JP6808926B2 - Manufacturing method of polyarylene sulfide resin - Google Patents

Description

The present invention relates to a method for producing a polyarylene sulfide resin.

Polyarylene sulfide resin (hereinafter, may be referred to as PAS) represented by polyarylene sulfide resin (hereinafter, may be referred to as PPS) has excellent heat resistance and chemical resistance, and is used for electrical and electronic parts and automobiles. Widely used in parts, water heater parts, textiles, film applications, etc.

As a method for producing a high molecular weight polyarylene sulfide resin, a so-called "S dropping method" is known in which an alkali metal sulfide is dropped and polymerized in the presence of a polyhaloaromatic compound and an organic polar solvent. ..

For example, a hydrous sulfide agent consisting of alkali metal hydrosulfide and / or alkali metal sulfide is introduced into a mixture containing an organic polar solvent and a polyhalo aromatic compound at a rate at which water can be removed from the reaction mixture to carry out the reaction. Thereby, a technique for producing a high-molecular-weight and linear polyarylene sulfide and improving the toughness of the polyarylene sulfide is disclosed. However, although the polyarylene sulfide obtained by the above method has a high molecular weight and some improvement in toughness, it is still insufficient. Further, in order to improve the toughness of polyarylene sulfide, a method of modifying with a silane coupling agent is also known, but the polyarylene sulfide obtained by this method has an increased molecular weight, but reacts with an acid or an alkali. Since there are few active sites, it is difficult to modify with a coupling agent such as a silane coupling agent, and in the end, practical toughness cannot be obtained.

Therefore, the aliphatic cyclic compound is hydrolyzed in the presence of a polyhalo aromatic compound, an aliphatic cyclic compound, an alkali metal hydroxide and water (step 1), and then an alkali metal sulfide or an alkali metal hydrosulfide. A method has been proposed in which a polymerization reaction (step 2) is carried out while dropping substances into a system and sequentially adding them (see Patent Document 2).

This method sequentially adds alkali metal sulfide or alkali metal hydrosulfide and alkali metal hydroxide into the system in the presence of a hydrolyzate of an aliphatic cyclic compound and a polyhaloaromatic compound (DCB). The hydrolyzate of the aliphatic cyclic compound produces an alkali metal salt (SMAB), and the SMAB and the polyhaloaromatic compound cause a side reaction to cause the following structural formula (1).

（式中、ｎは０〜２であり、Ｙ^１はハロゲン原子を、Ｙ^２は水素原子又はハロゲン原子を、Ｒ^１は水素原子又は炭素原子数１〜３のアルキル基又はシクロヘキシル基を表し、Ｒ^２は炭素原子数３〜５のアルキレン基を、Ｘは水素原子又はアルカリ金属原子を表す。）で表されるカルボキシアルキルアミノ基含有化合物（以下、ＣＰ−ＭＡＢＡと表すことがある。）を生成するため、見かけ上のカルボキシ基量が多く測定されるものであった。
また、この方法は、反応系にスルフィド化剤を順次加えるため、原料中に占める硫黄源の存在割合が低く、該脂肪族系環状化合物の加水分解物のアルカリ金属塩の割合も低くなることから、ポリマーの成長末端が副反応を起こす確率も低くなる。その結果、反応活性点となるポリマー末端のカルボキシ基量を充分増加させることができていなかった。このため、ＣＰ−ＭＡＢＡを精製工程で除去した後に得られるＰＡＳ樹脂は、シランカップリング剤や官能基含有熱可塑性エラストマー等で変性しても、靱性や耐衝撃性等の機械的強度の向上が充分なものとは言えなかった。また、ポリマーの成長末端が副反応を起こす確率が低くなるとはいえ、やはりＣＰ−ＭＡＢＡの存在により、さらにポリマーの高分子量化を図る際には、阻害要因となっており、この方法によって得られるポリアリーレンスルフィドも、分子量の高いポリマーが得られるものの、未だ十分なものではなかった。

