JPH069780A - Production of polyarylene thioether having phthalic anhydride group - Google Patents

Abstract

(57) [Summary] [Purpose] A method for producing a granular polyarylene thioether containing a high molecular weight maleic anhydride group, which has good heat resistance and does not reduce the effect of functional groups due to decarboxylation even at polymer processing temperatures. To provide. In a method for producing a polyarylene thioether by polymerizing a dihalogen-substituted aromatic compound and an alkali metal sulfide in a polar organic solvent containing water, a monohalogen-substituted phthalic acid compound is present in the polymerization reaction system. In addition, the ratio a / b of the mole number a of the charged dihalogen-substituted aromatic compound and the mole number b of the charged alkali metal sulfide is set in the range of 0.8 <a / b <1. Process for producing group-containing polyarylene thioether.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a polyarylene thioether containing a phthalic anhydride group, and more specifically, a phthalic anhydride group-containing polyarylene thioether obtainable as a high molecular weight granular polymer. Manufacturing method.

[0002]

2. Description of the Related Art Polyarylene thioethers represented by polyphenylene sulfide (PPS) (hereinafter referred to as PAT)
(Abbreviated as E) is known as a polymer having a high melting point and excellent in heat resistance and mechanical properties. In particular, PATE obtained by two-step temperature-programmed polymerization of an alkali metal sulfide and a dihalogen-substituted aromatic compound in an organic amide solvent in the presence of a specific controlled amount of water has a high molecular weight and It can be obtained as a granular polymer (Japanese Patent Publication No. 63-33775).

By the way, the commonly used PATE
Have problems such as insufficient compatibility with different polymers or poor adhesion with other materials such as metals. Therefore, attempts have been proposed to overcome these problems by introducing various functional groups into the molecule of PATE. PATE introduced with a functional group can also be used to produce various modified products or derivatives by using the functional group.

For example, in JP-A-63-305131, a dihalogen-substituted aromatic carboxylic acid such as dichlorobenzoic acid or an alkali metal salt thereof, a dihalogen-substituted aromatic compound, and an alkali metal sulfide are substantially anhydrous. Has been proposed for producing a copolymer having a functional group by polymerizing in the presence of a polar solvent.
However, according to this method, it is difficult to separate and purify the polymer from the reaction system at the time of production because only the powdery copolymer can be obtained, and the measuring property and the handling property are also obtained at the time of molding. However, there is a problem in that the environment is deteriorated due to the scattering of fine powder. Furthermore, it is difficult to obtain a sufficiently high molecular weight polymer by this method.

JP-A-61-2249 discloses that PATE having a disulfide introduced into the main chain is produced and then reacted with a reducing agent in the presence of a monofunctional compound to give a PATE having a functional end group. Are disclosed. However, in this method, it is difficult to obtain a high-molecular weight polymer because the molecular chain is cleaved, and the melting point of the obtained polymer is somewhat low.

JP-A-2-283763 discloses a resin composition containing a modified PPS obtained by reacting a polyphenylene sulfide resin with a carboxylic acid anhydride. Specifically, this modification reaction is
This is carried out by a method in which PS powder and carboxylic acid anhydride are dry blended, and then melt-kneaded in an extruder set at 290 to 310 ° C. and then pelletized. However, the modified PPS obtained by this method is melt-extracted with a solvent such as N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) to remove the carboxylic acid component, resulting in the loss of PPS and carboxylic acid. It cannot be said that a strong bond is formed with the anhydride.

In Japanese Patent Laid-Open No. 18422/1992, a PATE in which a structural unit composed of aminobenzene is introduced into the main chain is prepared, and then a carboxylic acid halide is reacted to introduce a carboxyl group or a carboxylic acid anhydride group. Disclosed is a method of manufacturing the above-mentioned PATE. By this method, a polymer having a relatively high molecular weight can be obtained, but since the functional group is introduced along the main chain, not at the terminal of the polymer, the crystallinity of the polymer is lowered, and as a result,
The heat resistance tends to decrease.

Further, as described above, P having a functional group
When the ATE is used alone or when mixed with other polymers and molded, it is desirable that the ATE be obtained in the form of granules that are easy to handle, not in the form of powder. However, according to the conventional method, when the content of the functional group in PATE is increased, fine powder is easily formed.

On the other hand, by reacting a dihalogen-substituted aromatic carboxylic acid, a dihalogen-substituted aromatic compound and an alkali metal sulfide in a polar solvent containing water in the presence of an alkaline earth metal compound, a carboxyl group is obtained. A PATE copolymer having a group or a metal salt thereof can be produced (Japanese Patent Application No. 2-4100, which is a prior application of the present applicant).
82; JP-A-4-214729). According to this method, a PATE copolymer having a functional group can be obtained in the form of granules, but the use of an alkaline earth metal compound is essential, and the functional group in the obtained PATE copolymer is The heat stability tends to be slightly insufficient.

