Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/0204—Polyarylenethioethers
  • C08G75/025—Preparatory processes
  • C08G75/0254—Preparatory processes using metal sulfides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/14—Polysulfides
  • C08G75/16—Polysulfides by polycondensation of organic compounds with inorganic polysulfides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/14—Polysulfides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/02—Polythioethers; Polythioether-ethers

Definitions

• the present invention relates to a highly efficient method for producing a linear high molecular weight polyarylene sulfide resin.
• a polyarylene sulfide resin (hereinafter abbreviated as “PAS resin”) represented by polyphenylene sulfide resin (hereinafter abbreviated as “PPS resin”) is excellent in heat resistance, chemical resistance and the like. Widely used in electrical and electronic parts, automotive parts, water heater parts, textiles, film applications, etc. In these applications, high molecular weight PAS resins have recently been widely used because of their high strength and excellent moldability. However, since a high molecular weight PAS resin is usually made into a high molecular weight by synthesizing a low molecular weight PAS resin and then thermally oxidized and cross-linked, the resulting high molecular weight PAS resin is difficult to be melt-extruded and used. It was limited.
• PAS resin for example, hydrated alkali metal sulfide, less than 1 mol of N-methylpyrrolidone per mol of hydrated alkali metal sulfide, and polyhaloaromatic compound are used.
• the mixture is mixed and subjected to azeotropic dehydration to obtain a slurry-like composition containing fine particulate anhydrous alkali metal sulfide, and then heated to polymerize the PAS resin with high production efficiency.
• a method for producing a molecular PAS resin is known (for example, see Patent Document 1).
• the above-mentioned method can suppress side reactions and can efficiently produce a linear high molecular weight PAS resin, in order to polymerize by a heterogeneous reaction in which raw material components are reacted in a slurry state, the reaction system Moisture such as a small amount of crystal water remaining inside induces a side reaction and does not reach the level of high molecular weight required in recent years.
• an alkali metal sulfide and a dihaloaromatic compound are reacted by heating in an organic amide solvent to produce a PAS resin, an anhydrous alkali metal having a purity of 95% or more and an alkali metal hydrosulfide content of 2% by mass or less
• a manufacturing method has been proposed (see, for example, Patent Document 2).
• the PAS resin production method using the anhydrous alkali metal sulfide does not proceed as it is because the anhydrous alkali metal sulfide is a solid. Therefore, it is necessary to dissolve the solid anhydrous alkali metal sulfide and supply it as a sulfidizing agent into the reaction system.
• water is added to promote dissolution of the solid anhydrous alkali metal sulfide.
• this water has a problem that it is difficult to induce a side reaction and to increase the molecular weight.
• the problem to be solved by the present invention is to provide a method for producing a polyarylene sulfide resin which has high productivity on an industrial scale and can significantly increase the molecular weight of the obtained PAS resin.
• the present inventors have reacted polyhaloaromatic compounds, alkali metal hydrosulfides and organic acid alkali metal salts to produce polyarylene sulfide resins. It is carried out in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, and the amount of the organic acid alkali metal salt is determined according to the amount of sulfur atoms present in the reaction system, that is, solid alkali metal sulfide and alkali metal water.
• the PAS resin can be made to have a higher molecular weight than conventional by controlling to a certain range with respect to the total number of moles of sulfides and reacting with the water existing in the reaction system below a certain amount, The present invention has been completed.
• the present invention provides a polyhaloaromatic compound (a), an alkali metal hydrosulfide (b) and an organic acid alkali metal salt (c) in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent.
• the polyarylene sulfide is characterized in that it is used at a ratio of 0.9 mol or less and the water content existing in the reaction system is reacted at 0.02 mol or less with respect to 1 mol of the aprotic polar organic solvent.
• a method for producing a resin is provided.
• the method for producing a polyarylene sulfide resin according to the present invention comprises a polyhaloaromatic compound (a), an alkali metal hydrosulfide (b), and an organic acid alkali in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent.
• the polyhaloaromatic compound (a), the alkali metal hydrosulfide (b), and the organic acid alkali metal salt (c) are reacted in the presence of the solid alkali metal sulfide and the aprotic polar organic solvent as described above.
• the amount of the organic acid alkali metal salt (c) to the amount of sulfur atoms present in the reaction system, that is, the total amount of the solid alkali metal sulfide and alkali metal hydrosulfide (b) is 1 mol.
• the alkali metal salt (c) is controlled so as to have a ratio of 0.01 mol or more and less than 0.9 mol, and the sulfidizing agent is reacted by reacting in a state where the water content in the reaction system is reduced as much as possible
• the “water content existing in the reaction system” refers to the total amount of water actually present in the reaction system as crystal water, H 2 O, etc., out of the total water content in the reaction system.
• the proportion of the organic acid alkali metal salt (c) in the reaction system is 0.01 mol or more and less than 0.9 mol with respect to 1 mol of sulfur atoms present in the reaction system, In particular, the range of 0.04 to 0.4 mol is preferable in that the effect of suppressing side reactions becomes remarkable.
