0.05 to 0.999: 0.001, m + n = 1, and m: n represents a molar ratio. The present invention relates to a method for producing a polyarylene sulfide copolymer having a melt viscosity of 10 to 100,000 poise as shown by

 The details will be described below.

The polyarylene sulfide copolymer of the present invention represented by the general formula (A) or (B) has a melt viscosity (300 ° C., a die diameter of 0.5 mm, a length of 2 mm, and a shear rate of 200 (sec) ⁻¹ ). Measured using a Koka type flow tester)
Polyarylene sulfide in the range of 100,000 poise, preferably 100 to 30,000 poise. The polyarylene sulfide represented by the general formula (B) may be either a random or block copolymer.

Polyarylene sulfides having a hydroxyl group used in the present invention are disclosed in JP-A-64-48828 and JP-A-64-48828.
-Polymer phenol is obtained by adding a mono- or polyhalogenated phenol to a known method for producing a polyarylene sulfide disclosed in, for example, JP-A-48829.

Further, as the polyarylene sulfide having a hydroxyl group suitably used in the present invention, the melt viscosity (300
℃, die diameter 0.5mm, length 2mm, shear rate 200 (sec) ^-1
Value measured using a Koka flow tester under the conditions of
Is a polyarylene sulfide in the range of 10 to 100,000 poise, preferably 100 to 30,000 poise, and may be linear or oxidatively crosslinked in the presence of oxygen.

Further, halogenated aliphatic hydrocarbons used in the present _{invention, X-C n H 2n +} 1 (X: fluorine, chlorine, bromine, iodine, n
= 1 to 50), and the number of carbon atoms is particularly preferably n = 2 to 20.

Specific examples thereof include brominated ethane, brominated hexane, brominated octane, chlorinated octane, brominated decane, brominated tetradecane, chlorinated tetradecane, brominated octadecane, and chlorinated octadecane.

The method for producing the polyarylene sulfide copolymer of the present invention can be considered in the following two steps.

(A) One or two or more selected from hydroxyl group-containing polyarylene sulfide and alkali metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, etc.
A step of reacting in a temperature range of 0 ° C. to convert hydroxyl groups of polyarylene sulfide to alkoxides.

(B) a step of reacting the alkoxylated polyarylene sulfide with a halogenated aliphatic hydrocarbon in a temperature range of 90 to 270 ° C, particularly preferably 150 to 250 ° C.

The above reaction can be carried out in a single-stage reaction in which batch charging is performed or in two or more independent reactions.

As the reaction solvent, a polar organic solvent used in a general polycondensation reaction can be used.

Specific examples thereof include N-methylpyrrolidone, dimethylsulfone, dimethylformamide and the like.

The polyarylene sulfide copolymer obtained as described above has the same thermal decomposition temperature as compared with conventional polyarylene sulfide, and has a higher crystallization rate than conventional polyarylene sulfide. Even when injection molding is performed using a low-temperature mold, it is sufficiently crystallized,
A molded article having excellent heat resistance can be obtained.

In the resin of the present invention, as necessary, reinforcing fillers such as glass fibers, carbon fibers, ceramic fibers such as alumina fibers, aramid fibers, wholly aromatic polyester fibers, metal fibers, and potassium titanate whiskers, and calcium carbonate. ,
Mica, talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nepheline sinite, attapulgite, wollastonite, PMF, ferrite, calcium silicate, magnesium carbonate, dolomite, three Antimony oxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum,
Inorganic fillers such as glass beads, glass powder, glass balloons, quartz and quartz glass, and organic and inorganic pigments can also be blended.

In addition, release agents, silane-based and titanate-based coupling agents, lubricants, heat stabilizers, weathering stabilizers, foaming agents, rust inhibitors, ion trapping agents, flame retardants, flame retardant assistants, etc. as required May be added.

Further, if necessary, polyethylene, polybutadiene, polyisoprene, polychloroprene, polystyrene, polybutene, polyvinyl acetate, polyvinyl chloride, polyacrylate, polymethacrylate, polyacrylonitrile, nylon 6, nylon 66, nylon 4
Polyesters such as 6, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyurethane, polyacetal, polycarbonate, polyphenylene oxide, polysulfone, polyether sulfone, polyallylsulfone, polyphenylene sulfide sulfone, polyether ketone, polyphenylene sulfide ketone, poly One or more of homopolymers such as ether ether ketone, polyimide, polyamide imide, silicone resin, phenoxy resin, and fluororesin, and random or block and graft copolymers may be used in combination.

[Examples] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to only these examples.

The crystallization rate of the polyarylene sulfide copolymer obtained in the following examples was determined by quenching the melted sample to obtain an amorphous sample obtained from Seiko Denshi Co., Ltd.
The crystallization temperature (Tc ₁ ) when the temperature was raised at a rate of 10 ° C./min. In nitrogen using DSC200 and the melted sample was 10 ° C./mi
The evaluation was performed by measuring the recrystallization temperature (Tc ₂ ) when the temperature was lowered at the cooling rate of n.

The thermal decomposition temperature (Td) of the obtained resin was measured at a heating rate of 40 ° C./min. In nitrogen using TG / DTA200 manufactured by Seiko Instruments Inc.

Melt viscosity is 0.5mm in diameter by Koka type flow tester.
The measurement was carried out at 300 ° C. and a shear rate of 200 (sec) ⁻¹ using a 2 mm long die.

