JPH055032A - Polyarylene sulfide ether, production and composition thereof - Google Patents

Abstract

PURPOSE:To obtain an expensive polymer having extremely improved melt fluidity while maintaining heat resistance, mechanical characteristics and thermal stability in good balance, producible by a simple process, having a large ratio of S/O and a specific structure. CONSTITUTION:A polyarylene sulfide ether shown by formula I (Ar1 is bifunctional aromatic halogen residue wherein C bonded to O or S contains electron attracting group at p-position or o-position; Ar2 is bihydric aromatic phenol residue shown by formula II to formula IV; R<1> to R<5> are H, halogen, etc.; a, b, c are 0-4; are d, e are 0-3; Y is single bond, -S-, -CO-, etc.; n and m show degree of polymerization, 100>n>0 and m>1). The polyarylene sulfide ether is obtained by reacting a dihalo aromatic compound shown by the formula X-Ar1-X (X is halogen) with a sulfiding agent in an organic polar solvent to form an arylene sulfide oligomer intermediate containing a halogen group at the end and reacting the oligomer intermediate with a bihydric phenol shown by the formula HO-Ar2-OH.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyarylene sulfide ether, a method for producing the same, and a heat resistant thermoplastic resin composition containing the polymer. The present invention relates to a polyarylene sulfide ether having an ether bond having a degree of polymerization of m, a polyarylene sulfide ether having a degree of polymerization of n, a method for producing the same, and a heat-resistant thermoplastic resin composition containing the polymer.

[0002]

2. Description of the Related Art Polyarylene sulfides have hitherto been known as heat-resistant resins. For example, Japanese Patent Publication No. 45-3
No. 368 describes polyarylene sulfides obtained from various polyhaloaromatic compounds. Furthermore,
JP-A-60-58435 discloses heat-resistant polyphenylene ketone sulfides, and US Pat.
4016145, 4301274, 4070349
Nos. 4,125,525 and 4,127,713 describe heat-resistant polyphenylene sulfone sulfides, respectively.

However, although these polyarylene sulfides have good heat resistance and fluidity at the time of molding, they have the drawbacks of being hard and brittle and lacking in toughness. Furthermore,
The polyarylene sulfide containing a sulfone or a ketone bond has a drawback in that the melt viscosity has poor thermal stability and the viscosity is remarkably increased during processing, and it is difficult to obtain a certain quality.

On the other hand, aromatic polyethers are also known. For example, Japanese Examined Patent Publication No. 42-7799, R.I. N,
Jonhson et al .; Polyn. Sci. , A-
1,5,2375 (1967) describes aromatic polyethers having various structures. Among them, aromatic polyether having an electron-withdrawing group such as a ketone group or a sulfone group in the main chain is known to be a resin excellent in heat resistance, mechanical properties and electrical properties, and particularly Excellent toughness and tenacity.

However, it lacks chemical resistance to an organic polar solvent such as a chlorine-based solvent or a cyclic ether, has a high melt viscosity at the time of molding, and has a small shear rate dependency. Therefore, in particular, an inorganic filler is blended. The resin temperature to 3
It has a defect that it cannot be molded unless it is heated to a high temperature such as 50 ° C to 410 ° C.

Several proposals have been made in the past to improve the drawbacks of both polyarylene sulfide and aromatic polyether. For example, JP-A-61-25211
No. 8, JP-A-61-247755, JP-A-62-20.
5157 and JP-A-62-119268 disclose block copolymers of polyphenylene sulfide and polysulfone, for example,

[0007]

[Chemical 2]

Etc. are exemplified. In addition, JP-A-61-7
2020, JP 61-76523, JP 61-
168629 and JP-A-63-187683, block copolymers of polysulfone and polyphenylene sulfone sulfide, for example,

[0009]

[Chemical 3]

Is disclosed. In addition, JP-A-1-30
No. 6427 discloses a polymer-[-Ar-(-O-Ar-O-Ar-) m-S-] n- obtained by sulfiding a polysulfone intermediate having a terminal halogen. However, in each of the above methods, the ratio (S / O) of the intramolecular sulfide bond (-S-) to the ether bond (-O-) is small, and therefore the melt viscosity is high and the fluidity is poor. It was enough. Further, there is a problem that the selection range of the required balance between heat resistance and toughness is narrow.