• the organic acid alkali metal salt (c) is specifically an alkali metal salt of a lower fatty acid such as formic acid, acetic acid or propionic acid; an alkali of an aminocarboxylic acid such as glycine, alanine, glutamic acid or 4-aminobutyric acid.
• a lower fatty acid such as formic acid, acetic acid or propionic acid
• an alkali of an aminocarboxylic acid such as glycine, alanine, glutamic acid or 4-aminobutyric acid.
• NMP N-methyl-2-pyrrolidone
• NMP N-cyclohexyl-2-pyrrolidone
• 2-pyrrolidone 1,3-dimethyl-2-imidazolidinone
• ⁇ -caprolactam N -An alkali metal salt of a hydrolyzate of an aliphatic cyclic compound that can be opened by hydrolysis of an aliphatic cyclic amide compound such as methyl- ⁇ -caprolactam, or a sulfolane such as sulfolane or dimethylsulfolane.
• the alkali metal salt include lithium salt, sodium salt, potassium salt, rubidium salt, and cesium salt.
• These organic acid alkali metal salts (c) are preferably used so as to be liquid in the reaction system.
• the alkali metal salt (c2) of the hydrolyzate of the aliphatic cyclic compound (c1) is preferable from the viewpoint of good reactivity.
• An alkali metal salt of a ring-opened product, particularly an alkali metal salt of a hydrolyzate of N-methyl-2-pyrrolidone is preferable from the viewpoint of reactivity.
• These alkali metal salts are preferably used as lithium salts and sodium salts, and sodium salts are particularly preferable.
• aprotic polar organic solvent examples include NMP, N-cyclohexyl-2-pyrrolidone, N-methyl- ⁇ -caprolactam, formamide, acetamide, N-methylformamide, N, N-dimethylacetamide, 2-pyrrolidone, ⁇ -caprolactam, hexamethylphosphoramide, tetramethylurea, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone amidourea, and lactams; sulfolanes such as sulfolane and dimethylsulfolane; benzo Examples thereof include nitriles such as nitrile; ketones such as methyl phenyl ketone and mixtures thereof.
• NMP is particularly preferable from the viewpoint of improving the reactivity of the sulfiding agent.
• a more specific production process includes a method through the following processes 1 to 3.
• Step 1 In the presence of a non-hydrolyzable organic solvent, Hydrous alkali metal sulfide, or Hydrous alkali metal hydrosulfide and alkali metal hydroxide; A step of producing a slurry (I) containing a solid alkali metal sulfide by reacting an aliphatic cyclic compound (c1) that can be ring-opened by hydrolysis with dehydration, Step 2: After the production of the slurry (I), a step of further adding an aprotic polar organic solvent, distilling off water to perform dehydration, Step 3: Next, in the slurry (I) obtained through the dehydration step of Step 2, the polyhaloaromatic compound (a), the alkali metal hydrosulfide (b), and the hydrolyzate of the compound (c1) A step of polymerizing the alkali metal salt (c2) of 1 mol of the aprotic polar organic solvent with a water content existing in the reaction system of 0.02 mol or less.
• Step 1 includes a hydrous alkali metal sulfide, or a hydrous alkali metal hydrosulfide and an alkali metal hydroxide, an aliphatic cyclic compound (c1) that can be ring-opened by hydrolysis, a non-hydrolyzable organic solvent, Is a step of producing slurry (I) by reacting while dehydrating.
• the hydrous alkali metal sulfide and the aliphatic cyclic compound (c1) capable of ring opening by hydrolysis are reacted in the presence of a non-hydrolyzable organic solvent while dehydrating,
• the aliphatic cyclic compound (c1) that can be opened by hydrolysis is reacted with dehydration to form a slurry (I) in which solid alkali metal sulfide is dispersed in a non-hydrolyzable organic solvent. It is a process.
• the alkali metal hydrosulfide (b) and the alkali metal salt (c2) of the hydrolyzate of the compound (c1) co
• Examples of the hydrated alkali metal sulfide used herein include liquid or solid hydrates of compounds such as lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and the solid content concentration thereof is 10 to 80% by mass. In particular, the content is preferably 35 to 65% by mass.
• a sodium sulfide hydrate is preferable from the viewpoint of reactivity.
• water-containing alkali metal sulfide is used as the sulfur source, in addition to the water-containing alkali metal sulfide, addition of an alkali metal hydroxide to perform dehydration further promotes the production of solid alkali metal sulfide. This is preferable.
• the hydrated alkali metal hydrosulfide includes, for example, liquid or solid hydrates of compounds such as lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, and cesium hydrosulfide. Is preferably 10 to 80% by mass. Among these, hydrated lithium hydrosulfide and hydrated sodium hydrosulfide are preferable, and hydrated sodium hydrosulfide is particularly preferable.
• examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and aqueous solutions thereof.
• this aqueous solution it is preferable that it is an aqueous solution with a density
• lithium hydroxide, sodium hydroxide, and potassium hydroxide are particularly preferable, and sodium hydroxide is particularly preferable.