Therefore, if PATE having a granular, high molecular weight and highly heat-resistant functional group such as a carboxyl group can be produced by a simple method, the use of PATE will be broadened and useful.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a phthalic anhydride group-containing polyarylene thioether which has good heat resistance and does not reduce the effect of functional groups due to decarboxylation even at the processing temperature of polymers. To do. Another object of the present invention is to provide a method for producing a granular, high-molecular-weight phthalic anhydride group-containing polyarylene thioether.

The inventors of the present invention have conducted extensive studies in order to overcome the above-mentioned problems of the prior art. As a result, a dihalogen-substituted aromatic compound and an alkali metal sulfide are polymerized in a polar organic solvent containing water. In the method for producing a polyarylene thioether, by allowing a monohalogen-substituted phthalic acid compound to be present in the polymerization reaction system, and adjusting the molar ratio of the charged dihalogen-substituted aromatic compound and the charged alkali metal sulfide to within a specific range, It was found that a polyarylene thioether containing a phthalic anhydride group, which has excellent heat resistance and does not decompose even at the processing temperature of the polymer, can be obtained.

In this case, if the polymerization reaction mixture is allowed to undergo a liquid-liquid phase separation state before the completion of the polymerization reaction, a granular polymer can be easily obtained. Furthermore, according to this method, a high molecular weight phthalic anhydride group-containing polyarylene thioether can be produced. The present invention has been completed based on these findings.

[0014]

Thus, according to the present invention, there is provided a method for producing a polyarylene thioether by polymerizing a dihalogen-substituted aromatic compound and an alkali metal sulfide in a polar organic solvent containing water. A monohalogen-substituted phthalic acid compound is present in the polymerization reaction system, and the ratio a / b of the molar number a of the charged dihalogen-substituted aromatic compound to the molar number b of the charged alkali metal sulfide is
Is set in the range of 0.8 <a / b <1. A method for producing a phthalic anhydride group-containing polyarylene thioether is provided. Hereinafter, the present invention will be described in detail.

(Dihalogen-Substituted Aromatic Compound) Examples of the dihalogen-substituted aromatic compound used in the present invention include dihalogen-substituted benzenes such as p-dihalobenzene and m-dihalobenzene; 2,3-dihalotoluene, 2,
4-dihalotoluene, 2,6-dihalotoluene, 3,4
-Dihalogen-substituted alkylbenzenes such as dihalotoluene and 2,5-dihalo-p-xylene; 1-phenyl-2,
Examples thereof include dihalogen-substituted arylbenzene such as 5-dihalobenzene; dihalogen-substituted biphenyl such as 4,4′-dihalobiphenyl; dihalogen-substituted naphthalene such as 2,6-dihalonaphthalene and 1,5-dihalonaphthalene.

The halogen elements in these dihalogen-substituted aromatic compounds are fluorine, chlorine, bromine and iodine, which may be the same or different. Among the dihalogen-substituted aromatic compounds, preferred are dihalogen-substituted benzenes, and p-dichlorobenzene is particularly preferred. In the present invention, these dihalogen-substituted aromatic compounds may be used alone or in combination of two or more, and dihalogen-substituted aromatic compounds other than the above may be used together as a minor component. . Further, in the present invention, in order to adjust the molecular weight of the polymer obtained, trihalogen-substituted benzene, dihalogen-substituted aniline and the like may be used together as a minor component, if necessary.

(Monohalogen-substituted phthalic acid compound) Examples of the monohalogen-substituted phthalic acid compound used in the present invention include 4-halophthalic acid, 3-halophthalic acid, and phthalic acid containing halophenyl group, halophenoxy group, and halo. Examples thereof include substituted phthalic acid derivatives in which a phenylthio group, a halobenzenesulfonyl group, a halobenzenesulfinyl group, a halobenzyl group, a 2-halophenyl-2-propyl group and the like are substituted. The monohalogen-substituted phthalic acid compound used in the present invention can also be used in the form of a salt with an alkali metal or an alkaline earth metal (phthalic acid monometal salt or phthalic acid dimetal salt).

The halogen element in these monohalogen-substituted phthalic acid compounds is fluorine, chlorine, bromine, or iodine, respectively. In the present invention, these monohalogen-substituted phthalic acid compounds may be used alone or in combination of two or more kinds. Among these monohalogen-substituted phthalic acid compounds, sodium hydrogen chlorophthalate, disodium chlorophthalate, and chlorophthalic acid are particularly preferably used.