(In the formula, n is 0 to 2, Y ¹ represents a halogen atom, Y ² represents a hydrogen atom or a halogen atom, and R ¹ represents a hydrogen atom or an alkyl group or a cyclohexyl group having 1 to 3 carbon atoms. R ² represents an alkylene group having 3 to 5 carbon atoms, and X represents a hydrogen atom or an alkali metal atom.) A carboxyalkylamino group-containing compound (hereinafter, may be referred to as CP-MABA). Since it was produced, a large amount of apparent carboxy group was measured.
Further, in this method, since the sulfidizing agent is sequentially added to the reaction system, the abundance ratio of the sulfur source in the raw material is low, and the ratio of the alkali metal salt of the hydrolyzate of the aliphatic cyclic compound is also low. , The probability that the growth end of the polymer will cause a side reaction is also low. As a result, the amount of carboxy group at the polymer terminal, which is the reaction active site, could not be sufficiently increased. Therefore, even if the PAS resin obtained after removing CP-MABA in the purification step is modified with a silane coupling agent or a functional group-containing thermoplastic elastomer, the mechanical strength such as toughness and impact resistance can be improved. It wasn't enough. In addition, although the probability that the growth end of the polymer causes a side reaction is low, the presence of CP-MABA is also an inhibitory factor when further increasing the molecular weight of the polymer, which can be obtained by this method. Polyarylene sulfide also provides a polymer with a high molecular weight, but it is still insufficient.

Japanese Unexamined Patent Publication No. 8-100064 Japanese Unexamined Patent Publication No. 2001-40090

Therefore, an object to be solved by the present invention is to provide a method for producing a polyarylene sulfide resin having a large amount of carboxy groups at the polymer terminal and a large amount of polyarylene sulfide resin with high productivity.

As a result of various studies by the inventors of the present application, in the method described in Patent Document 1, the dropping sodium sulfide elutes the metal atom in the wetted portion of the reactor, which becomes a factor that inhibits the polymerization reaction. In addition, in the method described in Patent Document 2, the fact that a large amount of CP-MABA is already present in the reaction system before the addition of the sulfidizing agent is an inhibitory factor for the PAS polymerization reaction. I found it and came to solve the above problem.

That is, the present invention is characterized in that an alkali metal hydroxide and an alkali metal hydrosulfide are independently supplied and polymerized in a reaction vessel containing an aliphatic cyclic compound and a polyhaloaromatic compound. The present invention relates to a method for producing a polyarylene sulfide resin.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing a polyarylene sulfide resin having a large amount of carboxy groups at the polymer terminal and a large amount of polyarylene sulfide resin with high productivity.

It is a schematic diagram of an example of a reactor that can be used in carrying out the present invention (schematic diagram of the reactor used in Example 1).

The method for producing polyarylene sulfide of the present invention polymerizes an alkali metal hydroxide and an alkali metal hydrosulfide in a reaction vessel containing an aliphatic cyclic compound and a polyhaloaromatic compound while independently supplying them. It is characterized by reacting. The details will be described below.

The present invention first comprises a step (1) of obtaining a solution for a polymerization reaction containing an aliphatic cyclic compound and a polyhaloaromatic compound in a reaction vessel.

As the aliphatic cyclic compound used in the present invention, known ones can be used without particular limitation as long as they can be opened by hydrolysis, and specific examples of such an aliphatic cyclic compound. N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, N-methyl-ε-caprolactam, formamide, acetamide, N-methylformamide, N, N-dimethylacetamide. , 2-Pyrrolidone, ε-caprolactam, hexamethylphosphoramide, tetramethylurea, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone acid and other aliphatic cyclic amide compounds, amidourea, and lactam. Kind. Among these, an aliphatic cyclic amide compound, particularly NMP, is preferable from the viewpoint of good reactivity.

Specific examples of the polyhaloaromatic compound used in the present invention include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3. 5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6-trihalonaphthalene, 2,5-dihalotoluene, 1,4-dihalo Naphthalene, 1-methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-di Halonitrobenzene, 2,4-dihaloanisole, p, p'-dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4 , 4'-Dihalodiphenylsulfide, and compounds having an alkyl group having 1 to 18 carbon atoms as a nuclear substituent in the aromatic ring of each of the above compounds. Further, it is desirable that the halogen atom contained in each of the above compounds is a chlorine atom or a bromine atom.