• the amount of alkali metal hydroxide used is preferably in the range of 0.8 to 1.2 mol per mol of alkali metal hydrosulfide (b) from the viewpoint of promoting the formation of solid alkali metal sulfide. In particular, the range of 0.9 to 1.1 mol is more preferable.
• the method of performing the dehydration process in Step 1 includes the following methods.
• Method 1-A A predetermined amount of the aliphatic cyclic compound (c1) that can be ring-opened by hydrolysis, a non-hydrolyzable organic solvent, a hydrous alkali metal sulfide, and, if necessary, the alkali metal hydrosulfide or alkali metal hydroxide.
• the reaction vessel is charged and heated to a temperature above the boiling point of the hydrated alkali metal sulfide and to the temperature at which water is removed azeotropically, specifically in the range of 80 to 220 ° C, preferably in the range of 100 to 200 ° C. To dehydrate.
• Method 1-B A predetermined amount of an aliphatic cyclic compound (c1) that can be opened by hydrolysis, a non-hydrolyzable organic solvent, a hydrous alkali hydrosulfide, and an alkali metal hydroxide is charged into a reaction vessel, and water is contained almost simultaneously with the charging. After the alkali metal sulfide is formed, the temperature is equal to or higher than the boiling point of the hydrated alkali metal sulfide and the water is removed by azeotropy, specifically in the range of 80 to 220 ° C, preferably 100 to 200 ° C. The method of dehydrating by heating to the range.
• azeotropic distillation of water and non-hydrolyzable organic solvent is separated with a decanter, and only the non-hydrolyzable organic solvent is returned to the reaction system or azeotropic distillation is performed.
• An additional amount of the non-hydrolyzable organic solvent corresponding to the amount that has been added may be added, or an excess of the non-hydrolyzable organic solvent that is azeotropically distilled off or more may be charged in advance.
• the method 1-B is particularly preferable because the slurry can be easily adjusted and the effects of the present invention become remarkable.
• the reaction system in the initial stage of dehydration consists of two layers of an organic layer and an aqueous layer.
• anhydrous alkali metal sulfide precipitates in the form of fine particles, resulting in a non-hydrolyzable organic layer. Disperse uniformly in the solvent. Further, dehydration is continued until almost all of the aliphatic cyclic compound (c1) that can be opened by hydrolysis in the reaction system is hydrolyzed.
• step 1 of the present invention water is discharged out of the reaction system by dehydration treatment, and the aliphatic cyclic compound (c1) that can be ring-opened by hydrolysis is hydrolyzed, and at the same time, an anhydrous solid alkali metal This is a step of depositing sulfide. Therefore, if excessive water is present in the reaction system after dehydration, a large amount of by-products are generated in the subsequent polymerization step, and a growth end-stopping reaction is induced to increase the molecular weight of the target PAS resin. There is a problem that is easily disturbed.
• the total water content in the reaction system after the dehydration treatment in Step 1 is as small as possible.
• the hydrated alkali metal sulfide (Method 1-A) or hydrated alkali hydrosulfide used in Step 1 is used.
• Method 1-B Moisture amount per mole, that is, per mole of sulfur atoms in the reaction system is in the range of more than 0.1 mole and not more than 0.99 mole, preferably 0
• the amount of water is preferably 6 to 0.96 mol.
• total amount of water in the reaction system means water consumed for hydrolysis of the compound (c1), crystal water remaining in a trace amount in the solid alkali metal sulfide, and other water present in the reaction system. Is the total mass of all.
• the amount of water in the reaction system after the dehydration treatment in step 1 is more than 0.1 mole and less than or equal to 0.99 mole per mole of sulfur atoms in the reaction system as described above, in particular, The range is 0.6 to 0.96 mol, and the amount of water existing in the reaction system is 0.03 to 0.11 mol per mol of sulfur atoms in the reaction system. Is preferred.
• the amount of water existing in the reaction system means water excluding the water consumed for hydrolysis of the compound (c1) out of the total amount of water in the reaction system, that is, crystal water, H 2. O or the like refers to the total amount of moisture actually present in the reaction system (hereinafter referred to as “crystal water or the like”).
• Step 1 the reaction in Step 1 can be expressed by, for example, the following formula (1).
• Step 1 water generated as a by-product when the solid alkali metal sulfide is formed is removed from the system, and the aliphatic cyclic compound (c1) is hydrolyzed, and at the same time, the alkali metal hydrosulfide.
• Step 2 water generated as a by-product when the solid alkali metal sulfide is formed is removed from the system, and the aliphatic cyclic compound (c1) is hydrolyzed, and at the same time, the alkali metal hydrosulfide.
• Step 2 water generated as a by-product when the solid alkali metal sulfide is formed is removed from the system, and the aliphatic cyclic compound (c1) is hydrolyzed, and at the same time, the alkali metal hydrosulfide.
• x and y represent a number where (x + y) satisfies 0.1 to 30, z represents a number of 0.01 or more and less than 0.9, and M represents an alkali metal atom.
• X represents the compound (c1), and X ′ represents a hydrolyzate thereof.
