WO2014103317A1 - 環式ポリアリーレンスルフィドの製造方法 - Google Patents
環式ポリアリーレンスルフィドの製造方法 Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- the present invention relates to a method for producing cyclic polyarylene sulfide. More specifically, the present invention relates to a method for efficiently producing a cyclic polyarylene sulfide by an economical and simple method.
- Aromatic cyclic compounds have attracted attention in recent years due to the properties resulting from their cyclicity, ie, the specificity derived from their structure. Specifically, it is an effective monomer for use in high-functional material applications and functional materials, for example, as a compound having inclusion ability, and for the synthesis of high-molecular-weight linear polymers by ring-opening polymerization. It is expected to be used as Cyclic polyarylene sulfide (hereinafter, polyarylene sulfide may be abbreviated as PAS) also belongs to the category of aromatic cyclic compounds and is a notable compound as described above.
- PAS Cyclic polyarylene sulfide
- Examples of the method for producing cyclic polyarylene sulfide include a method in which a diaryl disulfide compound is oxidatively polymerized under ultradilution conditions (see, for example, Patent Document 1), and a copper salt of 4-bromothiophenol in ultradilution conditions in quinoline. A method of heating under (for example, see Patent Document 2) is disclosed. In these methods, ultradilution conditions were essential.
- cyclic polyarylene sulfide is produced with high selectivity, and the production amount of linear polyarylene sulfide can be suppressed to a very small amount, but the reaction takes a long time, and the cyclic polyarylene sulfide obtained per unit volume of the reaction vessel
- the amount of polyarylene sulfide was very small, and it was a method with many problems from the viewpoint of efficiently obtaining cyclic polyarylene sulfide. Further, purification was difficult, and the resulting cyclic polyarylene sulfide was low in purity.
- the amount of sodium sulfide relative to N-methylpyrrolidone is 0.1 mol / liter.
- a method of adding dichlorobenzene and causing a catalytic reaction at reflux temperature is disclosed (for example, see Non-Patent Document 1).
- the amount of the organic polar solvent relative to 1 mol of sulfur atom of the sulfiding agent is 1.25 liters or more, so that it is possible to obtain cyclic polyarylene sulfide.
- a very small amount of cyclic polyarylene sulfide is obtained.
- the obtained cyclic polyarylene sulfide has a low purity, and there is a problem that a long time is required for the reaction.
- linear polyarylene sulfide, a sulfidizing agent, and a dihalogenated aromatic compound are reacted by heating them in an organic polar solvent of 1.25 liters or more per mole of sulfur component in the reaction mixture.
- an organic polar solvent of 1.25 liters or more per mole of sulfur component in the reaction mixture.
- the amount of monomer used can be reduced because linear polyarylene sulfide is used as a raw material, so that the yield of cyclic polyarylene sulfide relative to the monomer can be improved, and industrial feasibility can be expected.
- the amount of cyclic polyarylene sulfide obtained per container volume was also small, and an improvement in yield was desired.
- a reaction mixture containing at least a linear polyarylene sulfide, a sulfidizing agent, and an organic polar solvent is heated to carry out the reaction, and then a dihalogenated aromatic compound is added to the obtained reaction mixture to obtain a reaction mixture.
- a method is disclosed in which the reaction is carried out by heating in an organic polar solvent of 1.25 liters or more with respect to 1 mol of the sulfur component therein (for example, see Patent Document 5).
- this method also uses linear polyarylene sulfide as a raw material, the amount of monomer to be used can be reduced, but the reaction mixture is dilute and dihalogenated aromatic compound addition and the process is complicated and the operation is complicated. There was little cyclic polyarylene sulfide obtained per container volume, and further higher efficiency was desired.
- a monomer mixture containing at least one sulfur source selected from alkali metal sulfides and alkali metal hydrates, a dihalogenated aromatic compound, and an organic polar solvent is used as a method for obtaining polyarylene sulfide.
- a method is disclosed in which a monomer mixture is fed through a polymerization line in which a continuous tubular reactor having the product inside is incorporated, and the monomer mixture is polymerized (see, for example, Patent Document 6). This method aims to reduce the production cost of polyarylene sulfide, and no mention is made of the production of cyclic polyarylene sulfide.
- An object of the present invention is to solve at least a part of the above problems and to provide a method for efficiently producing a cyclic polyarylene sulfide by an economical and simple method.
- Embodiment of this invention has at least one part of the structure mentioned below in order to solve at least one part of the said subject.
- a method for producing a cyclic polyarylene sulfide by heating and reacting a raw material mixture (a) containing at least a sulfidizing agent, a dihalogenated aromatic compound and an organic polar solvent, the raw material mixture (a)
- An operation (A) for supplying the raw material mixture (a) to the reaction mixture (b) in the reaction vessel containing the reaction product generated from the reaction vessel, and a part of the reaction mixture (b) in the reaction vessel from the reaction vessel A method for producing a cyclic polyarylene sulfide, wherein the operation (B) for extracting and the operation (C) for heating the inside of the reaction vessel are each continuously performed.
- the concentrations of the unreacted sulfidizing agent and dihalogenated aromatic compound in the reaction mixture (b) in the reaction vessel are respectively set to the sulfidizing agent and dihalogenated aromatic compound in the raw material mixture (a).
- the concentration is maintained at 30% or less of each concentration, and the unreacted sulfidizing agent and dihalogenated aromatic compound contained in 1 kg of the reaction mixture (b) are each maintained at 0.15 mol or less.
- the reaction vessel is provided with a circulation line that is connected to the reaction vessel and circulates the reaction mixture (b) between the reaction vessel and the reaction vessel using a pump.
- the reaction vessel is connected to the reaction vessel and supplies the raw material mixture (a) to the reaction vessel in the operation (A), and / or connected to the reaction vessel and the operation ( Any one of [1] to [15], wherein the reaction mixture (b) extracted from the reaction vessel in B) is connected to a receiving vessel and is equalized by a pressure equalization line.
- the manufacturing method of cyclic polyarylene sulfide can be provided, More specifically, the method of manufacturing cyclic polyarylene sulfide efficiently by an economical and simple method can be provided. In particular, by employing the method of the present invention, cyclic polyarylene sulfide can be obtained at a high production rate.
- the sulfidation agent used in the embodiment of the present invention is any one that can introduce a sulfide bond into a dihalogenated aromatic compound and that can produce an arylene thiolate by acting on an arylene sulfide bond. Good.
- the sulfidizing agent include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.
- alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures of two or more thereof. Of these, lithium sulfide and / or sodium sulfide are preferable, and sodium sulfide is more preferably used.
- These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.
- the aqueous mixture refers to an aqueous solution, a mixture of an aqueous solution and a solid component, or a mixture of water and a solid component. Since generally available inexpensive alkali metal sulfides are hydrates or aqueous mixtures, it is preferred to use such forms of alkali metal sulfides.
- alkali metal hydrosulfide examples include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture of two or more selected from these. Of these, lithium hydrosulfide and / or sodium hydrosulfide are preferable, and sodium hydrosulfide is more preferably used.