The proportion of the aliphatic cyclic compound used varies depending on the type of the compound used and the proportion of water in the system, and is not particularly limited, but maintains the viscosity of the reaction system capable of a uniform polymerization reaction. Further, in order to maintain a certain degree of productivity, the amount to be charged should be in the range of 1.0 to 6.0 mol per 1 mol of sulfur atom of the alkali metal hydrosulfide charged in the step (2) described later. Preferably, from the viewpoint of further increasing productivity, the range of 1.2 to 5.0 mol is more preferable, and the range of 1.5 to 4.5 mol is most preferable.

Among the polyhaloaromatic compounds, the bifunctional dihaloaromatic compound is preferable in the present invention because a linear high molecular weight PAS resin can be efficiently produced, and in particular, the mechanical strength of the finally obtained PAS resin and the like. From the viewpoint of improving moldability, p-dichlorobenzene, m-dichlorobenzene, 4,4'-dichlorobenzophenone and 4,4'-dichlorodiphenylsulfone are preferable, and p-dichlorobenzene is particularly preferable. If it is desired to have a branched structure in a part of the polymer structure of the linear PAS resin, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, or 1 together with the above dihaloaromatic compound. , 3,5-Trihalobenzene is preferably used in combination.

In addition, a copolymer containing two or more different reaction units can be obtained by an appropriate selective combination of polyhaloaromatic compounds, for example, p-dichlorobenzene and 4,4'-dichlorobenzophenone or 4, It is preferable to use it in combination with 4'-dichlorodiphenyl sulfone because a polyarylene sulfide having excellent heat resistance can be obtained.

The amount of the polyhalo aromatic compound charged is not particularly limited, but since the amount charged is directly used for the polymerization reaction, the sulfur atom 1 of the alkali metal hydrosulfide charged in the step (2) described later is considered from the viewpoint of productivity or economy. The range of 0.7 to 1.2 mol is preferable, the range of 0.8 to 1.1 mol is more preferable, and the ratio of equimolar is particularly preferable.

The condition inside the reaction vessel in the step (1) may be either an open system or a closed system, but it is preferable to react in the closed system in the presence of an inert gas from the viewpoint of improving productivity. The temperature condition is not particularly limited, but is preferably in the range of 120 to 280 ° C, preferably 180 to 250 ° C.

Next, in the present invention, the alkali metal hydroxide and the alkali metal hydrosulfide are independently contained in the reaction vessel containing the aliphatic cyclic compound and the polyhaloaromatic compound obtained through the step (1). It has a step (2) of carrying out a polymerization reaction while supplying to.

Alkali metal hydroxides and alkali metal hydrosulfides are independently stored in storage tanks and supplied to reaction vessels through pipes. At that time, it is preferable to control the supply rate of the alkali metal hydroxide or the alkali metal hydrosulfide by appropriately adjusting the pressure of the pump. With the part of the reactor in contact with the alkali metal hydroxide or alkali metal hydrosulfide (hereinafter referred to as the wetted part), for example, with the alkali metal hydroxide or alkali metal hydrosulfide in the storage tank (tank), piping and pump. For the wetted part, a material having excellent corrosion resistance such as titanium or zirconium on stainless steel and further subjected to corrosion resistance processing can be used, but in the present invention, stainless steel can be used as it is, and it is produced. It is preferable from the viewpoint of sex.

Since the present invention uses an alkali metal hydroxide or an alkali metal hydrosulfide which is less corrosive than an alkali sulfide as a sulfidizing agent, it is possible to suppress elution of metal atoms by using stainless steel as it is. Therefore, a special processing process for the sulfidizing agent supply device is not required, which is preferable from the viewpoint of simplifying the manufacturing equipment.

Specific examples of the alkali metal hydrosulfide used in the present invention include hydrates of alkali metal hydrosulfide, and examples of the alkali metal hydrosulfide include lithium hydrosulfide, sodium hydrosulfide, and potassium hydrosulfide. , Rubidium hydrosulfide, cesium hydrosulfide and the like. Each of these may be used alone, or two or more thereof may be mixed and used. Among these alkali metal hydrosulfides, sodium hydrosulfide and potassium hydrosulfide are preferable, and sodium hydrosulfide is particularly preferable. These alkali metal hydrosulfides can be used as anhydrides, hydrates, etc., and are particularly preferably used as liquid or solid hydrates having water of crystallization in the compound because of their availability. These alkali metal hydrosulfides can also be used as an aqueous solution because they are excellent in handleability when charged in the reaction system. The alkali metal hydrosulfide can also be obtained by reacting hydrogen sulfide with an alkali metal hydrosulfide, but those prepared in advance outside the reaction system may be used.