[0011]

Therefore, the inventors of the present invention diligently researched an inexpensive polymer which can be produced by a process as simple as possible without impairing the balance of heat resistance, mechanical properties, thermal stability and the like. As a result, by producing an arylene sulfide oligomer intermediate having a specific structure having a halogen group at the terminal and then reacting it with a divalent phenol in the presence of a base, heat resistance, mechanical properties, The present invention has been completed by finding that high molecular weight polyarylene sulfide ethers having thermal stability and the like can be obtained, and an object of the present invention is to increase the S / O ratio as much as possible to achieve melt flow. It is an object of the present invention to provide a novel poly (arylene sulfide ether) having improved properties and having the above-mentioned properties, and a method for producing the same.

[0012]

That is, the gist of the present invention is as follows.
The polyarylene sulfide represented by the following general formula
Tells. -[-Ar ₁ -(-S-Ar _1- ) n-O-Ar ₂ -O-] m- (I) [In the formula, Ar ₁ represents a carbon atom bonded to O or S. A divalent aromatic halogen residue having an electron-withdrawing group at least in the para or ortho position, Ar ₂ represents a divalent aromatic phenol residue selected from the following formula,

[0013]

[Chemical 4]

(Here, R ^{1 to} R ⁵ represent hydrogen, halogen, or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and a to c are 0 to 4 and d to e are It is an integer of 0 to 3 and may be the same or different.Y is a single bond or -O.
-, - S -, - SO -, - SO 2 -, - CO -, - C
R is selected from the group consisting of (R) ₂ — and R represents hydrogen, a hydrocarbon having 1 to 6 carbon atoms, or a halogen-substituted hydrocarbon. ) In addition, n and m indicate the degree of polymerization, and 100>n> 0, m> 1.
Is. ]

As a method for producing the same, the following general formula X-Ar ₁ -X ... (II) (wherein Ar ₁ is at least the para-position or ortho of the carbon atom bonded to X) is used. A divalent aromatic residue having an electron-withdrawing group at the position, X represents a halogen group), and a sulfidizing agent are reacted in an organic polar solvent, An arylene sulfide oligomer-intermediate (IV) having a halogen group at the terminal is formed, and then the arylene sulfide oligomer-intermediate (IV) is added in the presence of a base with the general formula HO-Ar ₂ -OH. (III) (wherein Ar ₂ represents a divalent aromatic residue) is reacted with a divalent phenol represented by the general formula-[-Ar ₁ -(- _{S-Ar 1 -) n-} O-Ar 2 -O-] m- ...... (I (Wherein, Ar _1, Ar _2, m and n are as described above) polyarylene represented by - Rensurufidoe - it is ether production method of.

The method for producing the polyarylene sulfide ether represented by the general formula (I) of the present invention (hereinafter referred to as PASE) is shown by a reaction formula as follows.

[0017]

[Chemical 5]

[0018]

[Chemical 6]

However, M ₂ S represents an alkali metal sulfide. The reaction of the reaction formula (1) is carried out by reacting the dihaloaromatic compound of the general formula (II) with a sulfidizing agent (for example, sodium sulfide) in the presence of an organic polar solvent to give an arylene having a terminal halogen group. A sulfide oligomer intermediate (IV) is obtained. In this reaction, it is necessary to use the dihaloaromatic compound in excess with respect to the sulfiding agent in a molar ratio. By controlling this excess amount, the degree of polymerization n of the arylene sulfide oligomer intermediate (IV) can be controlled. This excess amount means that n of the arylene sulfide oligomer intermediate (IV) is 1 or more and about 1 or less.
00 or less, more preferably 1 or more and about 50 or less. 1.0 per mol of sulfiding agent
1 to 2.0 mol, preferably 1.02 to 1.8 mol of dihaloaromatic compound is used. This excess dihaloaromatic compound may be used from the beginning of the reaction (1), or the equivalent amount may be used at the beginning, and the remaining amount may be added during or near the end of the reaction. ..

Next, the present invention will be described in more detail. First, specific examples of the dihalo aromatic compound that can be used in the present invention include 4,4′-dichlorobenzophenone,
4,4'-dibromobenzophenone, 4,4'-difluorobenzophenone, 2,6-dichloroanthraquinone, 4,4'-dichlorodiphenyl sulfone, 2,6-
Examples thereof include dichlorobenzonitrile, 4,4'-dichlorodiphenyl sulfoxide, 4,4'-difluorodiphenyl sulfoxide and 2,4-dichloronitrobenzene.