• step 1 the amount of the alkali metal sulfide and the amount of the alkali metal hydrosulfide (b), which are solids in the reaction system, are adjusted by adjusting the amount of the aliphatic cyclic compound (c1) charged. can do.
• the alkali metal sulfide is present in the form of a slurry in the form of a solid, and then the remaining crystal water is extracted into the solution by further adding an aprotic polar organic solvent in Step 2, followed by dehydration treatment,
• the amount of the alkali metal salt of the hydrolyzate of the aliphatic cyclic compound (c1) can be reduced by performing the heterogeneous reaction in the slurry state in Step 3, and the side reaction during the polymerization of the PAS resin can be performed. It is characterized by being able to suppress and increase the molecular weight.
• the charged amount of the aliphatic cyclic compound (c1) in Step 1 is 0 with respect to 1 mol of the hydrated alkali metal hydrosulfide (Method 1-A) or the hydrated alkali metal hydrosulfide (Method 1-B). It is preferably used at a ratio of 0.01 mole or more and less than 0.9 mole. In particular, 0.04 to 0.4 mol with respect to 1 mol of the hydrated alkali metal hydrosulfide (Method 1-A) or the hydrated alkali metal hydrosulfide (Method 1-B) from the point that such an effect becomes remarkable. It is preferable to use in the ratio which becomes.
• Step 2 the aprotic polar organic solvent used in Step 2 may be the same as described above.
• the alkali metal salt of the hydrolyzate of the aliphatic cyclic compound (c1) may be a lithium salt, sodium salt, potassium salt, rubidium salt or cesium salt of the hydrolyzate of the aliphatic cyclic compound (c1). Is mentioned.
• These organic acid alkali metal salts (c2) are preferably in a liquid state in the reaction system.
• the alkali metal salt (c2) of the hydrolyzate of the aliphatic cyclic compound (c1) is preferable from the viewpoint of good reactivity, and the aliphatic cyclic amide compound.
• An alkali metal salt of a ring-opened product, particularly an alkali metal salt of a hydrolyzate of NMP is preferable from the viewpoint of reactivity.
• These alkali metal salts are preferably used as lithium salts and sodium ion salts.
• non-hydrolyzable organic solvent used in step 1 may be any organic solvent inert to water as described above, and for example, general-purpose aliphatic hydrocarbons, aromatic hydrocarbons, etc. are used.
• the use of the polyhaloaromatic compound (a) subjected to the reaction in Step 3 as the organic solvent makes the reaction or polymerization in the next Step 3 good and the production efficiency is drastically improved. It is preferable from the point which improves to.
• polyhaloaromatic compound (a) used herein examples 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-dihalonaphthalene 1-methoxy-2,5-dihalobenzene, 4,4′-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalo Nitrobenzene, 2,4-dihaloanisole, p, p'-dihalodiphenyl ether, 4,4'-di
• a bifunctional dihaloaromatic compound is preferable and particularly finally obtained because the present invention can efficiently produce a linear high molecular weight PAS resin.
• PAS resin From the viewpoint of good mechanical strength and moldability of the PAS resin, p-dichlorobenzene, m-dichlorobenzene, 4,4′-dichlorobenzophenone and 4,4′-dichlorodiphenyl sulfone are preferable, and p-dichlorobenzene is particularly preferable. preferable.
• 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, or 1 3,5-trihalobenzene is preferably used in combination.
• the amount of the non-hydrolyzable organic solvent used is not particularly limited, but is preferably an amount that provides good fluidity of the slurry (I) obtained in Step 1.
• the polyhaloaromatic compound (a) is used as the non-hydrolyzable organic solvent
• the hydrated alkali metal sulfide (Method 1-A) or the hydrated alkaline water is used because of excellent reactivity and polymerizability in Step 2.
• a range of 0.2 to 5.0 moles per mole of sulfide (Method 1-B) is preferred, and a range of 0.3 to 2.0 moles is particularly preferred.
• the polyhaloaromatic compound (a) can be used as it is in the subsequent production process of the PAS resin, and may be additionally used if necessary in the subsequent production process of the PAS resin. May be used in a reduced form.
• a copolymer containing two or more different reactive units can be obtained by appropriately selecting and combining the polyhaloaromatic compounds (a).
• a polyhaloaromatic compounds
• p-dichlorobenzene and 4,4′-dichlorobenzophenone it is particularly preferable to use 4,4′-dichlorodiphenylsulfone in combination since polyarylene sulfide having excellent heat resistance can be obtained.
• the aprotic polar organic solvent is further added to the slurry (I) obtained in the step 1, the water is distilled off, and the aprotic polar organic present in the reaction system at the start of the step 3
• dehydration is performed until the amount of water existing in the reaction system is 0.02 mol or less per 1 mol of the solvent.
• the water distilled off in this step 2 is crystal water that could not be removed in step 1.
• the amount of water existing in the reaction system is the amount of crystal water and the like existing in the reaction system as described above.
• the slurry (I) usually contains water of crystallization in a ratio of 0.03 to 0.11 mole per mole of sulfur atoms in the reaction system.