- alkali metal sulfides generated from alkali metal hydrosulfides and alkali metal hydroxides in the reaction system can also be used.
- an alkali metal sulfide prepared by previously contacting an alkali metal hydrosulfide and an alkali metal hydroxide can be used.
- These alkali metal hydrosulfides and alkali metal hydroxides can be used in the form of compounds selected from hydrates, aqueous mixtures, and anhydrides. Hydrates or aqueous mixtures are preferred from the standpoint of availability and cost.
- alkali metal sulfides generated in the reaction system from alkali metal hydroxides such as lithium hydroxide and sodium hydroxide and hydrogen sulfide can also be used.
- alkali metal sulfides prepared by previously contacting alkali metal hydroxides such as lithium hydroxide and sodium hydroxide with hydrogen sulfide can also be used.
- Hydrogen sulfide can be used in any form of gas, liquid, and aqueous solution.
- the amount of the sulfidizing agent is determined based on the actual charge amount when a partial loss of the sulfidizing agent occurs before the reaction with the dihalogenated aromatic compound due to dehydration operation or the like. It shall mean the remaining amount after deduction.
- alkali metal hydroxide and / or an alkaline earth metal hydroxide in combination with the sulfidizing agent.
- alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more selected from these.
- alkaline earth metal hydroxide include calcium hydroxide, strontium hydroxide, and barium hydroxide, and sodium hydroxide is preferably used.
- the amount of alkali metal hydroxide used can be 0.95 mol or more, preferably 1.00 mol or more, more preferably 1.005 mol, per 1 mol of alkali metal hydrosulfide. That's it.
- the amount of the alkali metal hydroxide used can be 1.50 mol or less, preferably 1.25 mol or less, more preferably 1.200 mol or less with respect to 1 mol of the alkali metal hydrosulfide. It is.
- the amount of the alkali metal hydroxide used can be 2.0 mol or more, preferably 2.01 mol or more, more preferably 2.04 mol or more with respect to 1 mol of hydrogen sulfide. .
- the usage-amount of an alkali metal hydroxide can be 3.0 mol or less with respect to 1 mol of hydrogen sulfide, Preferably it is 2.50 mol or less, More preferably, it is 2.40 mol or less.
- the dihalogenated aromatic compound used in the embodiment of the present invention is an aromatic compound having an arylene group which is a divalent group of an aromatic ring and two halogeno groups.
- One mole of the dihalogenated aromatic compound has 1 mole of an arylene unit and 2 moles of a halogeno group.
- compounds having a phenylene group which is a divalent group of a benzene ring as an arylene group and two halogeno groups include p-dichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dibromobenzene, o-dibromo.
- dihalogenated benzenes such as benzene, m-dibromobenzene, 1-bromo-4-chlorobenzene, and 1-bromo-3-chlorobenzene.
- dihalogenated aromatic compounds include 1-methoxy-2,5-dichlorobenzene, 1-methyl-2,5-dichlorobenzene, 1,4-dimethyl-2,5-dichlorobenzene, 1,3-dimethyl.
- compounds containing a substituent other than a halogen group such as -2,5-dichlorobenzene and 3,5-dichlorobenzoic acid.
- dihalogenated aromatic compounds mainly composed of p-dihalogenated benzene represented by p-dichlorobenzene are preferable. Particularly preferably, it contains 80 to 100 mol% of p-dichlorobenzene, and more preferably 90 to 100 mol%. It is also possible to use two or more different dihalogenated aromatic compounds in combination in order to obtain a cyclic polyarylene sulfide (hereinafter also referred to as cyclic PAS) copolymer.
- cyclic PAS cyclic polyarylene sulfide
- an organic polar solvent is used as a reaction solvent, and an organic amide solvent is preferably used.
- N-alkylpyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone, caprolactams such as N-methyl- ⁇ -caprolactam, 1,
- An aprotic organic solvent typified by 3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, etc., and a mixture thereof can improve the reaction stability. It is preferably used because it is expensive. Of these, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone are preferably used.
- the cyclic polyarylene sulfide in the embodiment of the present invention is a cyclic compound having a repeating unit of the formula — (Ar—S) — as a main structural unit, preferably the repeating unit.
- a repeating unit of the formula — (Ar—S) — as a main structural unit, preferably the repeating unit.
- Ar is an arylene group, and examples thereof include units represented by the following formulas (B) to (M), among which the formulas (B) to (K) are preferable, and the formula (B) and the formula (C) is more preferred, and formula (B) is particularly preferred.
- R1 and R2 are substituents selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen group, and R1 and R2 are the same or different. May be.
- R1 and R2 are substituents selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen group, and R1 and R2 are the same or different. May be.
- R1 and R2 are substituents selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen group, and R1 and R2 are the same or different. It is good.
- the cyclic polyarylene sulfide may be any of a random copolymer, a block copolymer and a mixture thereof containing repeating units such as the above formulas (B) to (M).
- Representative examples of the cyclic polyarylene sulfide of the embodiment of the present invention include cyclic polyphenylene sulfide, cyclic polyphenylene sulfide sulfone, cyclic polyphenylene sulfide ketone, cyclic random copolymers containing these, and cyclic block copolymers. Examples thereof include polymers and mixtures thereof.
- the cyclic polyarylene sulfide of the embodiment of the present invention includes a p-phenylene sulfide unit as a main structural unit. Is preferable, and cyclic polyphenylene sulfide containing 90 mol% or more is particularly preferable.
- m is preferably 4 to 50, more preferably 4 to 30, and still more preferably 4 to 25.
- a polyarylene sulfide prepolymer containing a cyclic polyarylene sulfide is used as a raw material and a high molecular weight polyarylene sulfide (hereinafter, a high molecular weight polyarylene sulfide obtained using a polyarylene sulfide prepolymer as a raw material is simply converted into (Also referred to as arylene sulfide or PAS), it is desirable that the polyarylene sulfide prepolymer is heated at a temperature at which the polyarylene sulfide prepolymer melts, so that the polyarylene sulfide can be obtained efficiently. It becomes.
- the melting temperature of the cyclic PAS tends to be 275 ° C. or lower, preferably 260 ° C. or lower, more preferably 255 ° C. or lower. Therefore, the melting temperature of such a polyarylene sulfide prepolymer containing cyclic PAS also tends to be lowered accordingly. Therefore, when the range of the cyclic PAS repeating number m is in the above-described range, it is desirable that the heating temperature of the polyarylene sulfide prepolymer can be set low in the production of the polyarylene sulfide.
- the melting temperature of cyclic PAS and polyarylene sulfide is an endothermic peak observed when the temperature is raised to 360 ° C. at a scanning rate of 20 ° C./min after holding at 50 ° C. for 1 minute with a suggested scanning calorimeter. The peak temperature of is shown.
- the cyclic polyarylene sulfide in the embodiment of the present invention may be either a single compound having a single repeating number or a mixture of cyclic polyarylene sulfides having different repeating numbers.