Further, examples of the sulfidizing agent used in the reaction (1) include (a) alkali metal sulfides,
At least one selected from the group consisting of (b) alkali metal hydrosulfide and alkali metal hydroxide and (c) hydrogen sulfide and alkali metal hydroxide is preferable. As the alkali metal sulfide (a), lithium sulfide, potassium sulfide, sodium sulfide, rubidium sulfide, and the like, and mixtures thereof can be used. Instead of or in addition to the alkali metal sulfide, a compound capable of forming an alkali metal sulfide by the reaction, that is, an alkali metal sulfide-forming compound can be used. Specific examples thereof include (b) lithium,
Combinations of alkali metal hydrosulfides such as potassium, sodium, rubidium with the corresponding hydroxides, and (c) hydrogen sulfide with alkali metal hydroxides are mentioned.

The alkali metal sulphides and the alkali metal sulphide-forming compounds can also be used as hydrates or aqueous mixtures. Among the alkali metal sulfides, sodium sulfide is particularly preferable because it is easily available and inexpensive.
Since industrially available sodium sulfide is a water-containing material having a sodium sulfide content of 60% or 45%, it may be heated and dehydrated in an organic polar solvent, if necessary, prior to the reaction. Dehydration is carried out by heating to near the boiling point of the solvent in an inert gas stream under normal pressure, reduced pressure, or under pressure so that the sodium sulfide water of hydration falls within the range of 0.2 to 5.0 mol. It is better to reduce to If necessary, NaHS, Na present in these sodium sulfides
_An equivalent amount of sodium hydroxide can be used together to neutralize impurities such as ₂ S ₂ O ₃ .

As the organic polar solvent used in the reaction (1), an aprotic organic solvent inert to the reaction can be used. Examples of such a solvent include sulfones such as dimethyl sulfone, sulfolane, diphenyl sulfone and ditolyl sulfone, ketones such as benzophenone, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2. -Pyrrolidone, N-cyclohexyl-2-pyrrolidone, 1,3-dimethyl-2-
Examples include amides such as imidazolidinone, N, N, N ′, N′-tetramethylurea, hexamethylphosphoric triamide, etc., urea and lactams, nitriles such as benzonitrile, and mixtures thereof. I can do things. Among these solvents, amides, lactams, sulfones and the like are preferable, and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and sulfolane are particularly preferable. The amount of the organic polar solvent used is in the range of 1 to 10 and preferably in the range of 2 to 6 by weight ratio with respect to the amount of the oligomer component produced.

In the reaction of (1), usually, a sulfidizing agent is put in an organic polar solvent, dehydration is carried out if necessary to adjust the water of hydration to a predetermined value, and then the dihaloaromatic compound of the general formula (II) is added. It is added as it is or after being dissolved in an organic polar solvent. At that time, the reaction temperature is 100 ° C. to 350 ° C., more preferably 150 ° C. to 270 ° C., and the reaction time depends on the reaction temperature, but is 0.5 to 48 hours, more preferably 0.5.
~ 20 hours range. If necessary, a known catalyst such as lithium acetate or lithium chloride may be used in combination.

After the reaction of (1) is completed and prior to the reaction of (2), the by-produced alkali metal halide may be decomposed and removed, or may be carried out without being removed. Furthermore, after the reaction of (1) is completed, a small amount of the unreacted remaining starting material may or may not be separated and removed. It is also possible to neutralize and decompose with an equivalent amount of acid (for example, carbonic acid, oxalic acid, etc.) for the purpose of removing the remaining trace amount of alkali metal sulfide. It is also possible to isolate the arylene sulfide oligomer intermediate obtained in the reaction of (1) and use it in the reaction of (2). In the case of isolation, methanol or n which is a non-solvent of the produced oligomer is used.
-Adding the polymerization solution to hexane or water, or removing the organic polar solvent by filtration or the like, and if necessary, washing with water or a non-solvent several times and then drying. Then, the halogen content at the oligomer end is quantified by a fluorescent X-ray method or another halogen quantification method.

When this oligomer is not isolated,
After the reaction of (1), it is necessary to remove in advance a small amount of residual alkali metal sulfide and water derived from the subsequent treatment. The reaction of (2) is carried out in an organic polar solvent under substantially anhydrous conditions with the unterminated dihalo-ary-lene sulfide oligomer intermediate and an alkali metal divalent phenol of the general formula (III). A novel poly (arylene sulfide ether) is obtained by reacting a salt and polymerizing it.