• the process is to reduce the content of crystal water and the like in the reaction system as much as possible.
• Step 3 When water such as crystal water is present in the reaction system in Step 3, the solid alkali metal sulfide is dissociated into alkali metal hydrosulfide and alkali metal hydroxide, and the alkali metal hydroxide and polyhaloaromatic compound (There is a problem of inducing a phenol-based growth terminal termination reaction caused by a side reaction with a) or a side reaction between an alkali metal hydroxide and a polymer end group halogen (see the following formula (2)).
• Step 2 when an aliphatic cyclic compound (c1) that can be ring-opened by hydrolysis is added as an aprotic polar organic solvent, the aliphatic cyclic compound is added by water existing in the reaction system.
• the water of crystallization that cannot be dehydrated in Step 1 and remains in the reaction system is extracted into the solution, and the water of crystallization is reduced as much as possible by the subsequent dehydration treatment. It becomes possible.
• aprotic polar organic solvent present in the reaction system at the start of Step 3 with a water content existing in the reaction system of 0.02 mol or less, alkali metal hydroxide and polyhaloaromatic
• a high molecular weight product can be obtained by suppressing a side reaction with the compound (a) or a phenol-based growth end-stopping reaction caused by a side reaction between an alkali metal hydroxide and a polymer terminal group halogen.
• the dehydration treatment in the step 2 is more preferably performed after the slurry (I) is formed in the step 1, and more preferably the abundance of crystal water and the like in the slurry (I) is the sulfur atom 1 in the reaction system.
• an aprotic polar organic solvent is added to the reaction system to perform dehydration.
• the amount of the aprotic polar organic solvent added is 0.5 to 5 moles per mole of sulfur atoms present in the reaction system. This is preferable because the crystal water and the like can be efficiently extracted into the solution.
• the dehydration treatment in step 2 is usually performed under conditions of a temperature of 180 to 220 ° C.
• a gauge pressure of 0.0 to 0.1 MPa particularly a temperature of 180 to 200 ° C. and a gauge pressure of 0.0 to 0.05 MPa.
• a mixture of an aprotic polar organic solvent and water is isolated by distillation under the temperature and pressure conditions described above, and this mixed vapor is condensed with a condenser, separated with a decanter, etc.
• a method of returning the aromatic compound (a) into the reaction system can be mentioned.
• the amount of water existing in the reaction system at the start of the step 3 is 0.02 mol or less with respect to 1 mol of the aprotic polar organic solvent in the reaction system.
• the amount of water present in the reaction system at the start of Step 3 is preferably 0.02 mol or less with respect to 1 mol of the aprotic polar organic solvent in the reaction system.
• NMP is especially preferable among these.
• step 3 of the present invention in the slurry (I) obtained through the dehydration step of step 2, the polyhaloaromatic compound (a), the alkali metal hydrosulfide (b), and the compound (c1) ) And the alkali metal salt (c2) of the hydrolyzate to perform polymerization (see the following formula (3)).
• M represents an alkali metal atom.
• the decomposition product is characterized in that the alkali metal salt (c2) of the decomposition product is reacted in the state of a slurry and with the amount of water in the reaction system reduced as much as possible.
• the organic acid alkali metal salt (c2) is present in an amount of 0.01 mol or more and less than 0.9 mol, particularly 0.04 to 0.4 mol, per 1 mol of sulfur atoms present in the reaction system. It is preferable from the viewpoint that the effect of suppressing side reactions becomes remarkable.
• the polyhaloaromatic compound (a) in the reaction of Step 3 may be added to the reaction system in Step 2, but as described above, in Step 1, the polyhaloaromatic compound (a) is used as a non-hydrolyzable organic solvent.
• the reaction of step 2 can be performed as it is.
• the alkali metal hydrosulfide (b) can be subjected to the reaction in Step 2 by using the alkali metal hydrosulfide (b) present in the slurry (I) as it is after Step 3.
• the hydrolyzate of the aliphatic cyclic compound (c1) involved in the reaction is again subjected to an alkali metal hydrosulfide (b) by an ion exchange reaction with the solid alkali metal sulfide in the slurry.
• the polymerization reaction represented by the above formula (2) can be advanced.
• the solid alkali metal sulfide gradually becomes a necessary amount of the alkali metal hydrosulfide (b) and the alkali metal salt (c2) of the hydrolyzate of the compound (c1) by such a cycle. ) And supplied as a sulfidizing agent in the reaction system, side reactions are suppressed.
• a lithium salt compound may be added to the reaction system and the reaction may be performed in the presence of lithium ions.