- a mixture of cyclic polyarylene sulfides having different numbers of repeats is preferred because it has a lower melting solution temperature and a smaller amount of heat required for melting than a single compound having a single number of repeats.
- the ratio of the content of cyclic PAS in which the number of repetitions m of the formula (A) is 6 with respect to the total amount of cyclic polyarylene sulfide ([m 6
- the cyclic PAS (weight)] / [cyclic PAS mixture (weight)] ⁇ 100 (%)) is preferably less than 50% by weight, more preferably less than 40% by weight, and even more preferably less than 30% by weight.
- cyclohexa (p-phenylene sulfide) in which Ar is a paraphenylene sulfide unit and cyclic PAS having a repeating number m of 6.
- the content of cyclic PAS in which m in the formula (A) is 6 is preferably in the above-mentioned range.
- the cyclic PAS in the raw material for producing polyarylene sulfide has a different number of repetitions.
- the cyclic PAS contained in the cyclic PAS mixture when the total amount of the cyclic PAS having the m of 4 to 13 in the formula (A) is 100% by weight, the cyclic PAS having the m of 5 to 8 is used.
- cyclic PAS mixture containing 5% by weight or more of each, and it is more preferable to use a cyclic PAS mixture containing 7% by weight or more of cyclic PAS having m of 5 to 8.
- the cyclic PAS mixture having such a composition ratio is particularly preferable from the viewpoint of lowering the melting temperature because the melting peak temperature tends to be low and the heat of fusion tends to be small.
- each cyclic PAS having a different number of repetitions m with respect to the total amount of cyclic polyarylene sulfide in the cyclic PAS mixture is determined when the cyclic PAS mixture is divided into components by high performance liquid chromatography equipped with a UV detector.
- the qualitative characteristics of each peak divided into components by this high performance liquid chromatography can be obtained by separating each peak by preparative liquid chromatography and performing an absorption spectrum or mass analysis in infrared spectroscopic analysis.
- linear polyarylene sulfide in the embodiment of the present invention is composed mainly of a repeating unit of the formula — (Ar—S) —.
- the unit is preferably a linear homopolymer or a linear copolymer containing 80 mol% or more of the repeating unit.
- Ar includes units represented by the above formulas (B) to (M), among which the formula (B) is particularly preferable.
- this repeating unit is a main constituent unit, it can contain a small amount of branching units or crosslinking units represented by the following formulas (N) to (Q).
- the copolymerization amount of these branch units or cross-linking units is preferably in the range of 0 to 1 mol% with respect to 1 mol of the main structural unit represented by — (Ar—S) —.
- linear PAS in the embodiment of the present invention may be any of a random copolymer, a block copolymer, and a mixture thereof containing the above repeating unit.
- Typical examples thereof include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers thereof, block copolymers thereof, and mixtures thereof.
- a particularly preferred linear PAS is a p-phenylene sulfide unit as the main structural unit of the polymer.
- PPS polyphenylene sulfide
- polyphenylene sulfide sulfone polyphenylene sulfide ketone.
- linear PAS can be used as a raw material.
- the melt viscosity of the linear PAS used in that case is not particularly limited, but the melt viscosity of a general linear PAS is exemplified by a range of 0.1 to 1000 Pa ⁇ s (300 ° C., shear rate 1000 / sec). A range of 0.1 to 500 Pa ⁇ s can be exemplified.
- the molecular weight of the linear PAS is not particularly limited, and general PAS can be used.
- the weight average molecular weight of such a PAS can be 5,000 or more, preferably 7,500 or more, and more preferably 10,000 or more.
- the weight average molecular weight of PAS can be 1,000,000 or less, preferably 500,000 or less, and more preferably 100,000 or less.
- the weight average molecular weight of the linear PAS is a value determined as standard polystyrene conversion. In general, the lower the weight average molecular weight, the higher the solubility in an organic polar solvent. Therefore, the lower the weight average molecular weight, the shorter the time required for the reaction. Is possible.
- a linear PAS can be produced by a method described in known literatures represented by JP-B 45-3368, JP-B 52-12240 and JP-B 63-3375. That is, a linear PAS can be produced by a method in which an aromatic compound or thiophene containing at least one nucleus-substituted halogen is reacted with an alkali metal monosulfide at an elevated temperature in a polar organic solvent.
- linear PAS can be produced by a method described in a known document represented by, for example, JP-A No. 05-163349.
- linear PAS can be obtained by contacting a sulfiding agent and a dihalogenated aromatic compound in an organic polar solvent.
- molded products and molding waste using PAS produced by these methods, or waste plastics and off-spec products derived from PAS produced by these methods can be used widely as linear PAS.
- the reaction for producing a cyclic compound is a competitive reaction between the production of a cyclic compound and the production of a linear compound. Therefore, in a method aimed at producing a cyclic polyarylene sulfide, In addition to the cyclic polyarylene sulfide, a linear polyarylene sulfide is produced as a by-product. In the embodiment of the present invention, such byproduct linear polyarylene sulfide can be used as a raw material without any problem.
- cyclic PAS for example, an organic polar solvent having a sulfidizing agent and a dihalogenated aromatic compound in an amount of 1.25 liters or more per 1 mol of the sulfur component of the sulfidizing agent.
- a method for separating cyclic polyarylene sulfide from a polyarylene sulfide mixture containing the obtained cyclic polyarylene sulfide and linear polyarylene sulfide, and using the obtained linear polyarylene sulfide as a raw material Is a particularly preferred method.
- cyclic PAS described in Patent Document 4 that is, linear polyarylene sulfide, sulfidizing agent, and dihalogenated aromatic compound are added in an amount of 1. with respect to 1 mol of sulfur component in the reaction mixture. Heating using an organic polar solvent of 25 liters or more, separating the cyclic polyarylene sulfide from the resulting polyarylene sulfide mixture containing the cyclic polyarylene sulfide and the linear polyarylene sulfide, and the resulting linear polyarylene A method using sulfide as a raw material is also a preferable method.
- a method for producing a cyclic polyarylene sulfide by heating and reacting at least a raw material mixture (a) containing a sulfidizing agent, a dihalogenated aromatic compound and an organic polar solvent, and is produced from the raw material mixture (a)
- this byproduct linear polyarylene sulfide can be used as a raw material, and this is a viewpoint that enables a significant reduction in the amount of waste and a dramatic improvement in the yield relative to the raw material monomer. It is very significant.
- the powdery form of a dry state, a granular form, a granular form, and a pellet form may be sufficient.
- the linear polyarylene sulfide can be used in a state containing an organic polar solvent which is a reaction solvent, and can also be used in a state containing a third component which does not essentially inhibit the reaction. Examples of such a third component include inorganic fillers and alkali metal halides.
- the alkali metal halide includes any combination of alkali metals (ie, lithium, sodium, potassium, rubidium and cesium) and halogens (ie, fluorine, chlorine, bromine, iodine and astatine).