Reference Example 1 15 N-methylpyrrolidone 5 was charged into an autoclave and heated to 120 ° C., and then 2.8 sodium chloride sodium sulfide was added.
1866g charged, 205 ° C gradually with stirring over about 2 hours
The temperature was raised to 407 g of water. Thereafter, the mixture was cooled to 140 ° C., 2091 g of p-dichlorobenzene and 9.3 g of p-chlorophenol were added, the temperature was raised to 250 ° C., and the reaction was carried out for 3 hours to obtain a polyarylene sulfide having a hydroxyl group at a terminal. The melt viscosity of this polymer was 220 poise. In addition, p-
The conversion of chlorophenol was 55%.

Subsequently, the polymer was subjected to a heat treatment at 250 ° C. for 5 hours in an air atmosphere to obtain a polymer of the general formula (A) having a melt viscosity of 2560 poise.

Reference Example 2 15 N-methylpyrrolidone 5 was charged into an autoclave, heated to 120 ° C., and then 2.8 sodium hydrosulfide was added.
1866g charged, 205 ° C gradually with stirring over about 2 hours
The temperature was raised to 405 g of water. Thereafter, the mixture was cooled to 140 ° C., 2091 g of p-dichlorobenzene and 11.7 g of 2,4-dichlorophenol were added, the temperature was raised to 250 ° C., and the reaction was carried out for 3 hours to obtain a polyarylene sulfide having a hydroxyl group. The melt viscosity of this polymer was 270 poise. Further, the analysis by gas chromatography revealed that the conversion of 2,4-dichlorophenol was 70%. (M = 0.996,
Subsequently, this polymer was subjected to a heat treatment at 250 ° C. for 5 hours in an air atmosphere to obtain a polymer of the general formula (B) having a melt viscosity of 2870 poise.

Examples 1 to 5 In a 0.5 autoclave, 40 g of hydroxyl-containing polyarylene sulfide synthesized in Reference Example 2, 200 ml of N-methylpyrrolidone, 0.148 g of sodium hydroxide, brominated octadecane, chlorinated octadecane, brominated decane, bromination Hexane and brominated ethane were added in the specified amounts shown in Table 1, respectively, heated to 135 ° C and held for 30 minutes.
And the reaction was carried out for 1 hour. Thermal behavior of the respective resultant polymer _{(Tg, Tc 1, Tc 2} , the melting point (Tm), Td) Table -
1 is shown.

Regarding the introduction of aliphatic chains into the polymer, FT
It was confirmed by -IR that absorption was observed at 2920 and 2850 cm ^-1 .

These polymers, PPS Tc ₁ is significantly reduced without reducing any Tm compared with, also Tc ₂ was markedly elevated.

This result shows that the crystallization rate is increased without impairing the heat resistance of the polyarylene sulfide, and even when a low-temperature mold (mold temperature 100 ° C or less) is used during injection molding. The polyarylene sulfide copolymer is sufficiently crystallized, and a molded article having high heat resistance can be obtained without annealing.

Examples 6 to 7 In a 0.5 autoclave, Table 1 shows 40 g of the hydroxyl-containing polyarylene sulfide synthesized in Reference Example 1, 200 ml of N-methylpyrrolidone, 0.148 g of sodium hydroxide, brominated octadecane, and brominated hexane. Was added, and the temperature was raised to 135 ° C and held for 30 minutes.
C., and the reaction was carried out for 1 hour. Thermal behavior of each of the polymer obtained _{(Tg, Tc 1, Tc 2} , the melting point (Tm), Td) are shown in Table 1.

Regarding the introduction of aliphatic chains into the polymer, FT
It was confirmed by -IR that absorption was observed at 2920 and 2850 cm ^-1 .

These polymers, PPS Tc ₁ is significantly reduced without reducing any Tm compared with, also Tc ₂ was markedly elevated.

Comparative Example 1 The thermal behavior of the hydroxyl group-containing polyarylene sulfide synthesized in Reference Example 2 is shown in Table 1.

This polymer has a high Tc _1, also slow crystallization rate due to the low Tc _2, when molded at low temperature mold, because crystallization is not sufficient, they did not show sufficient heat resistance without annealing.

Comparative Example 2 PPS obtained by a known polymerization method was heat-treated at 250 ° C. in an air atmosphere to obtain a crosslinked PPS having a melt viscosity of 2600 poise. Table 1 shows the thermal behavior of this polymer.

This polymer has a high Tc _1, also did not show sufficient crystallization at low temperature mold due to the low Tc _2.

Comparative Example 3 Table 1 shows the thermal behavior of a linear PPS having a melt viscosity of 2580 poise obtained by a known polymerization method.

This polymer has a high Tc _1, also did not show sufficient crystallization at low temperature mold due to the low Tc _2.

[Effects of the Invention] As is clear from the above, according to the present invention, a polyarylene sulfide copolymer having a remarkably high crystallization rate can be easily obtained, and a molded article sufficiently crystallized even in injection molding using a low-temperature mold. Can be obtained.

Continuation of the front page (56) References JP-A-61-40319 (JP, A) JP-A-63-213526 (JP, A) JP-A-63-213527 (JP, A) JP-A-3-221528 (JP) (A) JP-A-4-7334 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 75/00-75/32 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] (1) a polar organic solvent at a reaction temperature of 90 to 270 ° C.
General formula (A) or (B) characterized in that a polyarylene sulfide having a hydroxyl group is reacted with a halogenated aliphatic hydrocarbon. (R is an alkyl group having 1 to 50 carbon atoms, 1 is an integer of 2 or more,
m: n = 0.95: 0.05 to 0.999: 0.001, m + n = 1, and m: n represents a molar ratio. A) a method for producing a polyarylene sulfide copolymer having a melt viscosity of 10 to 100,000 poise.