Specific examples of the alkali metal hydroxide used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Among these, lithium hydroxide, sodium hydroxide and potassium hydroxide are particularly preferable, and sodium hydroxide is particularly preferable. The alkali metal hydroxide is preferably used as an aqueous solution, and its concentration is preferably in the range of 10 to 50% by mass. The amount of the alkali metal hydroxide charged is preferably in the range of 0.5 to 1.2 mol, more preferably in the range of 0.6 to 1.1 mol, per 1 mol of the alkali metal hydrosulfide.

In step (2), a lithium salt compound may be added to the reaction system and the reaction may be carried out in the presence of lithium ions. Specific examples of the lithium salt compound that can be used here include lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium carbonate, lithium hydrogen carbonate, lithium sulfate, lithium hydrogen sulfate, lithium phosphate, and phosphoric acid. Lithium hydrogen hydrogen, lithium dihydrogen phosphate, lithium nitrite, lithium sulfite, lithium chlorate, lithium chromate, lithium molybdate, lithium formate, lithium acetate, lithium oxalate, lithium malonate, lithium propionate, lithium butyrate, iso Lithium butyrate, lithium maleate, lithium fumarate, lithium butane diate, lithium valerate, lithium hexanate, lithium octanate, lithium tartrate, lithium stearate, lithium oleate, lithium benzoate, lithium phthalate, benzenesulfonic acid Inorganic lithium salt compounds such as lithium, lithium p-toluenesulfonate, lithium sulfide, lithium hydroxide, lithium hydroxide; lithium methoxyd, lithium ethoxide, lithium poropoxide, lithium isopropoxide, lithium butoxide, lithium phenoxide, etc. Organic lithium salt compounds of. Among these, lithium chloride and lithium acetate are preferable, and lithium chloride is particularly preferable. Moreover, the said lithium salt compound can be used as an anhydride or a hydrous or an aqueous solution. When a lithium salt compound is added to the reaction system and the reaction is carried out in the presence of lithium ions, the amount charged is preferably 0.01 mol or more and 0.9 mol with respect to 1 mol of sulfur atom of the alkali metal hydrosulfide. It is preferable to use the polyarylene sulfide resin in a ratio of less than the range because the polyarylene sulfide resin can have a higher molecular weight.

The reaction conditions of the step (2) are not particularly limited, but are within a temperature at which the polymerization reaction can easily proceed, that is, in the range of 200 to 300 ° C., preferably 210 to 280 ° C., more preferably 215 to 260 ° C. It is preferable to react while dehydrating.

In the present invention, the introduction rate of the alkali metal hydrosulfide is set in the reaction system so that the amount of water in the reaction system is less than 1 mol with respect to 1 mol of sulfur atoms of the alkali metal hydrosulfide used for polymerization. It is preferable to adjust and control the amount of water in the reaction mixture so as to be removed from the reaction mixture.

The amount of water present in the polymerization reaction of the method for producing a polyarylene sulfide resin of the present invention tends to be as small as possible in order to avoid the occurrence of hydrolysis reaction, but on the other hand, the polymerization reaction is completely anhydrous. In the case of, there is a problem that the reaction speed becomes remarkably slow. Therefore, the amount of water that should be present in the reaction system in the polymerization reaction of the present invention is preferably less than 1 mol at the end of the polymerization reaction with respect to 1 mol of sulfur atoms of the alkali metal hydrosulfide used for the polymerization. Further, from the viewpoint that the reaction proceeds smoothly, it is preferable that 0.02 mol or more is present with respect to 1 mol of the sulfur atom of the alkali metal hydrosulfide used for the polymerization. Among these, the range of 0.03 to 0.60 mol is preferable, and the range of 0.05 to 0.50 is particularly preferable with respect to 1 mol of the sulfur atom of the alkali metal hydrosulfide used for the polymerization. When the above range is satisfied, both controllability of the reaction rate and high molecular weight can be more easily achieved.