- alkali metals ie, lithium, sodium, potassium, rubidium and cesium
- halogens ie, fluorine, chlorine, bromine, iodine and astatine.
- Specific examples include lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide, lithium iodide, sodium iodide, potassium iodide, and cesium fluoride.
- Preferable examples include alkali metal halides generated by the reaction of the aforementioned sulfiding agent and dihalogenated aromatic compound.
- Alkali metal halides resulting from combinations of sulfidizing agents and dihalogenated aromatic compounds that are generally readily available include lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide and iodide.
- Sodium can be exemplified, and sodium chloride, potassium chloride, sodium bromide, and potassium bromide can be exemplified as preferred, and sodium chloride is more preferred. It is also possible to use linear polyarylene sulfide in the form of a resin composition containing an inorganic filler or an alkali metal halide.
- linear PAS is generated as a by-product as described above.
- the melt viscosity of the linear PAS produced in the embodiment of the present invention is not particularly limited, but the melt viscosity of a general linear PAS is 0.1 to 1000 Pa ⁇ s (300 ° C., shear rate 1000 / sec).
- the range can be exemplified, and the range of 0.1 to 500 Pa ⁇ s can be said to be a range that tends to be generated.
- the molecular weight of linear PAS is not particularly limited, but the lower limit of the weight average molecular weight of general PAS can be exemplified by 1,000 or more, and is produced by the method for producing cyclic polyarylene sulfide of the embodiment of the present invention.
- the linear PAS that tends to be 2,500 or more tends to be 5,000 or more.
- an upper limit of the weight average molecular weight of general PAS 1,000,000 or less can be illustrated, and linear PAS produced
- the weight average molecular weight of the linear PAS is a value determined as standard polystyrene conversion. In general, the higher the weight average molecular weight, the more strongly the characteristics as linear PAS are expressed. Therefore, in the separation of cyclic PAS and linear PAS described later, the separation tends to be easily performed. It can be used without any essential problems.
- a cyclic polyarylene sulfide is produced by heating and reacting a raw material mixture containing at least a sulfidizing agent, a dihalogenated aromatic compound and an organic polar solvent.
- the operation (A) of supplying the raw material mixture (a) to the reaction mixture (b) in the reaction vessel containing the reaction product generated from the raw material mixture (a), and the reaction mixture (b) in the reaction vessel The operation (B) for extracting a part of the reaction vessel from the reaction vessel and the operation (C) for heating the inside of the reaction vessel are carried out continuously.
- the arylene sulfide can be obtained continuously, high productivity can be realized.
- the substrate concentration, the raw material mixture (a), the reaction mixture (b), the operation (A) and the operation (B), and other embodiments according to the embodiments of the present invention will be described in detail in order.
- the substrate concentration is the sulfur component in the raw material mixture (a) or reaction mixture (b) (hereinafter also referred to as reaction mixture etc.) as described in detail below.
- the relationship between the amount (number of moles) of each arylene unit and the amount of the organic polar solvent refers to the amount of organic polar solvent per sulfur component in the reaction mixture
- the substrate concentration of the arylene unit refers to the organic polarity per arylene unit in the reaction mixture. Refers to the amount of solvent.
- the substrate concentration of the sulfur component is defined by the amount of the organic polar solvent per mole of the sulfur component in the reaction mixture or the like.
- the molar amount of the sulfur component in the reaction mixture or the like is synonymous with the molar amount of the sulfur atom present in the reaction mixture or the like.
- 1 mol of alkali metal sulfide is present in the reaction mixture or the like, and other sulfur is removed.
- the sulfur component contained in the reaction mixture or the like corresponds to 1 mole.
- the sulfur component contained in the reaction mixture or the like corresponds to 1 mole.
- the raw material mixture (a) that is, the stage where the reaction of the sulfidizing agent and dihalogenated aromatic compound charged as raw materials is not progressing
- the sulfur component contained in a) means a sulfur component derived from a sulfidizing agent.
- the sulfur component derived from the sulfidizing agent contained in the reaction mixture and the arylene sulfide present in the reaction mixture and the like This refers to the total value of sulfur components derived from the compound.
- an arylene sulfide compound is produced by a reaction between a sulfidizing agent, a dihalogenated aromatic compound and / or a linear polyarylene sulfide. Therefore, in the reaction mixture, as the reaction proceeds, arylene sulfide units corresponding to the amount of consumed sulfiding agent are newly generated. That is, unless the sulfidizing agent contained in the reaction mixture is removed, missing, or added, the amount of sulfur component contained in the reaction mixture is the same as in the preparation stage regardless of the progress of the reaction. Therefore, when there is no removal, loss or addition of the organic polar solvent from the reaction mixture, it can be said that the substrate concentration of the sulfur component does not change even when the reaction proceeds.
- the operation (A) for supplying the raw material mixture (a) to the reaction mixture (b) in the reaction vessel containing the reaction product generated from the raw material mixture (a), and the reaction in the reaction vessel Since the operation (B) for extracting a part of the mixture (b) from the reaction vessel is continuously performed, the amount of the sulfur component and the organic polar solvent in the reaction mixture (b) varies. However, as long as there is no removal, loss or addition of the sulfur component or the organic polar solvent in the reaction mixture (b) that causes the composition to be biased to one side, the progress of each operation or reaction described above Regardless of the condition, it can be said that the substrate concentration of the sulfur component contained in the reaction mixture (b) does not always change.
- the amount of the sulfur component in the reaction mixture or the like can be determined by quantifying the amount of the sulfur component derived from the sulfidizing agent and the amount of the arylene sulfide compound present in the reaction mixture or the like.
- the amount of the sulfidizing agent in the reaction mixture or the like can be determined by an ion chromatography method described later.
- the amount of the arylene sulfide compound in the reaction mixture or the like is the amount of solid content obtained by dispersing a part of the reaction mixture or the like in a large excess of water to recover water-insoluble components and then drying. It is possible to obtain from
- the amount of the organic polar solvent relative to 1 mol of the sulfur component in the reaction mixture or the like is, for example, from the viewpoint of the production efficiency of the cyclic PAS. Is preferably 1.25 liters or more, more preferably 1.5 liters or more, and even more preferably 2 liters or more.
- the amount of the organic polar solvent relative to 1 mol of the sulfur component in the reaction mixture is preferably 50 liters or less, more preferably 20 liters or less, and even more preferably 15 liters or less from the viewpoint of production efficiency per reaction vessel volume.
- the amount of solvent here is shown by the volume of the solvent under normal temperature normal pressure.
- the production rate of cyclic PAS is the ratio of sulfur components contained in cyclic PAS per mole of total sulfur components in reaction mixture (b) in the production of cyclic PAS described in detail later. is there. That is, if the production rate of cyclic PAS is 100%, it means that all of the sulfur components in the reaction mixture (b) are present as cyclic polyarylene sulfide.
- Increasing the amount of the organic polar solvent per mole of sulfur component is preferable from the viewpoint of more efficiently converting the sulfur-containing raw material to the target product (cyclic PAS).