(Alkali metal sulfide) Examples of the alkali metal sulfide used in the present invention include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide,
Examples include cesium sulfide. These can be used in the form of anhydrate, hydrate or aqueous mixture. In addition, alkali metal sulfides prepared in situ from alkali hydrosulfide can also be used. These alkali metal sulfides
Each may be used alone or in combination of two or more.

(Polar Organic Solvent) The polar organic solvent used in the present invention is preferably an aprotic polar solvent which is stable to alkali at high temperature. Specific examples thereof include, for example, N, N-dimethylformamide,
Amide compounds such as N, N-dimethylacetamide; N-
N-alkyl- or N-cycloalkyl-lactam compounds such as methyl-ε-caprolactam, N-methyl-2-pyrrolidone and N-cyclohexylpyrrolidone; 1,
N, N-dialkylimidazolidinone compounds such as 3-dimethyl-2-imidazolidinone; tetraalkylurea compounds such as tetramethylurea; hexaalkylphosphoric triamides such as hexamethylphosphoric triamide; and the like. These solvents may be used alone or in combination of two or more.

(Polymerization Method) In the present invention, as a polymerization method, basically, in a polar organic solvent containing water,
A method of polymerizing an alkali metal sulfide and a dihalogen-substituted aromatic compound is adopted, in which case a monohalogen-substituted phthalic acid compound is present in the polymerization reaction system, and the number of moles of the charged dihalogen-substituted aromatic compound is a. The ratio a / b of the charged alkali metal sulfide to the mole number b is 0.8 <a
Adjust so that / b <1. a / b is 0.
If it is 8 or less, it is difficult to increase the molecular weight, and if it is 1 or more, it becomes difficult to introduce a phthalic acid group.

The monohalogen-substituted phthalic acid compound is usually used in an amount of 0.05 to 30 mol%, based on the total amount of the dihalogen-substituted aromatic compound and the monohalogen-substituted phthalic acid compound.
It is preferably used in the range of 0.1 to 25 mol%. If the amount of the monohalogen-substituted phthalic acid compound used is less than 0.05 mol%, the effect of introducing the phthalic acid group will be insufficient, while if it exceeds 30 mol%, it will be difficult to obtain a high molecular weight polymer. It is not preferable because the yield in granular form is also reduced.

The total amount of the dihalogen-substituted aromatic compound and the monohalogen-substituted phthalic acid compound relative to 1 mol of the alkali metal sulfide is usually 0.81 to 1.42 mol, preferably 0.83 to 1.40 mol. Is. If it deviates from this range, it becomes difficult to obtain a high-molecular weight polymer, which is not preferable. The amount of the polar organic solvent used is not particularly limited, but usually, the total number of moles (total number of moles) of the dihalogen-substituted aromatic compound and the monohalogen-substituted phthalic acid compound is 0. It is used in an amount of 1 to 5 mol, preferably 0.5 to 3.5 mol.

In the present invention, the polymerization reaction is carried out in a polar organic solvent containing water. The water content is usually in the range of 0.5 to 30 mol, preferably 1 to 25 mol, based on 1 kg of the polar organic solvent. A part of this water may be added during the polymerization reaction. When the alkali metal sulfide is a hydrate, the content of water can be adjusted by performing dehydration operation by azeotropic distillation or the like, if necessary. The content of water per kg of polar organic solvent is 0.
If it is less than 5 mol or more than 30 mol, undesirable side reactions and the like are likely to occur, and it is difficult to obtain a high molecular weight polymer.

In the present invention, the monohalogen-substituted phthalic acid compound may be added to the reaction system at any time. For example, (1) a reaction system containing an alkali metal sulfide is charged together with a dihalogen-substituted aromatic compound. Polymerization method, (2) a method in which an alkali metal sulfide and a dihalogen-substituted aromatic compound are first charged to start a polymerization reaction, and then a monohalogen-substituted phthalic acid compound is added,
(3) There is a method of combining these. The earlier the addition of the monohalogen-substituted phthalic acid compound, the easier the introduction of the phthalic acid group.

When the monohalogen-substituted phthalic acid compound is added to the reaction system in a state of being dissolved in water, a basic compound may be added together if desired. Further, in order to keep the polymerization reaction system alkaline, the polymerization reaction may be carried out by adding a basic compound. Such basic compounds include alkali metal hydroxides, alkali metal oxides,
At least one compound selected from the group consisting of alkaline earth metal hydroxides and alkaline earth metal oxides can be given.