In the production method of the present invention, it is preferable that the above-mentioned water content is satisfied at the end of polymerization, but it more preferably exceeds 60 mol% after the conversion rate of the polyhalo aromatic compound exceeds 80 mol%. It is preferable that the above range is satisfied from the time point onward, more preferably immediately after the start of polymerization.

Here, the conversion rate of the polyhalo aromatic compound is expressed by the following formula.
Conversion rate (%) = (charged amount-residual amount) / charged amount x 100
However, the "charged amount" represents the mass of the polyhaloaromatic compound charged in the reaction system, and the "residual amount" represents the mass of the polyhaloaromatic compound remaining in the reaction system.

Further, in the step (2), the dehydration method for maintaining the water content in the system is not particularly limited, and the temperature and pressure of the reaction system are controlled in addition to the introduction rate of the sulfide agent. Although this can be done, specifically, the temperature and pressure to be controlled are estimated from the vapor pressure curves of water, the solvent, and the polyhalo aromatic compound, and the desired in-system moisture is set by setting the pressure and temperature conditions. You can adjust the amount.

The reaction mixture containing the polyarylene sulfide resin obtained by the polymerization reaction can be subjected to a post-treatment step. The post-treatment step may be any known method and is not particularly limited. For example, after the polymerization reaction is completed, the reaction mixture is first used as it is, or after adding an acid or a base, the pressure is reduced or the pressure is normal. Then, the solid after distilling off the solvent is washed once or twice or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, and further neutralized, washed with water, filtered and dried, or After completion of the polymerization reaction, the reaction mixture is mixed with a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons (soluble in the polymerization solvent used and A method in which a solvent that is a poor solvent for at least a polyarylene sulfide resin) is added as a precipitant to precipitate solid products such as a polyarylene sulfide resin and an inorganic salt, and these are filtered off, washed, and dried. Alternatively, after completion of the polymerization reaction, a reaction solvent (or an organic solvent having the same solubility as that of the low molecular weight polymer) is added to the reaction mixture, and the mixture is stirred and then filtered to remove the low molecular weight polymer. Examples thereof include a method of washing once or twice or more with a solvent such as acetone, methyl ethyl ketone and alcohols, and then neutralizing, washing with water, filtering and drying.
In the post-treatment method as exemplified above, the polyarylene sulfide resin may be dried in vacuum, in air, or in an atmosphere of an inert gas such as nitrogen.

The polyarylene sulfide resin thus obtained can be used as it is for various molding materials and the like, but it may be subjected to heat treatment in air or oxygen-enriched air or under reduced pressure conditions to be oxidatively crosslinked. The temperature of this heat treatment is preferably in the range of 180 ° C. to 270 ° C., although it varies depending on the target crosslinking treatment time and the treatment atmosphere. Further, the heat treatment may be performed in a state where the polyarylene sulfide resin is melted at a temperature equal to or higher than the melting point of the polyarylene sulfide resin using an extruder or the like, but the melting point is increased because the possibility of thermal deterioration of the polyarylene sulfide resin is increased. It is preferably performed at plus 100 ° C. or lower.

The polyarylene sulfide resin obtained by the production method of the present invention described in detail above has been subjected to various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding to obtain heat resistance, molding processability, dimensional stability and the like. It can be processed into an excellent molded product.

Further, the polyarylene sulfide resin obtained by the present invention can be used as a polyarylene sulfide resin composition in combination with various fillers in order to further improve performance such as strength, heat resistance and dimensional stability. .. The filler is not particularly limited, and examples thereof include a fibrous filler and an inorganic filler. Examples of the fibrous filler include glass fibers, carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, potassium titanate, silicon carbide, calcium sulfate, calcium silicate and other fibers, and natural fibers such as wollastonite. Can be used. Examples of the inorganic filler include barium sulfate, calcium sulfate, clay, biloferrite, bentonite, sericite, zeolite, mica, mica, talc, attalpargit, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads and the like. Can be used. Further, various additives such as a mold release agent, a colorant, a heat-resistant stabilizer, an ultraviolet stabilizer, a foaming agent, a rust preventive, a flame retardant, and a lubricant can be contained as additives in the molding process.