• lithium salt compound examples include lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium carbonate, lithium hydrogen carbonate, lithium sulfate, lithium hydrogen sulfate, lithium phosphate, lithium hydrogen phosphate, phosphorus Lithium dihydrogen, lithium nitrite, lithium sulfite, lithium chlorate, lithium chromate, lithium molybdate, lithium formate, lithium acetate, lithium oxalate, lithium malonate, lithium propionate, lithium butyrate, lithium isobutyrate, malein Lithium oxide, lithium fumarate, lithium butanedioate, lithium valerate, lithium hexanoate, lithium octanoate, lithium tartrate, lithium stearate, lithium oleate, lithium benzoate, lithium phthalate, lithium benzenesulfonate Inorganic lithium salt compounds such as lithium p-toluenesulfonate, lithium sulfide, lithium hydro
• the amount of lithium ions in the reaction system in Step 3 is 0.01 mol or more when the total number of moles of the hydrous alkali metal sulfide used in Step 1 and the sulfiding agent added thereafter is 1 mol. It is preferable that the ratio is in a range of less than .9 mol from the viewpoint that the effect of improving the reactivity in step 3 is remarkable, and in particular, the sulfur atom in which the organic acid alkali metal salt (c) is present in the reaction system. And the amount of lithium ions in the reaction system is 1.8 on a molar basis with respect to the organic acid alkali metal salt (c). A range of ⁇ 2.2 mol is preferable from the viewpoint of higher molecular weight of the polyarylene sulfide resin.
• the alkali metal hydrosulfide (b) which is a raw material for the reaction or polymerization reaction in the step 3 gradually converts the alkali metal sulfide which is the solid content in the slurry (I) to the alkali metal hydrosulfide.
• an alkali metal hydrosulfide (b) may be added separately at any stage of step 3 if necessary.
• the alkali metal hydrosulfide (b) that can be used here include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and hydrates thereof. Among these, lithium hydrosulfide and sodium hydrosulfide are preferable, and sodium hydrosulfide is particularly preferable.
• alkali metal hydroxide may be added in order to react with alkali metal hydrosulfide (b) present in a trace amount in the alkali metal sulfide constituting the solid content of the slurry, or alkali metal thiosulfate.
• a specific method for carrying out the reaction and polymerization in Step 3 is as follows.
• a polyhaloaromatic compound (a), an alkali metal hydrosulfide (b), It is preferable to add a protic polar organic solvent and the lithium salt compound and react or polymerize in the range of 180 to 300 ° C, preferably in the range of 200 to 280 ° C.
• the polymerization reaction can be carried out at a constant temperature, but can also be carried out while raising the temperature stepwise or continuously.
• the amount of the polyhaloaromatic compound (a) in step 3 is specifically preferably in the range of 0.8 to 1.2 mol, particularly 0.9 to 1 mol per mol of sulfur atom in the reaction system.
• the range of 1 mol is preferable from the viewpoint of obtaining a higher molecular weight PAS resin.
• an aprotic polar organic solvent may be further added.
• the total amount of the aprotic polar organic solvent present in the reaction is not particularly limited, but it is aprotic so that it is 0.6 to 10 moles per mole of sulfur atoms present in the reaction system. It is preferable to add a polar organic solvent, and more preferably in the range of 2 to 6 mol from the viewpoint of further increasing the molecular weight of the PAS resin. Further, from the viewpoint of increasing the reactant concentration per volume of the reaction vessel, the range of 1 to 3 moles per mole of sulfur atoms present in the reaction system is preferable.
• the amount of water in the reaction system is substantially anhydrous in the initial stage of the reaction or polymerization in step 3. That is, the water used for the hydrolysis of the aliphatic cyclic compound (c1) in the dehydration step in Step 1 undergoes a ring-closing reaction after the solid content in the slurry disappears, Will appear. Therefore, in step 3 of the present invention, it is finally obtained that the water content in the polymerization slurry is 0.2 mass% or less when the consumption rate of the solid alkali metal sulfide is 10%. From the viewpoint of increasing the molecular weight of the PAS resin obtained.
• the dehydration vessel is equipped with a stirrer, a steam distillation line, a condenser, a decanter, a distillate return line, an exhaust line, and hydrogen sulfide capture.
• a device and a dehydrating device including a heating device examples thereof include a device and a dehydrating device including a heating device.
• the reaction vessel used in the dehydration process in Step 1 and Step 2 and the reaction or polymerization in Step 3 is not particularly limited, but a reaction vessel having a wetted part made of titanium, chromium, zirconium or the like is used. It is preferable to use it.
• step 3 For each step of dehydration treatment in step 1 and step 2 and reaction or polymerization in step 3, usual polymerization methods such as a batch method, a batch method or a continuous method can be adopted.
• the dehydration step and the polymerization step it is preferably performed in an inert gas atmosphere.
• the inert gas to be used include nitrogen, helium, neon, argon, etc. Among them, nitrogen is preferable from the viewpoint of economy and ease of handling.
• the post-treatment method of the reaction mixture containing the PAS resin obtained by the polymerization step is not particularly limited.
• the reaction mixture is first left as it is, or an acid or a base is added.
• the solvent is distilled off under reduced pressure or normal pressure, and then the solid after the solvent is distilled off is washed once or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, and further neutralized and washed with water.
• the reaction mixture is mixed with a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons ( Solvent that is soluble in the polymerization solvent used and a solvent that is at least a poor solvent for PAS resin) is added as a precipitating agent to form solids such as PAS resin and inorganic salts.