The polymerization reaction is usually carried out in an atmosphere of an inert gas such as nitrogen or argon at a temperature range of usually 150 to 300 ° C., preferably 180 to 280 ° C., usually 0.5 to 30 hours, preferably 1 to 30 ° C. It is carried out for a period of 20 hours. If the reaction temperature is too low, the polymerization reaction may be insufficient, and conversely, if it is too high, the decomposition reaction may occur. If the polymerization time is too short, the polymerization reaction may be insufficient, and conversely, if it is too long, the productivity will decrease.

The polymerization reaction can also be carried out by raising the temperature in multiple stages of two or more stages. According to this method, a higher molecular weight polymer can be easily obtained in a shorter time. For example, 2
There is a method in which the first stage polymerization is carried out at a temperature of 35 ° C. or lower, and then the second stage polymerization is carried out by raising the temperature to 240 ° C. or higher. In particular, in the two-step polymerization reaction, when the temperature is raised to 240 ° C. or higher in the subsequent stage, the water-added two-step polymerization method in which water is added before or after the temperature increase has a higher molecular weight and more excellent melt stability. Easy to obtain polymer.

As such a water-added two-step polymerization method,
High molecular weight P disclosed in JP-B-63-33775
A method in which the polymerization reaction is performed in at least the following two stages according to the method for producing ATE is preferable. First stage (first-stage polymerization): 1 state in the presence of 0.5 to 2.4 mol of water per mol of the charged alkali metal sulfide.
A step of carrying out a polymerization reaction at a temperature of 50 to 235 ° C., preferably 180 to 235 ° C. to adjust the polymerization conversion rate to 50 to 98 mol%, the second stage (second stage polymerization): 2 per 1 mol of the charged alkali metal sulfide. 0.0-7.0 mol, preferably 2.5-7.
Water is added so that 0 mol of water exists, and the temperature is 240 to 300 ° C., preferably 245 to 280.
A step of raising the temperature to ℃ and continuing the polymerization reaction.

The polymerization conversion in the first step is based on the conversion of the dihalogen-substituted aromatic compound. Although the molecular weight of the obtained polymer depends on the amount of the monohalogen-substituted phthalic acid compound added, it is easier and higher to add the monohalogen-substituted phthalic acid compound when water is added at the start of the second step. It can be molecular weight. Further, according to this two-step polymerization method, it is easy to obtain a granular polymer.

In the present invention, it is preferable to obtain a granular polymer by allowing the polymerization reaction mixture to undergo a liquid-liquid phase separation state in the polymerization reaction system before the completion of the polymerization.
Here, the liquid-liquid phase separation state means a state in which a polymer rich phase containing a large amount of a polymer produced by the progress of a polymerization reaction and a polymer dilute phase having a high solvent concentration coexist in a liquid state. .

The phase-separated state is PAT in a polar organic solvent.
This occurs when the solubility of the solvent in the polymer in the polymerization reaction system of E is low. Therefore, when water is mixed with the polar organic solvent, the solubility of PATE often decreases, which is a preferred embodiment of the method of the present invention. Also, by adding an alkali metal carboxylate such as lithium acetate, sodium acetate, sodium benzoate as a polymerization aid,
The phase separation state can be easily formed. It is also effective in improving the yield of the granular polymer.

The state in which both phases separated into two or more phases are liquid (liquid-liquid phase separation state) can be formed by adjusting the temperature at which the polymer-containing phase becomes liquid. Usually, in the process of raising the temperature of the polymerization reaction system from the first-stage polymerization to the second-stage polymerization, the liquid-liquid phase separation state is formed by setting the temperature in the system to the temperature at which the molten phase of the polymer is formed or higher.

The temperature at which each phase separated is in a liquid state is measured by, for example, visually observing that each phase is in a liquid state while putting a mixture having the same composition as the polymerization reaction system in a pressure-resistant glass tube and heating. , Can be performed by measuring the temperature at that time. Alternatively, for example, it can be known by measuring with a high pressure glass crucible with a differential scanning calorimeter (DSC) manufactured by Perkin Elmer. The temperature varies depending on the type of PATE to be synthesized, the degree of polymerization, or the polymer concentration in the solvent. For example, in the case of PATE mainly composed of polyphenylene sulfide, and in the case of NMP type,
The temperature is preferably 230 ° C. or higher.