Specific examples of the divalent phenol which can be used in the present invention include hydroquinone, resorcin, 4,4'-
Dihydroxydiphenyl, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ketone, 2,2-bis- (4-hydroxyphenyl)
) Propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 2,4'-dihydroxydiphenylmethane, bis (2-hydroxyphenyl) methane , Bis- (4-hydroxyphenyl) methane, 2,2-bis- (4-hydroxyphenyl) 1,1,3,3,3-hexafluoropropane, bis- (4-hydroxy-3-chlorophenyl) Ether, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether, tetraprombisphenol A, tetrachlorobisphenol A and the like.

The organic polar solvent used in the reaction (2) may be the same as or different from the solvent used in the reaction (1). In particular, examples of solvents other than the above,
Dimethylsulfoxide, diethylsulfoxide, tetrahydrothiophene-1-monooxide and the like can be used. The amount of the organic polar solvent used is in the range of 1 to 10, preferably in the range of 2 to 6, by weight ratio with respect to the amount of the polymer component. As the base for forming the alkali metal salt of divalent phenol, lithium, sodium, potassium,
Hydrides, hydroxides of alkali metals such as rubidium,
Carbonates, bicarbonates and the like can be mentioned. Preferred bases are sodium and potassium hydroxides and carbonates. The base used here is used in a theoretical amount (2 times the molar amount) with respect to the divalent phenol.

If necessary, in order to avoid side reactions, (2)
Prior to the reaction of 1. or in the temperature rising process, it is heated and dehydrated in an organic polar solvent in the presence or absence of an azeotropic agent to reduce the water content in the system to 1% or less, preferably 0.5% or less. Put. Examples of the azeotropic agent include benzene, toluene, xylene, halogenated benzene and the like. Generally, the azeotropic agent used is preferably removed prior to the reaction of (2). The molar ratio of the terminal dihalo-ary-lene sulfide oligomer intermediate to the alkali metal salt of divalent phenol in the reaction (2) is calculated on the basis of halogen,
It must be equimolar, but this can be varied slightly. By controlling this molar ratio, the overall degree of polymerization m can be controlled. Preferably, the molar ratio is 0.5 to 2.0, more preferably 0.9 to
A range of 1.05 is good.

The reaction (2) is generally carried out in a non-catalytic system, but if necessary, a known catalyst such as a quaternary phosphonium salt can be used. This reaction is 100
A reaction temperature in the range of ℃ to 300 ℃, more preferably 120 ℃ to 250 ℃ is used. Although the viscosity increases with the progress of the reaction, if necessary, the reaction is completed by successively diluting it with an organic polar solvent. After completion of the reaction, the by-produced alkali metal halide is separated by a known method such as filtration. Then, the polymer solution is dropped into a low boiling non-solvent such as methanol to precipitate and separate the polymer, and the polymer is dried under reduced pressure to obtain PASE.

One of the features of the present invention is that there are a wide range of options for the physical properties of the obtained polymer and the production cost. That is, by selecting a combination of a raw material dihalo aromatic compound and a divalent phenol, and selecting a polymerization degree n of a sulfide bond portion, a polymer having particularly high heat resistance to a polymer having toughness and flexibility, If the degree of polymerization n is increased, a polymer having a higher elastic modulus, better chemical resistance and a relatively low melt viscosity can be obtained. Even with the same combination of starting materials, it is possible to control the glass transition temperature and the melt viscosity depending on the degree of polymerization n of the sulfide bond portion. These characteristics are unthinkable in the conventionally known polyarylene sulfide and polyarylene polyether. Next, an example of the range of options of the present invention is shown in Table 1. Table 2 also shows the chemical structural formulas of commercial engineering plastics for reference.

[0032]

[Table 1]

[0033]

[Table 2]

The present invention further relates to a thermoplastic resin composition containing the above polyarylene sulfide ether and having excellent heat resistance. That is, although the polyarylene sulfide ether of the present invention may be used alone, it may be used as a polymer alloy in combination with other resins. In this case, any resin may be used as the resin to be combined, but especially polyester, polycarbonate, PBT, nylon, PPS, PES, P, which are known as heat resistant engineering plastics.
SF, PEEK and the like are particularly preferable. In some cases, these resins are compatible with each other, but when they are not compatible with each other, one polymer is dispersed in the other resin to form a polymer alloy. The feature of the present invention is that the polyarylene sulfide ether of the present invention has a large degree of freedom as described above and can bring out a wide range of characteristics even when the resin of the alloy partner is fixed.