- cyclic PAS if the amount of the organic polar solvent used to achieve a very high production rate is extremely increased, the production amount of cyclic PAS per unit volume of the reaction mixture (b) tends to decrease. In addition, the time required for the reaction tends to increase.
- the amount of the organic polar solvent is too large, the amount of cyclic polyarylene sulfide per unit amount in the reaction mixture (b) becomes very small. Operation becomes difficult. From the viewpoint of achieving both the production rate and productivity of the cyclic polyarylene sulfide, it is preferable that the amount of the organic polar solvent is within the above range.
- the amount of the solvent used in the production of a general cyclic compound is very large in many cases, and the cyclic compound is often not efficiently obtained within the preferable amount range of the embodiment of the present invention.
- cyclic PAS can be efficiently obtained even under conditions where the amount of solvent used is relatively small, that is, when the amount is not more than the above-mentioned upper limit value of the preferred amount of solvent used, compared to the case of general cyclic compound production. It is done. The reason for this is not clear at the present time, but in the method of the preferred embodiment of the present invention, the reaction is performed at a temperature exceeding the reflux temperature of the reaction mixture, so that the reaction efficiency is extremely high and the consumption rate of the raw material is high. It is presumed that the compound acts favorably in the production of the formula compound.
- the substrate concentration of the arylene unit is defined by the amount of the organic polar solvent per mole of the arylene unit in the reaction mixture or the like in the same manner as the above sulfur component.
- the molar amount of the arylene unit in the reaction mixture or the like is synonymous with the molar amount of the arylene unit present in the reaction mixture or the like.
- 1 mol of a dihalogenated aromatic compound is present in the reaction mixture or the like, and other arylene units are present.
- the arylene unit contained in the reaction mixture or the like corresponds to 1 mol.
- the arylene unit contained in the reaction mixture or the like corresponds to 1 mole.
- the raw material having an arylene unit is only a dihalogenated aromatic compound.
- the arylene unit contained in the mixture (a) refers to an arylene unit derived from a dihalogenated aromatic compound.
- the reaction mixture (b) or the raw material mixture (a) containing linear polyarylene sulfide the arylene unit contained in the reaction mixture or the like is derived from a dihalogenated aromatic compound contained in the reaction mixture or the like.
- an arylene sulfide compound is produced by a reaction between a sulfidizing agent, a dihalogenated aromatic compound and / or a linear polyarylene sulfide. Therefore, as the reaction proceeds, an arylene sulfide compound corresponding to the amount of the dihalogenated aromatic compound consumed is newly generated. That is, unless the arylene unit contained in the reaction mixture is removed, missing, or added, the amount of the arylene unit contained in the reaction mixture is the same as in the preparation stage regardless of the progress of the reaction. Therefore, if there is no removal, loss or addition of the organic polar solvent from the reaction mixture, it can be said that the substrate concentration of the arylene unit does not change even when the reaction proceeds.
- the operation (A) for supplying the raw material mixture (a) to the reaction mixture (b) in the reaction vessel containing the reaction product generated from the raw material mixture (a), and the reaction in the reaction vessel Since the operation (B) for extracting a part of the mixture (b) from the reaction vessel is continuously performed, the amount of the arylene component and the organic polar solvent in the reaction mixture (b) varies. However, as long as there is no removal, loss, or addition of the arylene component and the organic polar solvent in the reaction mixture (b) that causes the composition to be biased to one side, the progress of each operation or reaction described above Regardless of the condition, it can be said that the substrate concentration of the arylene unit contained in the reaction mixture (b) does not always change.
- the amount of the arylene unit in the reaction mixture or the like can be determined by quantifying the amount of the arylene unit derived from the dihalogenated aromatic compound and the amount of the arylene sulfide compound present in the reaction mixture or the like.
- the amount of the arylene unit in the reaction mixture or the like can be determined by a gas chromatography method described later.
- the amount of the arylene sulfide compound in the reaction mixture or the like is the amount of solid content obtained by dispersing a part of the reaction mixture or the like in a large excess of water to recover water-insoluble components and then drying. It is possible to obtain from
- the substrate concentration of the arylene unit in the production of the cyclic PAS according to the embodiment of the present invention is defined as the amount of the organic polar solvent per mole of the arylene unit in the reaction mixture or the like.
- the amount of the organic polar solvent with respect to 1 mol of the arylene units in the reaction mixture or the like is preferably 0.63 liters or more. More preferably 0.000 liters or more, and even more preferably 1.67 liters or more. Moreover, 55 liters or less are preferable, 22 liters or less are more preferable, and 16 liters or less are still more preferable.
- the substrate concentration of the arylene unit in the reaction mixture or the like is preferably determined in consideration of the substrate concentration of the sulfur component.
- the arylene unit in the reaction mixture or the like is preferably 0.90 mol or more, more preferably 0.92 mol or more, further preferably 0.95 mol or more with respect to 1 mol of the sulfur component in the reaction mixture or the like.
- the arylene unit relative to 1 mol of the sulfur component in the reaction mixture or the like is preferably 2.00 mol or less, more preferably 1.50 mol or less, and further preferably 1.20 mol or less.
- the substrate concentration in the reaction mixture (b) is kept constant, that is, each of the sulfur component amount and the arylene unit amount in the reaction mixture (b) It is preferable to keep the relationship with the amount of polar solvent constant.
- “maintaining the substrate concentration constant” is a characteristic of the embodiment of the present invention that the raw material mixture (a) is added to the reaction mixture (b) in the reaction vessel containing the reaction product generated from the raw material mixture (a).
- the substrate concentration of the sulfur component in the reaction mixture (b) is constant means that the variation range of the substrate concentration of the sulfur component is within ⁇ 30% based on the substrate concentration before each of the above operations. It means that.
- the fluctuation range is more preferably within ⁇ 20%, further preferably within ⁇ 15%, even more preferably within ⁇ 10%, and particularly preferably within ⁇ 5%.
- the amount of the organic polar solvent relative to 1 mol of the sulfur component in the reaction mixture (b) is preferably 1.25 liters or more, and 50 liters or less. It is preferable.
- the fact that the substrate concentration of the arylene unit in the reaction mixture (b) is constant means that when the substrate concentration of the sulfur component is determined, the fluctuation range of the amount of the arylene unit relative to 1 mol of the sulfur component in the reaction mixture or the like. Is within ⁇ 30% on the basis of the amount of arylene units relative to 1 mol of the sulfur component in the reaction mixture or the like before each of the above operations.
- the fluctuation range of the arylene unit amount relative to 1 mol of the sulfur component is more preferably within ⁇ 20%, further preferably within ⁇ 15%, still more preferably within ⁇ 10%, and particularly preferably within ⁇ 5%.
- the control of each operation of the operation (A) and / or the operation (B) is performed. Regardless of the method, it is possible to maintain a constant substrate concentration in the reaction mixture (b).