After completion of the polymerization reaction, PA having a phthalic acid group
TE is generated, but the phthalic acid of the phthalic acid group is usually
Since it exists in the form of phthalic acid or a metal salt of phthalic acid, in the case of a metal salt of phthalic acid, the polymer is previously treated with acidic water to form phthalic acid, which is then dehydrated and converted into a phthalic anhydride group. be able to. In this case, the dehydration reaction is
It can be performed by a drying treatment of the polymer.

(PATE containing phthalic anhydride group) According to the present invention, the melt viscosity as measured at 310 ° C. and a shear rate of 1200 sec ⁻¹ is usually 30 poises or more, preferably 100 poises or more, more preferably 300 poises or more. A phthalate group-containing PATE can be obtained. The amount of the phthalic anhydride group contained in the phthalic anhydride group-containing PATE of the present invention is determined by measuring the absorbance at 1850 cm ^-1 , which is the characteristic absorption band of the phthalic anhydride group, in the infrared absorption spectrum of the PATE. When expressed as an IR index (%) by multiplying 100 by the absorbance ratio divided by the absorbance at 1900 cm ⁻¹ which is the external variation angular overtone absorption band, it is usually 2% or more, preferably 3% or more. If the IR index is less than 2%, the effect of introducing the phthalic anhydride group is too small.

According to the manufacturing method of the present invention, 100
When sieving with a mesh screen, granular phthalic anhydride group-containing PATE having a size that remains on the screen is obtained. PATE containing phthalic anhydride groups according to the present invention
Is stable at the normal processing temperature of the PATE,
It does not decompose due to the decarboxylation reaction.

[0038]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The methods for measuring the physical properties are as shown below.

(1) IR Index of Phthalic Anhydride Group Content The phthalic anhydride group-containing PATE was hot-pressed at 320 ° C., then put in ice water and rapidly cooled.・ Elmer (Per
It was measured by FT-IR1760 manufactured by Kin Elmer). From the obtained spectrum, the value obtained by dividing the absorbance at 1850 cm ^-1 which is the characteristic absorption band of phthalic anhydride groups in the absorbance at 1900 cm ^-1 is CH out-of-plane deformation overtone absorption band%
Displayed in.

(2) Melt viscosity Using a Capirograph (manufactured by Toyo Seiki Co., Ltd.), a temperature of 310
The measurement was carried out under the conditions of ℃ and a shear rate of 1200 sec ^-1 . (3) Melting point (Tm) and glass transition temperature (Tg) A sheet obtained by hot pressing a polymer at 320 ° C. and then rapidly cooling the same was used in a nitrogen atmosphere at 10 ° C./min using a Perkin Elmer DSC. It measured at the temperature rising rate. (4) Thermogravimetric analysis Using a thermogravimetric analyzer (TGA) manufactured by METTLER CORPORATION, 20 ° C
/ Min, measured in a nitrogen stream.

Reference Example 1 6700 g of N-methyl-2-pyrrolidone (NMP) was placed in a titanium-lined autoclave.
Then, 3800 g of hydrous sodium sulfide [22.44 mol as S content (sulfur content)] was charged, and after nitrogen substitution, 1436 g of water (79.79 g) was added while gradually raising the temperature to 200 ° C.
2527 g of NMP solution containing 0.1 mol of hydrogen sulfide and 0.
453 mol were distilled off. The amount of water in the system after dehydration is 1.543 mol based on 1 mol of S content. Then p-
3395 g (23.09 mol) of dichlorobenzene and N
MP2637g was supplied and it was made to react at the temperature of 220 degreeC for 4.5 hours. At this stage, a small amount of the produced slurry in the polymerization reaction system was sampled, the amount of residual p-dichlorobenzene was determined by gas chromatography, and the conversion was calculated to be 92%. Next, 447.7 g of water (2
(4.85 mol) was injected under pressure (total amount of S: 1 mol, water: 2.63 mol). The temperature was raised to 255 ° C. and the reaction was carried out for 4.0 hours.

The obtained reaction mixture was sieved with a 100 mesh screen to separate the granular polymer, and then washed with acetone 3 times, washed with water 3 times, and adjusted to pH 3 with HC.
After washing with water, washing with water, dehydration and drying were performed to obtain a granular polymer (Polymer R). The physical properties of this polymer R were as follows. Melt viscosity: 510 poise, Tm: 282 ° C., Tg: 84 ° C.