When the polyarylene sulfide ether of the present invention is blended with another resin in an amount of less than 5% by weight of the polyarylene sulfide ether of the present invention, the characteristics are not exhibited and the effect cannot be expected. As a matter of course, silica powder, talc powder, carbonic acid, either alone or in the case of polymer alloy, are used for the purpose of resin cost reduction, strength improvement, molding shrinkage improvement, thermal conductivity improvement, etc. It is perfectly acceptable to mix an inorganic filler such as calcium and / or a fibrous filler such as glass fiber, carbon fiber or stainless fiber. The compounding amount of each of these inorganic filler and fibrous filler is 0 to 90% by weight. The present invention also includes the addition of various additives such as pigments, antioxidants, silane coupling agents, and release agents.

[0036]

EXAMPLES The embodiments of the present invention will be specifically described below with reference to examples, but these examples do not limit the scope of the present invention. The physical properties of the polymer of the present invention were measured as follows. (Reduced viscosity) phenol / 1,1,2,2-tetrachloroethane = 3/2 (weight ratio) In the solution, the polymer concentration was 0.
It was measured at 5 g / dl and a temperature of 30 ° C. (Terminal chlorine content) It was measured by a chlorine-sulfur analyzer TSX-10 (manufactured by Mitsubishi Kasei). (Glass transition temperature) By a differential scanning calorimeter (DSC),
The measurement was performed at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere.

(Melting Viscosity) Temperature was 300 ° C., load was 20 Kg, nozzle was 1.0 mmφ using a high flow tester.
It measured using x10mmL. (Thermal stability) The rate of change in melt viscosity during heating was determined by the following formula. Thermal stability = (V ₃₀ −V ₆ ) / V ₆ × 100 where V ₆ is the melt viscosity at a preheating time of 6 minutes, V ₃₀ is the melt viscosity at a preheating time of 30 minutes. (Thermal decomposition start temperature) Measurement was carried out by a thermobalance (TGA) at a temperature rising rate of 10 ° C / min in an air atmosphere.
The weight loss onset temperature obtained by extrapolation was used as the thermal decomposition onset temperature.

Example 1. 65.0 g (0.50 mol) of sodium sulfide (purity 60%) was added to a 1-liter titanium autoclave equipped with a stirrer and a cooling tube with a water condenser.
172.2 g of 4'-dichlorodiphenyl sulfone (0.
6 mol), and N-methyl-2-pyrrolidone (NMP)
350 g was charged, and 1 Kg / cm ^{2 of} nitrogen was pressurized and sealed. Next, the temperature was raised to 210 ° C. with stirring and the reaction was carried out for 5 hours. After cooling the autoclave, a part of the contents was sampled, precipitated with a large amount of methanol, and then heated with hot water.
100 times after washing three times and further with methanol three times.
It was dried under reduced pressure at ℃ to obtain a pale yellow powdery polyphenylene sulfone sulfide oligomer. This oligomer had a reduced viscosity of 0.07 and a terminal chlorine content of 3.92%.
The degree of polymerization n of the oligomer calculated from the chlorine content is 6.1.
It was 5.

Subsequently, 293.6 g of the above reaction mixture
In addition, 11.4 g (0.05 mol) of 2,2-bis- (4-hydroxyphenyl) propane (bisphenol A),
Caustic soda solution (purity 48.4%) 8.3 g (0.1
(0 mol) and 50 g of NMP were added, and the inside of the reaction system was replaced with nitrogen, and then the temperature was raised to 204 ° C. with stirring to distill off water. Then, it was cooled to 200 ° C., and the reaction was carried out at this temperature for 4 hours. After cooling, the content was diluted with 200 g of NMP, the by-product salt was removed by filtration, and then precipitated in a large amount of methanol, and the precipitate was extracted with hot water 5 times and further with methanol 3 times. It was washed and dried under reduced pressure at 100 ° C. to obtain a pale yellow powdery polymer.