Further, the polyarylene sulfide resin obtained by the present invention can be appropriately used as polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulphon, polyethersulphon, polyetheretherketone, or polyether, depending on the intended use. Synthetic resin such as ketone, polyarylene, polyethylene, polypropylene, polytetrafluorinated ethylene, polydifluorinated ethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, liquid crystal polymer, or polyolefin rubber , A polyarylene sulfide resin composition containing an elastomer such as fluororubber and silicone rubber may be used.

The polyarylene sulfide resin obtained by the production method of the present invention also has various performances such as heat resistance and dimensional stability inherent in the polyarylene sulfide resin. Therefore, for example, a connector, a printed substrate, a sealed molded product, etc. Electrical / electronic parts, automobile parts such as lamp reflectors and various electrical component parts, interior materials such as various buildings, aircraft and automobiles, or injection molding of precision parts such as OA equipment parts, camera parts and watch parts. It is widely useful as a material for various molding processes such as compression molding, extrusion molding of composites, sheets, pipes, etc., or pultrusion molding, or as a material for fibers or films.

The present invention will be specifically described below with reference to examples. These examples are exemplary and not limiting.

(Measurement of melt viscosity of PPS resin)
The value measured after holding the manufactured PPS resin for 6 minutes using a Shimadzu flow tester, CFT-500C, under the conditions of 300 ° C., load: 1.96 × 10 ⁶ Pa, L / D = 10/1. Was defined as the melt viscosity (V6), and the value measured after holding for 15 minutes under the same conditions was defined as the melt viscosity (V15).

(Quantification of carboxy group of PPS resin)
After pressing the quantification of the carboxy group of the PPS resin at 350 ° C., a film showing amorphousness is prepared by quenching, and the measurement is performed with a Fourier transform infrared spectroscope (hereinafter abbreviated as "FT-IR device"). did. It determined the relative intensity of the absorption of 1705 cm ^-1 for absorption of 630.6Cm ^-1 of infrared absorption spectrum, additional content of carboxyl group in the measurement sample using a calibration curve prepared by the method described later (hereinafter "carboxy Abbreviated as "total content of groups"). The content of the carboxy group is represented by the number of moles in 1 g of the resin composition, and the unit thereof is represented by μmol / g. The method for preparing the calibration curve is to add a predetermined amount of 4-chlorophenylacetic acid to 3 g of PPS resin containing a carboxylate at the end of the molecule without performing acid treatment, mix well, and then prepare a film in the same manner as described above. Measurement was performed with an FT-IR device, and a calibration curve was prepared by plotting the relative intensity ratio of the absorption to the carboxy group content. The higher the content of the carboxy group in the PPS resin, the better the reactivity with the impact resistance modifier such as the epoxy silane coupling agent and the functional group-containing thermoplastic elastomer. Therefore, the composition has excellent impact resistance. Is obtained.

(Method for quantifying CP-MABA)
Add 100 g of ion-exchanged water at 70 ° C. and 1 wt% aqueous sodium hydroxide solution to 50 g of the slurry of the polymerization mixture containing PPS resin, adjust the pH to 10.0 or higher, stir for 10 minutes, filter, and then filter. The cake was washed by adding 100 g of ion-exchanged water at 70 ° C. to the cake. This operation was repeated 3 times, and the total amount of the filtrate was collected and the amount of CP-MABA extracted by HPLC was measured. The concentration in the extract was determined from the peak area with the same retention time as the standard sample and the calibration curve, and the CP-MABA content per 1 g of PPS resin was calculated.

(Reactivity evaluation method)
After crushing the PPS resin with a small crusher, it was sieved using a test sieve having a mesh size of 0.5 mm according to Japanese Industrial Standard Z8801. 0.5 part by mass of 3-glycidoxypropyltrimethoxysilane was added to 100 parts by mass of the PPS resin that had passed through the sieve, and the mixture was uniformly mixed, and then the melt viscosity V15 was measured. The degree of increase in viscosity was calculated as a magnification from the ratio of the melt viscosity V15 after the addition / the melt viscosity V6 before the addition. The larger the degree of increase in viscosity, the higher the reactivity and the better.