• a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons ( Solvent that is soluble in the polymerization solvent used and a solvent that is at least a poor solvent for PAS resin) is added as a precipitating agent to form solids such as PAS resin and inorganic salts.
• the low molecular weight polymer is removed, followed by washing once or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc., followed by neutralization, washing with water, filtration and drying. Etc.
• a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc.
• the PAS resin may be dried in a vacuum, or in an inert gas atmosphere such as air or nitrogen. Good.
• the PAS resin thus obtained can be used as it is for various molding materials, but may be subjected to oxidative crosslinking by heat treatment in air or oxygen-enriched air or under reduced pressure.
• 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 atmosphere to be treated. Further, the heat treatment may be performed in a state where the PAS resin is melted at a temperature equal to or higher than the melting point of the PAS resin by using an extruder or the like. It is preferable.
• the PAS resin obtained by the production method of the present invention described in detail above is excellent in heat resistance, molding processability, dimensional stability, etc. by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding. It can be processed into a molded product.
• the PAS resin obtained by the present invention can be used as a PAS resin composition combined with various fillers in order to further improve performance such as strength, heat resistance, and dimensional stability.
• a filler for example, a fibrous filler, an inorganic filler, etc. are mentioned.
• the fibrous filler include glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium sulfate, calcium silicate, and other natural fibers such as wollastonite. Can be used.
• Inorganic fillers include barium sulfate, calcium sulfate, clay, viroferrite, bentonite, sericite, zeolite, mica, mica, talc, talpulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, etc. Can be used.
• various additives such as a mold release agent, a colorant, a heat stabilizer, a UV stabilizer, a foaming agent, a rust inhibitor, a flame retardant, and a lubricant can be added as additives during molding.
• the PAS resin obtained according to the present invention is suitably polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, depending on the application.
• the PAS resin obtained by the production method of the present invention also has various performances such as heat resistance and dimensional stability inherent to the PAS resin, for example, electrical / electronics such as connectors, printed circuit boards, and sealed molded products.
• Injection molding or compression molding of automotive parts such as parts, lamp reflectors and various electrical components, interior materials such as various buildings, aircraft and automobiles, or precision parts such as OA equipment parts, camera parts and watch parts, or It is widely useful as a material for various molding processes such as extrusion molding or pultrusion molding of composites, sheets and pipes, or as a material for fibers or films.
• the amount of NMP remaining in the slurry obtained in Step 1 and the amount of phenol produced in the slurry obtained in Step 3 are the gas chromatography “GC2014” manufactured by Shimadzu Corporation and the column manufactured by the Chemical Substance Evaluation Research Organization It is a value measured using “G300”.
• the amount of phenol produced was expressed in mol% with respect to sulfur atoms present in the autoclave.
• Example 1 A 150-liter autoclave with a stirring blade connected with a pressure gauge, a thermometer, a condenser, a decanter, and a rectifying tower was added with 33.222 kg (226 mol) of p-dichlorobenzene (hereinafter abbreviated as “p-DCB”), NMP2. 280 kg (23 mol), 47.33% by weight NaSH aqueous solution 27.300 kg (230 mol as NaSH), and 49.21 wt% NaOH aqueous solution 18.533 g (228 mol as NaOH) were charged under a nitrogen atmosphere with stirring. The temperature was raised to 173 ° C.
• p-DCB p-dichlorobenzene
• the amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atoms present in the autoclave.
• the theoretical dehydration amount is 27.921 g. Therefore, 401 g (22.3 mol) out of the remaining water amount 621 g (34.5 mol) in the autoclave. Is consumed in the hydrolysis reaction of NMP and NaOH and does not exist in the autoclave as water, and the remaining 220 g (12.2 mol) remains in the autoclave in the form of water or crystal water. Was showing.
• the amount of water in the autoclave was 0.053 mol per mol of sulfur atoms present in the autoclave.
• Step 2 After completion of the dehydration step, the internal temperature was cooled to 160 ° C., NMP 47.492 kg (479 mol) was charged, and the temperature was raised to 185 ° C. The amount of water in the autoclave was 0.025 mol per 1 mol of NMP charged in step 2. When the gauge pressure reached 0.00 MPa, the valve connected to the rectifying column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, the cooling and the valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower.
• the distilled vapor of p-DCB and water was condensed by a condenser and separated by a decanter, and p-DCB was returned to the autoclave.
• the amount of distilled water was 179 g (9.9 mol).
• Step 3 The water content in the autoclave at the start of Step 3 was 41 g (2.3 mol), 0.005 mol per mol of NMP charged in Step 2, and 0.010 mol per mol of sulfur atoms present in the autoclave. .
• the amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atoms present in the autoclave, as in Step 1.
• the temperature was raised from an internal temperature of 200 ° C. to 230 ° C. over 3 hours, stirred at 230 ° C. for 3 hours, then heated to 250 ° C. and stirred for 1 hour.
• the gauge pressure at an internal temperature of 200 ° C. was 0.03 MPa, and the final gauge pressure was 0.30 MPa.