Example 1 A titanium-lined autoclave was charged with 3200 g of NMP and 135 hydrated sodium sulfide.
1.1 g (8.00 mol as S content) was charged, the atmosphere was replaced with nitrogen, and the temperature was gradually raised to 200 ° C., while water 543.
NMP solution 1373.8 containing 1 g (30.15 mol)
g and 0.17 mol of hydrogen sulfide were distilled off. Then p-
Dichlorobenzene 1116.5 g (7.595 mol),
NMP1540.2g, and water 32.7g (1.82
Mol) was added and reacted at a temperature of 220 ° C. for 4.5 hours. At this stage, a small amount of the produced slurry in the polymerization reaction system was sampled to find the amount of residual p-dichlorobenzene and the conversion rate was calculated to be 91.5%. next,
Further, 282 g (15.67 mol) of water, 175.86 g (0.783 mol) of sodium hydrogen 4-chlorophthalate, and 31.32 g (0.78 mol) of sodium hydroxide.
(3 mol) was injected under pressure, the temperature was raised to 255 ° C., and the reaction was carried out for 5 hours.

The obtained reaction mixture was sieved with a 100 mesh screen to separate the granular polymer, then washed with acetone 3 times, washed with water 4 times, and washed with HCl water while adjusting the pH to 3 with HCl water. After 5 times, dehydration and drying (1
Granular polymer (Polymer A) after 10 ° C for 8 hours
Was obtained with a yield of 73%. The physical properties of this polymer A were as follows. Phthalic anhydride IR index: 26.4%, melt viscosity: 1340 poise, Tm: 276 ° C, Tg: 90 ° C.

The results of thermogravimetric analysis of polymer A are shown in FIG. Further, the results of thermogravimetric analysis of the polymer R obtained in Reference Example 1 are also shown in FIG. As is clear from comparison between FIG. 1 and FIG. 2, phthalic anhydride group-containing PATE (polymer A) obtained by the method of the present invention
Has good thermal stability in spite of containing a phthalic anhydride group, and its thermogravimetric curve is almost the same as that of the polymer R containing no phthalic anhydride group.

Example 2 A titanium-lined autoclave was charged with NMP of 8000 g and hydrous sodium sulfide 338.
After adding 2.7 g (20.0 mol as S content) and purging with nitrogen, 140 g of water was added while gradually raising the temperature to 200 ° C.
NMP solution 2555 containing 6.3 g (78.06 mol)
g and 0.49 mol of hydrogen sulfide were distilled off. Then p-
2838.9 g (19.31 mol) of dichlorobenzene,
NMP2885.5 g, and water 129.3 g (7.1
8 mol) was supplied and the reaction was carried out at a temperature of 220 ° C. for 4.5 hours. At this stage, a small amount of the produced slurry in the polymerization reaction system was sampled to find the amount of residual p-dichlorobenzene and the conversion was calculated to be 90%. Next, a further 527.2 g (29.29 mol) of water, 219.1 g (0.984 mol) of sodium 4-chlorophthalate hydrogenate and 39.02 g (0.97 mol) of sodium hydroxide.
(55 mol) was injected under pressure, the temperature was raised to 255 ° C., and the reaction was carried out for 5 hours.

Thereafter, post-treatment was carried out in the same manner as in Example 1 to obtain a granular polymer (Polymer B) with a yield of 67%. The physical properties of this polymer B were as follows. Phthalic anhydride IR index: 6.5%, melt viscosity: 2920 poise, Tm: 276 ° C, Tg: 91 ° C.

[Example 3] In a titanium-lined autoclave, 3200 g of NMP and 135 of hydrous sodium sulfide were added.
1.1 g (8.00 mol as S content) was charged, the atmosphere was replaced with nitrogen, and the temperature was gradually raised to 200 ° C., while water 535.
NMP solution containing 9 g (29.75 mol) 1381.3
g and 0.16 mol of hydrogen sulfide were distilled off. Then p-
Dichlorobenzene 1118.6 g (7.61 mol), N
MP1562.4g and water 24.7g (1.37mol) were supplied, and it was made to react at the temperature of 220 degreeC for 4.5 hours. At this stage, a small amount of the produced slurry in the polymerization reaction system was sampled to find the amount of residual p-dichlorobenzene, and the conversion rate was calculated to be 93%. Next, 212 g (11.77 mol) of water, 176.0 g (0.784 mol) of sodium hydrogen 4-chlorophthalate, and 31.36 g (0.784 mol) of sodium hydroxide were added under pressure, and the temperature was raised to 255 ° C. The mixture was heated and reacted for 5 hours.

Thereafter, post-treatment was carried out in the same manner as in Example 1 to obtain a granular polymer (Polymer C) with a yield of 65%. The physical properties of this polymer C were as follows. Phthalic anhydride IR index: 65.4%, melt viscosity: 310 poise, Tm: 279 ° C, Tg: 87 ° C.