The polymer had a reduced viscosity of 0.19, a glass transition temperature of 191 ° C., a thermal decomposition initiation temperature of 475 ° C., a melt viscosity of 530 poise, and a thermal stability of 3.8%.
When the IR spectrum of this polymer was measured, it was 1160
cm ^-1, absorption of the sulfonic to 1320cm ^-1, 1240c
The absorption of ether at m ^-1 and the absorption of sulfide at 1120 cm ^-1 were confirmed.

Example 2. Sodium sulfide 65.0 g
(0.50 mol), 4,4'-dichlorodiphenyl sulfone 215.3 g (0.75 mol), and NMP35.
4.5 g was charged in the same manner as in Example 1 and reacted at 210 ° C. for 5 hours. After cooling the autoclave, a part of the content was sampled and the same treatment as in Example 1 was performed. The reduced viscosity of the obtained polyphenylene sulfone sulfide oligomer was 0.05, the terminal chlorine content was 6.46%, and the degree of polymerization n of the oligomer calculated from this was 3.27.

Subsequently, to 317.4 g of the above reaction mixture, 28.5 g (0.125 mol) of bisphenol A, 20.4 g (0.25 mol) of an aqueous solution of caustic soda and NMP5 were added.
0 g was added, and the temperature was raised to 204 ° C. for dehydration. Then, the mixture was cooled to 200 ° C. and polymerized at the same temperature for 4 hours. After cooling, the content was treated in the same manner as in Example 1 to obtain a pale yellow powdery polymer. The reduced viscosity of this polymer is 0.
21, glass transition temperature is 175 ° C, thermal decomposition start temperature is 4
86 ℃, melt viscosity 230 poise, thermal stability 5.0%
Met.

Example 3. Sodium sulfide 65.0 g
(0.50 mol), 4,4'-dichlorodiphenyl sulfone 172.2 g (0.60 mol), and NMP35.
In the same manner as in Example 1, 4.5 g was reacted at 210 ° C. for 5 hours. After cooling the autoclave, the content was precipitated with a large amount of methanol and the same treatment as in Example 1 was carried out to obtain a polyphenylene sulfone sulfide oligomer.
The reduced viscosity of this oligomer was 0.07, the terminal chlorine content was 3.58%, and the degree of polymerization n calculated from this was 6.84.

Next, in a 1 l glass separable flask equipped with a stirrer and a water condenser condenser cooling tube, 90 g of the polyphenylene sulfone sulfide oligomer, 10.3 g (0.045 mol) of bisphenol A, and dimethyl sulfoxide 162. 5g and monochlorobenzene 500g
Was charged, and the temperature was raised to 70 ° C. with stirring in a nitrogen stream. Next, 7.4 g of caustic soda solution (purity 49%)
(0.09 mol) was added, and the temperature was further raised to dehydrate to 170 ° C. Immediately after the completion of dehydration, the mixture was cooled to 150 ° C. and polymerized at the same temperature for 5 hours. The contents are cooled, precipitated with a large amount of methanol, and the precipitate is washed with hot water.
After that, it was washed three times with methanol and dried under reduced pressure at 100 ° C. to obtain a pale yellow powdery polymer. The polymer had a reduced viscosity of 0.54, a glass transition temperature of 201 ° C., a thermal decomposition initiation temperature of 490 ° C., a melt viscosity of 144,000 poise, and a thermal stability of 109%.

Example 4. Sodium sulfide 65.0 g
(0.50 mol), 4,4'-dichlorodiphenyl sulfone 172.2 g (0.60 mol) and NMP354.
5 g was reacted at 210 ° C. for 5 hours in the same manner as in Example 1. After cooling the autoclave, a large amount of methanol was added to the contents.
And the same treatment as in Example 1 was performed to obtain a polyphenylene sulfone sulfide oligomer. This oligomer had a reduced viscosity of 0.07 and a terminal chlorine content of 3.
50%, and the degree of polymerization n calculated from this was 7.02.