• Example 2 [Step 1] In a 150 liter autoclave with a stirring blade connected with a pressure gauge, thermometer, condenser, decanter, and rectifying tower, p-DCB 33.222 kg (226 mol), NMP 4.560 kg (46 mol), 47.23 mass% NaSH aqueous solution 27 .300 kg (230 mol as NaSH) and 18.533 g of a 49.21% by mass NaOH aqueous solution (228 mol as NaOH) were heated to 173 ° C. over 5 hours under stirring in a nitrogen atmosphere, After distilling 794 kg, the autoclave was sealed.
• the p-DCB distilled azeotropically during dehydration was separated with a decanter and returned to the autoclave as needed.
• the finely divided anhydrous sodium sulfide composition was dispersed in p-DCB in the autoclave.
• the NMP content in this composition was 0.089 kg (0.9 mol), indicating that 98% (45.1 mol) of the charged NMP was hydrolyzed to SMAB.
• the amount of SMAB in the autoclave was 0.196 mole per mole of sulfur atoms present in the autoclave.
• Step 2 After completion of the dehydration step, the internal temperature was cooled to 160 ° C., 70.098 kg (707 mol) of NMP was charged, and the temperature was raised to 185 ° C. The water content in the autoclave was 0.025 mol per 1 mol of NMP charged in Step 2.
• the gauge pressure reached 0.00 MPa
• the valve connected to the rectifying column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, the cooling and the valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower.
• the distilled vapor of p-DCB and water was condensed by a condenser and separated by a decanter, and p-DCB was returned to the autoclave.
• the amount of distilled water was 273 g (15.2 mol).
• Step 3 The water content in the autoclave at the start of Step 3 was 42 g (2.3 mol), 0.003 mol per mol of NMP charged in Step 2, and 0.010 mol per mol of sulfur atoms present in the autoclave. .
• the amount of SMAB in the autoclave was 0.196 mol per mol of sulfur atoms present in the autoclave, as in Step 1.
• the temperature was raised from an internal temperature of 200 ° C. to 230 ° C. over 3 hours, stirred at 230 ° C. for 3 hours, then heated to 250 ° C. and stirred for 1 hour.
• the gauge pressure at an internal temperature of 200 ° C. was 0.02 MPa, and the final gauge pressure was 0.28 MPa.
• Example 1 The same operation as in Example 1 was performed except that the residual crystallization water was not removed in Step 2.
• the amount of water in the autoclave at the start of Step 3 was 220 g (12.2 moles), 0.025 mole per mole of NMP charged in Step 2, and 0.053 mole per mole of sulfur atoms present in the autoclave. It was.
• the amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atoms present in the autoclave, as in Step 1 of Example 1.
• the gauge pressure at an internal temperature of 200 ° C. was 0.05 MPa, and the final gauge pressure was 0.39 MPa.
• 150 g of white powdery PPS resin was obtained.
• the melt viscosity at 300 ° C. of this polymer was 85 Pa ⁇ s, and the amount of phenol produced was 0.57 mol%.
• Step 1 the same dehydration operation as in Example 1 was performed without charging NMP.
• the amount of distilled water after dehydration was 27.673 g, indicating that the residual water content of 248 g (13.8 mol) in the autoclave remained in the autoclave in the form of water or crystal water.
• the amount of water in the autoclave was 0.060 mol per mol of sulfur atoms present in the autoclave.
• Example 1 was carried out except that in Step 2, 414 g (23.0 mol) of water was added in addition to NMP without removing residual crystal water, and Step 3 was carried out without performing dehydration as it was. The same operation was performed.
• the amount of SMAB in the autoclave at the start of Step 3 was zero, and the amount of water present in the autoclave was 0.077 mol per mol of NMP charged in Step 2 and 0.160 mol per mol of sulfur atoms. It was. Further, the gauge pressure at an internal temperature of 200 ° C. was 0.10 MPa, and the final gauge pressure was 0.40 MPa. By this operation, 150 g of white powdery PPS resin was obtained. The melt viscosity at 300 ° C. of this polymer was 48 Pa ⁇ s, and the amount of phenol produced was 1.09 mol%.
• Table 1 summarizes the melt viscosity and the amount of phenol produced by the PPS resins obtained in Examples 1 and 2 and Comparative Examples 1 and 2.
• the PPS resins obtained in Examples 1 and 2 were found to have a very high melt viscosity of 274 to 315 Pa ⁇ s and a high molecular weight. On the other hand, it was found that the PPS resin obtained in Comparative Example 1 had a low melt viscosity of 48 to 85 Pa ⁇ s and did not have a high molecular weight.
• the PPS resins obtained in Examples 1 and 2 have a very low phenol production amount of 0.05 to 0.06 mol%, and the phenol-based growth end-stopping reaction is sufficiently suppressed. It was.
• the PPS resins obtained in Comparative Examples 1 and 2 had a high phenol production amount of 0.57 to 1.09 mol%, and it was found that the phenol-based growth terminal termination reaction could not be sufficiently suppressed.

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