- the substrate concentration in the reaction mixture (b) By maintaining the substrate concentration in the reaction mixture (b) within the above range, both the production rate and productivity of cyclic PAS can be achieved, and cyclic PAS can be obtained efficiently.
- the higher the concentration of the substrate the lower the production rate of cyclic PAS in the reaction mixture (b).
- the concentration the lower the consumption rate of the raw material and the longer the reaction time.
- the raw material mixture (a) in the embodiment of the present invention contains a sulfidizing agent, a dihalogenated aromatic compound and an organic polar solvent as essential components as raw material components.
- the raw material mixture (a) may further contain linear PAS, and in addition to the essential components, a third component that does not significantly inhibit the reaction and a third component that has an effect of accelerating the reaction may be added. Is possible.
- the composition of the raw material mixture (a) is based on the composition of all raw material components at the time when the raw material mixture is supplied into the reaction vessel, and the whole supplied raw material components are regarded as the raw material mixture (a).
- the mixing method, the preparation method, or the supply method is not particularly limited as long as all the raw material components can be supplied into the reaction vessel as the raw material mixture (a).
- the raw materials for the sulfidizing agent, dihalogenated aromatic compound and organic polar solvent may be separately supplied into the reaction vessel, or may be supplied into the reaction vessel after mixing two or more kinds of raw materials.
- the substrate concentration of the reaction mixture (b) is easily maintained constant, at least a sulfidizing agent, a dihalogenated aromatic compound and an organic polar solvent are mixed in advance according to a desired substrate concentration.
- the method of preparation is a particularly preferred method.
- the amount of the organic polar solvent in preparing the raw material mixture (a) is preferably 1.25 liters or more, more preferably 1.5 liters or more, and more preferably 2 liters or more with respect to 1 mole of the sulfur component in the raw material mixture (a). Is more preferable.
- the amount of the organic polar solvent relative to 1 mol of the sulfur component is preferably 50 liters or less, more preferably 20 liters or less, and even more preferably 15 liters or less.
- the amount of solvent here is shown by the volume of the solvent under normal temperature normal pressure.
- the amount of the arylene unit in preparing the raw material mixture (a) is preferably 0.90 mol or more, more preferably 0.92 mol or more, and 0.95 mol per mol of the sulfur component in the raw material mixture (a). Mole or more is more preferable.
- the amount of arylene units per mole of sulfur component is preferably 2.00 moles or less, more preferably 1.50 moles or less, and even more preferably 1.20 moles or less.
- the substrate concentration of the raw material mixture (a) is also preferably kept constant within the range of the preferred substrate concentration.
- the constant substrate concentration of the raw material mixture (a) means that the fluctuation range of the substrate concentration is within ⁇ 30% based on the substrate concentration before the fluctuation.
- the fluctuation range of the substrate concentration is more preferably within ⁇ 20%, further preferably within ⁇ 15%, still more preferably within ⁇ 10%, and particularly preferably within ⁇ 5%.
- a preferable method is to carry out the reaction with the water content in the raw material mixture (a) being small.
- the preferable water content in the raw material mixture (a) is, for example, 5 mol or less per 1 mol of the sulfur component in the raw material mixture (a), and preferably 3 mol or less.
- raw material components such as a sulfidizing agent and an organic polar solvent used for the preparation of the raw material mixture (a) are dehydrated in advance, so that the water content in the raw material mixture (a) is changed to sulfur in the raw material mixture (a).
- It can be less than 0.8 mol, preferably less than 0.7 mol, more preferably less than 0.6 mol, more preferably less than 0.5 mol based on 1 mol of the component.
- There is no lower limit of the amount of water in the reaction mixture and it is preferable that it is close to 0 mol.
- Another advantage of controlling the amount of water within this range is that there is a tendency that adhesion of colored substances to the finally obtained reaction solution and the reactor used in the reaction can be suppressed. This is preferable because not only the quality of the cyclic PAS is improved, but also the cleaning operation of the reactor is reduced.
- a method of bringing the water content in the raw material mixture (a) into the above preferred range for example, a method using an anhydrous or low water content as the raw material component can be exemplified as a preferred method.
- a method of using a dehydration step in advance before preparing the raw material mixture (a) to reduce the water content of each component to the desired range it is also possible to employ a method of dehydrating while mixing and reacting the raw material components with a large amount of water.
- dihalogenated aromatics and organic polar solvents are relatively readily available with sufficiently low water content, whereas sulfidizing agents such as hydrates containing water for alkali metal sulfides.
- aqueous mixtures are generally cheaper and easier to obtain. Therefore, from the viewpoint of availability and cost, it is preferable to use these hydrates or aqueous mixtures as sulfiding agents.
- the water content of the dihalogenated aromatic compound and the organic polar solvent is small, The water content in the reaction mixture tends to increase due to the sulfidizing agent containing water. Therefore, in order to adjust the water content in the reaction mixture to the above preferred range, it is desirable to provide a step of dehydration.
- the dehydration method in this dehydration step is not particularly limited as long as the amount of water can be adjusted.
- the following liquid removal method is preferably employed. That is, a mixture containing at least a water-containing sulfiding agent and an organic polar solvent is preferably prepared in an inert gas atmosphere at room temperature to 150 ° C., preferably from room temperature to 100 ° C., and at 150 ° C. under normal pressure or reduced pressure.
- the method of raising the temperature to 170 ° C. or higher and distilling off water can be exemplified.
- it is 250 degreeC as a preferable upper limit of the temperature which distills off the said organic polar solvent and a water
- the amount of the organic polar solvent used in the liquid removal method is preferably 0.1 liter or more, more preferably 0.15 liter or more, and further preferably 0.2 liter or more, per mole of sulfur component of the sulfidizing agent.
- the amount of the organic polar solvent is preferably 1 liter or less, more preferably 0.8 liter or less, and further preferably 0.6 liter or less, per mole of the sulfur component of the sulfidizing agent.
- the distillation may be carried out with stirring in order to accelerate the distillation, preferably through an inert gas stream, and azeotropic components such as toluene may be removed.
- distillation may be performed.
- a rectifying column may be provided for the purpose of selectively distilling off water in the apparatus used in the liquid removal method.
- the dehydration component prepared in the dehydration step as described above is a sulfidizing agent having a low water content, it is mixed with other components necessary for the raw material mixture (a), that is, at least a dihalogenated aromatic compound and an organic polar solvent. Thus, it is possible to prepare and react the raw material mixture (a) having a low water content.
- linear polyarylene sulfide may be included as a raw material component in the raw material mixture (a).
- the content of the linear polyarylene sulfide in the raw material mixture (a) Is not particularly limited as long as the raw material composition in the raw material mixture (a) is in the above range.
- the amount of the sulfur component derived from the linear polyarylene sulfide is the sum of the sulfur component derived from the linear polyarylene sulfide and the sulfur component derived from the sulfidizing agent, that is, the total sulfur component in the raw material mixture (a). It is preferable to be a majority of the amount.