Next, in a 1 liter glass separable flask equipped with a stirrer and a cooling tube with a water condenser, the polyphenylene sulfone sulfide oligomer-80 g, 4,4'- was added.
Dihydroxydiphenyl sulfone (bisphenol S)
Charge 9.9 g (0.04 mol), 162 g of sulfolane, and 500 g of monochlorobenzene, and in a nitrogen stream,
The temperature was raised with stirring to 0 ° C. Then, 7.4 g (0.08 mol) of an aqueous solution of caustic soda was added, and the temperature was further raised to dehydrate to 240 ° C. 240 ℃ after dehydration
The reaction was carried out for 5 hours. After the reaction is complete, cool the contents,
The same treatment as in Example 3 was carried out to obtain a pale yellow powdery polymer. The polymer had a reduced viscosity of 0.31, a glass transition temperature of 210 ° C., a thermal decomposition starting temperature of 461 ° C., a melt viscosity of 12,800 poise, and a thermal stability of 11.5%. When the infrared absorption spectrum is measured, it is 1169c.
Absorption of sulfone at m ^-1 , 1320 cm ^-1 , 1240c
The absorption of ether at m ⁻ and the absorption of sulfide at 1120 cm ⁻¹ were confirmed.

Comparative Example 1. (Synthesis of polyphenylene sulfone sulfide) Stirrer,
65.0 g (0.5 mol) of sodium sulfide, 143.5 g (0.5 mol) of 4,4′-dichlorodiphenyl sulfone were added to a 1 liter titanium autoclave equipped with a cooling pipe.
And NMP (350 g) were charged, and the mixture was pressure-filled with nitrogen at 1 Kg / cm ² . Then, while stirring, raise the temperature to 210 ° C. and
Polymerization was carried out for a period of time. After cooling the autoclave, the contents were precipitated with a large amount of methanol, washed with hot water 5 times and further washed with methanol 3 times, and then dried under reduced pressure at 100 ° C. to obtain a pale yellow powdery polyphenylene. A sulfone sulfide was obtained. This polymer has a reduced viscosity of 0.35 and a glass transition temperature of 2
The temperature was 14 ° C., the thermal decomposition start temperature was 460 ° C. The thermal stability of the melt viscosity could not be measured because the polymer gelled during the measurement.

Comparative Example 2. (Synthesis of polysulfone) 1 equipped with stirrer and water condenser
In a glass separable flask, 95.2 g (0.331 mol) of 4,4'-dichlorodiphenyl sulfone, 74.9 g (0.3285 mol) of bisphenol A, 500 g of monochlorobenzene, and 16 parts of dimethyl sulfoxide.
2.5 g was charged and the temperature was raised to 70 ° C. with stirring in a nitrogen stream. Next, an aqueous solution of sodium hydroxide (purity 49
%) 53.6 g (0.657 mol) was added, and the temperature was further raised to dehydrate to 170 ° C. Immediately after dehydration 1
After cooling to 50 ° C, polymerization was carried out at the same temperature for 1 hour. After cooling, the content was diluted with 500 g of monochlorobenzene, the by-product salt was removed by filtration, the polymer was precipitated in a large amount of methanol, and the precipitate was washed 3 times with methanol and heated to 100 ° C. After drying under reduced pressure, a white powdery polymer was obtained. This polymer had a reduced viscosity of 0.66, a glass transition temperature of 184 ° C., a thermal decomposition initiation temperature of 495 ° C., a melt viscosity of 125,400 poise, and a thermal stability of 11.0%.

Comparative Example 3. (Synthesis of Polyether Sulfone) In a 1 l glass separable flask equipped with a stirrer and a water condenser, 4,4'-dichlorodiphenyl sulfone 94.3 g (0.3285 mol) and bisphenol S 82.1 g (0. 3285 mol), monochlorobenzene 500 g, and sulfolane 1
Charge 62.5 g, 70 ° C with stirring in a nitrogen stream.
The temperature was raised to. Next, 53.6 g (0.657 mol) of an aqueous sodium hydroxide solution (purity 49%) was added, and the temperature was further raised to dehydrate to 240 ° C. After dehydration 240
Polymerization was carried out at ℃ for 4 hours. After cooling, the content was poured into a large amount of methanol to precipitate a polymer, and the precipitate was washed with hot water 5 times and further with methanol 3 times, and dried under reduced pressure at 100 ° C. to obtain a white powdery polymer. -I got it. This polymer had a reduced viscosity of 0.24, a glass transition temperature of 204 ° C., a thermal decomposition initiation temperature of 511 ° C., a melt viscosity of 1,970 poise, and a thermal stability of −11%. Table 3 shows the properties of the polymers obtained in the above Examples and Comparative Examples.