[Example 1]
(Step 1)
A stainless steel (SUS) sodium hydrosulfide and sodium hydroxide aqueous solution storage tank, piping, and pump in a 2-liter autoclave with a titanium lining with stirring blades equipped with a thermometer (not shown) and a pressure gauge (not shown). , And separately, a polymerization reaction was carried out using a reactor in which a condenser and a decanter were connected. First, 974 g of NMP and 432.18 g of DCB were charged into the autoclave, sealed, and heated to an internal temperature of 220 ° C. over 2 hours under a nitrogen atmosphere while stirring. After reaching 220 ° C., the valve (not shown) to which the capacitor was connected was opened, and the pressure inside the hook was adjusted to 0.20 MPa.

Next, while maintaining the internal temperature at 220 ° C. and the internal pressure at 0.20 MPa, 390.55 g (NaSH 3.36 mol) of 48.23 mass% NaOH aqueous solution and 214.38 g of 48.80 mass% NaOH aqueous solution (214.38 g). (2.62 mol) of NaOH was independently charged into the storage tank, and each of them was dropped over 4 hours while adjusting the pressure with a pump through each pipe. During the dropping, a dehydration operation was performed at the same time, and the distilled vapor of mixed p-DCB and water was condensed by a condenser, separated by a decanter, and the p-DCB was returned to the autoclave. After completion of the dropping, the valve was closed, the autoclave was sealed, and the mixture was held for 1 hour. After holding for 1 hour, the valve to which the condenser was connected was opened again, and the residual water was removed in 10 minutes until the pressure inside the kettle reached 0.07 MPa. The amount of distilled water was 363 g, and the amount of hydrogen sulfide scattered outside the system (scattered S) was 16 g. Then, the temperature was raised to an internal temperature of 230 ° C. over 20 minutes, and the temperature was maintained at 230 ° C. for 3 hours. The pressure in the final pot was 0.09 MPa. After completion of the reaction, the mixture was cooled to room temperature to obtain a polymerized slurry. The amount of water in the reaction system at the end of the reaction was 0.46 mol per mol of sulfur atoms present in the autoclave.

400 g of ion-exchanged water at 70 ° C. was added to 100 g of the obtained polymer slurry and stirred for 10 minutes, filtered, and 600 g of ion-exchanged water at 70 ° C. was added to the filtered cake to wash the cake. After adding 400 g of ion-exchanged water at 70 ° C. to the obtained hydrous cake and stirring for 10 minutes, the cake was filtered, and 600 g of ion-exchanged water at 70 ° C. was added to the filtered cake to wash the cake. This operation was repeated twice. To the obtained hydrous cake, 400 g of ion-exchanged water at 70 ° C. and acetic acid were added to adjust the pH to 4.0, and the cake was stirred for 10 minutes, filtered, and 600 g of ion-exchanged water at 70 ° C. was added to the filtered cake. The cake was washed. After adding 400 g of ion-exchanged water at 70 ° C. to the obtained hydrous cake and stirring for 10 minutes, the cake was filtered, and 600 g of ion-exchanged water at 70 ° C. was added to the filtered cake to wash the cake. The obtained hydrous cake was dried at 120 ° C. for 4 hours using a hot air dryer to obtain a white powdery polymer. The melt viscosity of the obtained polymer was 132 Pa · s, the carboxy group content was 38 μmol / g, the CP-MABA production amount was 38 μmol / g, and the reactivity was 6 times.

(Comparative Example 1)
Except for changing the solution added dropwise to 38.41 wt% Na ₂ S aqueous solution 609.50g _(Na 2 S3.00 mol) was subjected to the same procedure as in Example 1. The amount of distilled water was 356 g, and the amount of hydrogen sulfide scattered outside the system (scattered S) was 15 g. The pressure in the final pot was 0.10 MPa. The amount of water in the reaction system at the end of the reaction was 0.49 mol per mol of sulfur atoms present in the autoclave. The melt viscosity of the obtained polymer was 21 Pa · s, the carboxy group content was 10 μmol / g, the CP-MABA production amount was 16 μmol / g, and the reactivity was 1.0 times.