[Example 4] In a titanium-lined autoclave, 3200 g of NMP and 135 hydrated sodium sulfide were added.
After charging 1.1 g (8.00 mol as S content) and purging with nitrogen, 562 g of water was added while gradually raising the temperature to 200 ° C.
1341 g of NMP solution containing (31.19 mol) and 0.18 mol of hydrogen sulfide were distilled. Next, 1138.4 g (7.74 mol) of p-dichlorobenzene, NMP14
84.5 g, sodium 4-chlorophthalate hydrogen 52.
69 g (0.2346 mol), sodium hydroxide 12.
51 g (0.3128 mol), and water 122.1 g
(6.78 mol) was supplied, and the reaction was carried out at a temperature of 220 ° C. for 2.0 hours, a temperature of 230 ° C. for 2.0 hours, and a temperature of 240 ° C. for 2.0 hours, and then 140.9 g of water ( 7.
82 mol) was introduced under pressure, the temperature was raised to 255 ° C., and the reaction was carried out for 3.5 hours.

Thereafter, post-treatment was carried out in the same manner as in Example 1 to obtain a granular polymer (Polymer D) with a yield of 75%. The physical properties of this polymer D were as follows. Phthalic anhydride IR index: 27.6%, melt viscosity: 990 poise, Tm: 279 ° C, Tg: 88 ° C.

Example 5 A titanium-lined autoclave was charged with 6000 g of NMP and 3200 of hydrous sodium sulfide.
g (18.88 mol as S content), sodium 4-chlorophthalate hydrogen 125.5 g (0.56 mol), sodium hydroxide 45.1 g (1.13 mol), sodium acetate 77.1 g (0.94 mol) ) Was charged and after nitrogen substitution, 1306.7 g of water was added while gradually raising the temperature to 200 ° C.
2798.4 g of an NMP solution containing (72.5 mol) and 0.405 mol of hydrogen sulfide were distilled. Then, 2661.5 g (18.11 mol) of p-dichlorobenzene, NM
P2899.1 g and water 93.8 g,
The reaction was carried out at a temperature of 0 ° C. for 4.5 hours. At this stage, a small amount of the produced slurry in the polymerization reaction system was sampled to find the amount of residual p-dichlorobenzene, and the conversion rate was calculated to be 91%. Next, 832 g of water (46.
(2 mol) was introduced under pressure, the temperature was raised to 255 ° C., and the reaction was carried out for 5 hours.

Thereafter, post-treatment is performed in the same manner as in Example 1,
A granular polymer (Polymer E) having a relatively uniform particle size was obtained with a yield of 77%. The physical properties of this polymer E were as follows. Phthalic anhydride IR index: 24.0%, melt viscosity: 900 poise, Tm: 277 ° C, Tg: 89 ° C.

Example 6 In a titanium-lined autoclave, 3200 g of NMP and 135 hydrated sodium sulfide were added.
1.5 g (8.00 mol as S content), 53.9 g (0.24 mol) of sodium hydrogen 4-chlorophthalate, and 9.6 g (0.24 mol) of sodium hydroxide were charged, and the atmosphere was replaced with nitrogen. Water while raising the temperature to 200 ° C
NMP solution 137 containing 3.1 g (30.15 mol)
3.8 g and 0.17 mol of hydrogen sulfide were distilled off. Subsequently, 1139.5 g (7.75 mol) of p-dichlorobenzene, NMP1540.2g, and 32.7 g of water were supplied, and it was made to react at the temperature of 220 degreeC for 4.5 hours. At this stage, a small amount of the produced slurry in the polymerization reaction system was sampled to find the amount of residual p-dichlorobenzene, and the conversion rate was calculated to be 91%. Next, water 211
g (11.7 mol) was injected under pressure, the temperature was raised to 255 ° C., and the reaction was carried out for 5 hours.

Thereafter, post-treatment was carried out in the same manner as in Example 1 to obtain a granular polymer (Polymer F) with a yield of 78%. The physical properties of this polymer F were as follows. Phthalic anhydride IR index: 16.0%, melt viscosity: 1000 poise, Tm: 277 ° C, Tg: 89 ° C.

Comparative Example 1 PATE having a melt viscosity of about 1400 poise (Fortron KPSW21 manufactured by Kureha Chemical Industry Co., Ltd.)
4), phthalic anhydride was dry blended in a weight ratio of 98/2, and then the mixture was extruded using a twin-screw extruder BT-30 at a maximum set temperature of 310 ° C. and pelletized to obtain a melt-modified polymer a. The melt-modified polymer a had a phthalic anhydride group content of 119% by IR index. Similarly, the P
ATE was dry-blended with sodium hydrogen 4-chlorophthalate in a weight ratio of 98/2, and then extruded with a twin-screw extruder BT-30 at a maximum preset temperature of 310 ° C to be pelletized to obtain a melt-modified polymer b. It was The phthalic anhydride group content of the melt-modified polymer b was 29% by IR index.