[0050]

[Table 3]

In Table 3, * 1 means that measurement is impossible. Further, ηsp / c is a reduced viscosity, M. V is melt viscosity, T.V. S
Represents thermal stability, Tg represents glass transition temperature, and Td represents thermal decomposition initiation temperature. Example 5 10 g of the poly (arylene sulfide ether) obtained in Example 4 and 15 g of PPS resin (Toprene T-1) were premixed and then kneaded for 3 minutes with a Brabender tester heated to 300 ° C. After that, use a 1 mm spacer to do 3
After vacuum hot pressing at 00 ° C, it is rapidly cooled to a 1 mm thick sheet.
Created.

Example 6 Instead of the PPS resin of Example 5, PES (manufactured by ICI, 3
A sheet was prepared in the same manner except that 600P) was used. Comparative Examples 4, 5, and 6 PPS and PES in Example 5 and PPSS of Comparative Example 1 were used alone.

The tensile strength and Tg of each sheet of Examples 5 and 6 and Comparative Examples 4 and 5 were measured. The results are shown in Table 4.

[0054]

[Table 4]

[0055]

As described above, the present invention is a novel polyarylene sulfide ether having excellent heat resistance, mechanical properties, electrical properties, chemical properties and moldability. Polymer, method for producing the same, and polymer
The present invention provides a thermoplastic resin composition containing: The polymer obtained by the present invention is combined with a carbon fiber or the like as various molded products by a method such as injection molding or extrusion molding, as films, sheets, mono- and multi-filament fibers, as a covering material for electric wires and the like. It can be used in a wide range of industrial fields such as combined composite materials, paints, etc.

In particular, as one of the features of the present invention, a selective combination of a dihaloaromatic compound as a raw material and a divalent phenol, or a combination of the same starting materials by changing the S / O ratio, It is possible to control the glass transition temperature and the melt viscosity depending on the degree of polymerization n of the sulfide bond portion, and the polymer obtained has high heat resistance and is tough and flexible. The effect that various things which have the characteristic of the polymer which it has can be obtained is exhibited.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08L 101/00 LTA 7167-4J

Claims (1)

Claims: 1. A polyarylene sulfide ether represented by the following general formula. -[-Ar ₁ -(-S-Ar _1- ) n-O-Ar ₂ -O-] m- (I) [In the formula, Ar ₁ represents a carbon atom bonded to O or S. A divalent aromatic halogen residue having an electron-withdrawing group at least in the para or ortho position, Ar ₂ represents a divalent aromatic phenol residue selected from the following formula: (Here, R ^{1 to} R ⁵ represent hydrogen, halogen, or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, a to c are 0 to 4, and d to e are 0 to 3; And may be the same or different and Y is a single bond, -O-, -S-,
Selected from the group consisting of —SO—, —SO ₂ —, —CO—, and —C (R) ₂ —, where R represents hydrogen, a hydrocarbon having 1 to 6 carbon atoms, or a halogen-substituted hydrocarbon), , N and m represent the degree of polymerization, and are 100>n> 0 and m> 1. [Claim 2] The following general formula X-Ar ₁ -X (II) (wherein Ar ₁ is electron-attracting to at least the para-position or ortho-position of the carbon atom bonded to X). A divalent aromatic residue having a volatile group, wherein X represents a halogen group) and a sulfidizing agent are reacted in an organic polar solvent to form a halogen group at the terminal. To form an arylene sulfide oligomer intermediate having the general formula HO—Ar ₂ —OH (III) (wherein Ar ₂ represents a divalent aromatic residue) and is reacted with a divalent phenol represented by the general formula-[-Ar ₁ -(-S-Ar _1- ) n-O. _{-Ar 2 -O-] m- ...... (I} ) ( wherein, Ar _1, Ar _2, m及Polyarylene n is represented by as defined above) - Rensurufidoe - ether production method of. 3. The sulfidizing agent is selected from the group consisting of (a) alkali metal sulfide, (b) alkali metal hydrosulfide and alkali metal hydroxide, and (c) hydrogen sulfide and alkali metal hydroxide. 3. The method for producing a polyarylene sulfide ether according to claim 2, which is at least one. 4. The polyarylate according to claim 2, wherein after the sulfidation reaction, the etherification reaction is carried out subsequently without separating the by-produced alkali metal halide.
Method for producing rensulfide ether. 5. At least 5% by weight or more of the polyarylene sulfide ether according to claim 1, 0 to 95% by weight of at least one thermoplastic resin, and 0 to 95% by weight of at least one inorganic filler. % And 0 to 95% by weight of at least one fiber filler, a thermoplastic resin composition.