- the lower limit of the ratio of the sulfur component of the linear polyarylene sulfide in the reaction mixture (a) to 1 mol of the total sulfur component in the reaction mixture (a) is preferably 0.5 mol or more, and 0.6 mol or more. Is more preferable, and 0.7 mol or more is more preferable.
- the upper limit is preferably 0.99 mol or less, more preferably 0.95 mol or less, and even more preferably 0.90 mol or less. If the content of the linear polyarylene sulfide is within the above preferable range, in the reaction mixture (b) described later, the production rate of the cyclic polyarylene sulfide with respect to the sulfidizing agent in the raw material mixture (a) tends to increase. Yes, it can be said that it is economically efficient when the linear polyarylene sulfide by-produced by the method of the embodiment of the present invention is used as the linear polyarylene sulfide of the raw material mixture (a).
- the properties of the raw material mixture (a) thus obtained vary depending on the types of sulfidizing agent, dihalogenated aromatic compound and organic polar solvent, the presence or absence of linear PAS and the third component, and their quantitative relationship. Therefore, although it is not uniquely determined, it is often a solution or a slurry.
- the slurry refers to a fluid in which solid particles are suspended in a liquid.
- reaction mixture (b) in the method for producing a cyclic PAS means at least a cyclic PAS, a linear PAS, a metal halide and a reaction mixture obtained by heating and reacting the raw material mixture (a).
- the reaction mixture (b) contains a sulfidizing agent and / or a dihalogenated aromatic compound in order to continuously react the raw material mixture (a) with the reaction mixture (b). May be.
- the substrate concentration of the reaction mixture (b) is kept constant, but the component composition of the reaction mixture (b) can be varied and is not always constant.
- the operation (A) for supplying the raw material mixture (a) into the reaction vessel containing the reaction mixture (b) and the reaction in the reaction vessel are performed. It is characterized in that the operation (B) for extracting a part of the mixture (b) from the reaction vessel is continuously performed, and the reaction vessel including the time when the production of the cyclic PAS according to the embodiment of the present invention is started is included. There is always a reaction mixture (b). Therefore, the starting point for the production of the cyclic PAS according to the embodiment of the present invention is the time when the reaction mixture (b) can be prepared in the reaction vessel.
- the reaction mixture (b) at the start of production (hereinafter sometimes referred to as the initial reaction mixture) is not particularly limited as long as it is obtained from the raw material mixture (a).
- the concentration of the unreacted sulfiding agent is preferably 30% or less, more preferably 20% or less, further preferably 10% or less, with respect to the concentration of the sulfiding agent in the raw material mixture (a). The following is particularly preferable, and 3% or less is particularly preferable.
- the concentration of the unreacted sulfidizing agent in the initial reaction mixture is the same as that in the raw material mixture (a).
- the concentration of the unreacted sulfidizing agent is the unreacted sulfide contained in 1 kg of the reaction mixture (raw material mixture (a), initial reaction mixture, or reaction mixture (b)). Expressed in moles of agent.
- the concentration of the unreacted dihalogenated aromatic compound described later is represented by the number of moles of the unreacted dihalogenated aromatic compound contained in 1 kg of the reaction mixture or the like.
- the sulfur component of the unreacted sulfiding agent contained per kilogram of the initial reaction mixture is preferably 0.15 mol or less. More preferably, it is 0.10 mol or less, 0.05 mol or less is further more preferable, 0.025 mol or less is especially preferable, and 0.015 mol or less is still more preferable.
- the concentration of the unreacted dihalogenated aromatic compound in the initial reaction mixture the arylene unit of the unreacted dihalogenated aromatic compound contained per kilogram of the initial reaction mixture is 0.15 mol or less. preferable.
- the concentration of the unreacted sulfidizing agent and dihalogenated aromatic compound in the initial reaction mixture within the above range, the production rate of cyclic PAS in the reaction mixture (b) increases and tends to stabilize. It is in.
- the initial reaction mixture at the start of production for example, a mixture obtained by heating and reacting the raw material mixture (a) in a container different from the reaction container used in the method for producing cyclic PAS of the embodiment of the present invention is transferred.
- B-1 a product obtained by supplying the reaction mixture (a) to a reaction vessel in advance and heating and reacting in a batch system (b-2), or at least an organic polar solvent in advance in the reaction vessel
- the operation of introducing and supplying the raw material mixture (a) into the reaction vessel and the operation of extracting a part of the reaction mixture in the reaction vessel from the reaction vessel are performed in parallel, and the substrate concentration is in a certain range as described above. Examples (b-3) obtained up to this point can be exemplified.
- (b-1) or (b-2) is preferred, and (b-2) is more preferred.
- (b-2) is employed, it is not necessary to prepare a reaction vessel separately or transfer the liquid, and the initial reaction mixture (b) tends to be obtained in an extremely short time compared to (b-3). It is particularly preferable because it is industrially efficient.
- the operation (A) for supplying the raw material mixture (a) into the reaction vessel containing the reaction mixture (b) generated from the raw material mixture (a) is the same as the operation (A).
- An operation (B) for extracting a part of the reaction mixture (b) in the reaction vessel from the reaction vessel and an operation (C) for heating the inside of the reaction vessel are continuously performed. Any method may be applied to these operations (A) and (B) as long as the reaction mixture (b) can be obtained continuously.
- the term “continuous” as used herein includes not only a configuration in which both operations are continuously continued, but also a configuration in which at least one operation is continued intermittently, for example, an aspect in which both operations are continuously performed alternately. .
- the additional addition of the raw material mixture (a), that is, the supply (A) and the operation (B) of extracting the reaction mixture (b) are continuously performed, and the amount of the reaction mixture (b) is determined by the volume of the reaction vessel.
- the method of the present invention is used. Compared with the low production rate of cyclic PAS, since the raw material mixture (a) is charged and a time is required for the temperature raising process every time the reaction is performed, the productivity of cyclic PAS becomes low. Further, when only the operation (A) is performed and (B) is not performed, the production rate of the cyclic PAS is improved as described above, but the productivity of the cyclic PAS is low due to the limit of the volume of the reaction vessel. Become. Therefore, in order to produce a cyclic PAS with a high production rate and productivity, it is extremely important to perform the operations (A) and (B) continuously.
- Examples of the method of continuously performing the operation (A) and the operation (B) in the embodiment of the present invention include a method of performing each operation alternately at different timings, or a method of performing each operation simultaneously. Alternatively, there may be a time when neither operation is performed, a time when both operations are performed, and a time when only one operation is performed. From the viewpoint that the productivity of the cyclic PAS can be improved by maintaining the amount of the reaction mixture (b) in the reaction vessel constant in the vicinity of the maximum allowable amount of the reaction vessel, there is a method of performing each operation simultaneously. preferable.
- a method of continuously performing the operation (A) and the operation (B) a method of performing each operation intermittently, a method of performing each operation continuously, or performing one operation intermittently and continuously performing the other.
- a method in which the above is continuously performed is preferable.