(Comparative Example 2)
Using the same reactor as in Example 1, 487 g of NMP and 18.29 g (0.225 mol) of 49.21 mass% NaOH aqueous solution were charged in an autoclave, and the temperature was raised to 100 ° C. over 20 minutes under a nitrogen atmosphere while stirring. After warming, the system was closed, the temperature was further raised to 220 ° C. over 40 minutes, and the temperature was maintained at 220 ° C. for 2 hours. The final gauge pressure was 0.27 MPa.

Next, the valve to which the capacitor was connected was opened, and the gauge pressure was adjusted to 0.20 MPa. Next, while maintaining the internal temperature at 220 ° C. and the gauge pressure at 0.20 MPa, 178.04 g (1.500 mol) of the 47.23 mass% NaOH aqueous solution and 98.76 g (1.) of the 49.21 mass% NaOH aqueous solution. 215 mol) and 220.5 g (1.5 mol) of p-DCB were added dropwise over 3 hours. During the dropping, a dehydration operation was performed at the same time, and the distilled vapor of mixed p-DCB and water was condensed by a condenser, separated by a decanter, and the p-DCB was returned to the autoclave. After the dripping was completed, the valve was closed and the autoclave was sealed. The amount of distilled water was 174 g, and the amount of hydrogen sulfide scattered outside the system was 1 g. Then, the temperature was raised to an internal temperature of 230 ° C. over 10 minutes, and the temperature was maintained at 230 ° C. for 3 hours. The final gauge pressure was 0.28 MPa. After completion of the reaction, the mixture was cooled to room temperature to obtain a polymerized slurry. The amount of water in the reaction system at the end of the reaction was 0.20 mol per mol of sulfur atoms present in the autoclave.

The obtained polymer slurry was subjected to the same operation as in Example 1 to obtain a polymer. The melt viscosity of the obtained polymer was 43 Pa · s, the terminal carboxy group content was 8 μmol / g, the CP-MABA production amount was 62 μmol / g, and the reactivity was 1.1 times.

1 Reaction vessel 2 Stirring blade 3 Piping for supplying alkali metal hydrosulfide (sodium hydroxide) to the reaction vessel 4 Pump for supplying alkali metal hydrosulfide (sodium hydroxide) to the reaction vessel 5 Alkali metal water Storage tank for sulfide (sodium hydroxide) 6 Piping for supplying alkali metal hydroxide (sodium hydroxide) to the reaction vessel 7 Pump for supplying alkali metal hydroxide (sodium hydroxide) to the reaction vessel 8 Alkali metal hydroxide (sodium hydroxide) storage tank 9 rectification tower 10 Condenser (condenser)
11 Decanter for statically separating the liquid component from the condenser 12 Reflux pump that returns the liquid in the lower layer of the decanter to the rectification tower 13 Pressure control valve that adjusts the pressure of the gas component inside the rectification tower and the condenser 14 Scattered Hydrogen sulfide recovery device

Claims (4)

In a reaction vessel containing an aliphatic cyclic compound and polyhalo aromatic compounds, alkali metal hydroxide, which is stored in the storage bath of A alkali metal hydrosulfide oxides was fed to the reaction vessel through the piping, and A alkali A method for producing a polyarylene sulfide resin in which an alkali metal hydrosulfide stored in a metal hydrosulfide storage tank is supplied to a reaction vessel through a pipe and subjected to a polymerization reaction.
A method for producing a polyarylene sulfide resin, wherein the wetted portion with the alkali metal hydroxide and the wetted portion with the alkali metal hydrosulfide in the reactor are each made of stainless steel. The method for producing a polyarylene sulfide resin according to claim 1, wherein the amount of the aliphatic cyclic compound charged is in the range of 1.0 to 6.0 mol per mol of sulfur atoms in the alkali metal hydrosulfide. The method for producing a polyarylene sulfide resin according to claim 1 or 2, wherein the amount of the polyhalo aromatic compound charged is in the range of 0.7 mol to 1.2 mol per 1 mol of sulfur atom of the alkali metal hydrosulfide. The polyarylene sulfide according to any one of claims 1 to 3, wherein the amount of the alkali metal hydroxide charged is in the range of 0.5 to 1.2 mol per 1 mol of sulfur atom of the alkali metal hydrosulfide. Resin manufacturing method.

Images