Next, the melt-modified polymer a, the melt-modified polymer b, and the polymer F prepared in Example 6 were subjected to remelting treatment by NMP, and then the amount of functional groups was evaluated by IR. That is, 50 g of each polymer was separately put into a 1 liter autoclave, and NMP500 was added.
g, 30 g of water, and 4 g of NaOH were added, and after nitrogen substitution, the temperature was raised from room temperature to 255 ° C. in about 1 hour to melt the polymer, and while stirring, the temperature reached 255 ° C. Immediately after stopping heating and up to 80 ° C. Cooled in about 1.5 hours. The slurry taken out after cooling was sieved with a 100-mesh screen, washed with NaOH (PH: 12.5) three times to remove the phthalic acid extracted by remelting with NMP, and HCl to obtain the acid form. After washing twice with water (PH: 2) and drying, a quenched press sheet was prepared at 320 ° C., and the phthalic anhydride group content was examined by infrared absorption spectrum measurement.

After remelting treatment with NMP, both IR indices of the melt-modified polymer a and the melt-modified polymer b are 0.
%, The IR index of the polymer F obtained in Example 6 of the present invention was 12%. That is, PA
The modified polymers obtained by mixing and extruding TE and phthalic anhydride or PATE and sodium hydrogen 4-chlorophthalate all show the content of phthalic anhydride, but phthalic acid is remelted and extracted by NMP. Infrared characteristic absorption band of anhydride is no longer detected, IR of unmodified PATE
It becomes the same as the spectrum.

On the other hand, in the polymer F produced by the method of the present invention, the presence of phthalic anhydride is clearly confirmed even after the remelting treatment by PATE. Therefore, according to the method of the present invention, it can be seen that a polymer having different binding force of phthalic acid groups can be obtained as compared with the modified polymer obtained by simple mixing and melt extrusion.

[0060]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a granular phthalic anhydride group-containing PATE in which the functional phthalic anhydride group has good thermal stability. According to the production method of the present invention, the phthalic anhydride group content can be adjusted within a desired range, and a high molecular weight phthalic anhydride group-containing PATE can be produced. The phthalic anhydride group-containing PATE according to the production method of the present invention has an effect that the reactivity of the functional group can be fully utilized because the thermal stability of the functional group is particularly good. For example, as an alloy with another resin, Alternatively, it can be used for the purpose of improving the adhesiveness of the filler. In addition, the high-molecular-weight phthalic anhydride group-containing PATE produced by the production method of the present invention has a phthalic anhydride group at the terminal and thus has good crystallinity and retains the original good physical properties, heat resistance, chemical resistance, etc. of PATE. Has been done. Furthermore, since the phthalic anhydride group-containing PATE produced by the production method of the present invention is granular, it has the advantage of facilitating the separation and purification of the polymer during production, and also has the effect of deteriorating occupational health due to fine powder during molding and reducing the environment. It has an effect of improving pollution and excellent handleability. The phthalic anhydride group-containing PATE obtained by the production method of the present invention is used alone or as a blend with other resins for a wide range of applications such as injection molded products, extruded products, films, sheets, encapsulants, and fibers. Can be used.

[Brief description of drawings]

1 shows the results of thermogravimetric analysis of polymer A obtained in Example 1. FIG.

FIG. 2 shows the results of thermogravimetric analysis of polymer R obtained in Reference Example 1.

Claims (3)

[Claims] 1. A method for producing a polyarylene thioether by polymerizing a dihalogen-substituted aromatic compound and an alkali metal sulfide in a polar organic solvent containing water, wherein a monohalogen-substituted phthalic acid compound is added to the polymerization reaction system. Anhydrous, characterized in that the ratio a / b of the number of moles a of the charged dihalogen-substituted aromatic compound to the number b of moles of the charged alkali metal sulfide is 0.8 <a / b <1. Process for producing phthalic acid group-containing polyarylene thioether. 2. The amount of the monohalogen-substituted phthalic acid compound is in the range of 0.05 to 30 mol% with respect to the total amount of the dihalogen-substituted aromatic compound and the monohalogen-substituted phthalic acid compound. Manufacturing method. 3. The production method according to claim 1, wherein the polymerization reaction mixture undergoes a liquid-liquid phase separation state before the completion of the polymerization reaction.