- a method in which the operation (A) and the operation (B) are performed simultaneously and continuously can be preferably employed. In this case, it is easy to continuously obtain a cyclic PAS having a constant quality with high productivity.
- the quantity of the reaction mixture (b) in reaction container in manufacture of cyclic PAS of embodiment of this invention is the quantity from which reaction mixture (b) exists in reaction container and becomes below the volume of reaction container.
- the reaction mixture (b) there is no particular limitation as long as it can be maintained, and it may be kept constant or varied.
- “the amount of the reaction mixture (b) in the reaction vessel is constant” means that the fluctuation range of the amount of the reaction mixture (b) in the reaction vessel is the amount of the reaction mixture (b) before the change. Is within ⁇ 30% with reference to.
- the fluctuation range is more preferably within ⁇ 20%, further preferably within ⁇ 15%, even more preferably within ⁇ 10%, and particularly preferably within ⁇ 5%.
- the reaction mixture (b) exists in the reaction vessel and the volume of the reaction vessel There is no particular limitation as long as the following amounts can be maintained, and they may be different or the same. However, they are preferably the same, and in that case, the amount of the reaction mixture (b) in the reaction vessel can be kept constant, which is preferable from the viewpoint of the productivity of the cyclic PAS as described above.
- the supply amount of the raw material mixture (a) in the operation (A) and the extraction amount of the reaction mixture (b) in the operation (B) are the same.
- a method in which the amount of the reaction mixture (b) in the reaction vessel is kept constant at the same time and continuously can also be preferably employed.
- the reaction system is a continuous reaction system, and in a steady state, the reaction mixture (b) is maintained at a constant composition. Therefore, it is easy to continuously obtain a cyclic PAS with a high production rate and a constant quality. Become a method.
- the supply amount of the raw material mixture (a) in the operation (A) usually means the weight of the raw material mixture (a) in the reaction vessel.
- the supply is intermittent, it is expressed by the weight per one supply, and when the supply is continuous, it is expressed by the weight per unit time.
- the amount of the reaction mixture (b) extracted in the operation (B) usually means the weight of the reaction mixture (b) extracted from the reaction vessel. When there is a component that volatilizes after extraction, it indicates the total including the weight of that component.
- the extraction is intermittent, it is expressed by the weight per extraction, and when the extraction is continuous, it is expressed by the weight per unit time.
- the supply amount of the raw material mixture (a) in these operations (A) and the extraction amount of the reaction mixture (b) in the operation (B) are the volume of the reaction vessel used, the type and amount of the raw material used, the reaction temperature, etc. However, it is difficult to define it unconditionally, but the relative relationship between the supply amount, the withdrawal amount, and the amount of the reaction mixture (b) in the reaction vessel is expressed as the average residence time of the reaction mixture (b). be able to.
- the average residence time means [average weight of the reaction mixture (b) in the reaction vessel] / [unit when the supply amount of the raw material mixture (a) and the extraction amount of the reaction mixture (b) become the same.
- the feed weight of the raw material mixture (a) per hour or the withdrawal weight of the reaction mixture (b) per unit time For example, if the average weight of the reaction mixture (b) in the reaction vessel is 40 kg, and the feed weight of the raw material mixture (a) and the withdrawal weight of the reaction mixture (b) per unit time are 20 kg, The residence time is 2 hours.
- the supply weight of the raw material mixture (a) per unit time in this relational expression, or the per unit time is calculated from the time until the end of the extraction and the supply amount of the raw material mixture (a) or the extraction amount of the reaction mixture (b), with the initial supply as a base point. For example, if it takes 12 hours from the first supply to the end of extraction, and the supply amount of the raw material mixture (a) is 240 kg during this period, the supply weight of the raw material mixture (a) per unit time Or the extraction weight of the reaction mixture (b) per unit time is 20 kg.
- the average residence time depends on various conditions such as the type and amount of raw materials used or the reaction temperature, and thus cannot be specified unconditionally, but is preferably 0.1 hours or more, more preferably 0.5 hours or more. On the other hand, the average residence time is not particularly limited, but the reaction proceeds sufficiently even within 40 hours, preferably within 10 hours, more preferably within 6 hours.
- the raw material mixture (a) in the operation (A), is supplied into the reaction vessel.
- the property of the raw material mixture (a) is a solution or slurry
- the supply is caused by its own weight drop, This can be done either by pressure difference or by a pump.
- the raw material mixture (a) When the raw material mixture (a) is supplied by falling under its own weight, for example, a pipe for supplying the raw material mixture (a) is routed from above the reaction vessel, and a valve is installed between the pipe and the reaction vessel.
- the supply amount can be adjusted by controlling.
- the pressure in the reaction vessel exceeds normal pressure.
- the vessel containing the raw material mixture (a) and the reaction vessel are pressure-equalized by a known method. With its own weight fall can be adopted.
- an inert gas such as nitrogen gas
- pressurization of the raw material mixture (a) by the vapor pressure of the raw material mixture (a), or the like can be used.
- the pump to be used cannot be uniquely determined because the suitability varies depending on the physical properties and supply conditions of the raw material mixture (a), but pumps classified into positive displacement pumps and turbo pumps are preferable. Among these, a rotary pump is preferable as the positive displacement pump, and more specifically, a gear pump is preferable.
- the turbo pump is preferably a centrifugal pump, more specifically a spiral pump, more specifically a canned motor pump, a magnet pump, or the like. Of the above pumps, any pump having a mechanical seal structure can be supplied without any problem even when the raw material mixture (a) is a slurry.
- the pressure in the reaction vessel exceeds the normal pressure, but in this case, the above pump can be used.
- the raw material mixture (a) can be stably supplied, and the pressure in the reaction vessel can be increased to a pressure exceeding the normal pressure.
- a vessel containing the raw material mixture (a) (a container connected to the reaction vessel and supplying the raw material mixture (a) to the reaction vessel, also referred to as a supply vessel) is provided with a circulation line through the pump.
- the raw material mixture (a) is circulated to the vessel, and the flow rate of the branch line is controlled by controlling the valve opening degree of the branch line provided from the circulation line via the valve.
- a method of supplying the raw material mixture (a) can also be preferably employed. That is, the supply container is provided with a circulation line that is connected to the supply container and circulates at least a part of the raw material mixture (a) with the supply container using the pump, and the raw material mixture that flows through the circulation line ( A part of a) may be supplied into the reaction vessel.
- the uniformity of the slurry-like raw material mixture (a) is easily maintained even in the line, and the composition of the supplied raw material mixture (a) is likely to be uniform.
- the reaction mixture (b) is extracted from the reaction vessel, and the extraction can be performed by dropping by its own weight, a pressure difference, or a pump.
- a valve can be installed at the opening of the reaction vessel, and the valve opening can be controlled to adjust the extraction amount.
- the pressure in the reaction vessel exceeds the normal pressure as described later.
- the reaction vessel containing the reaction mixture (b) and the extracted reaction mixture (b) are supplied.
- the self-weight fall can be adopted by equalizing the pressure of the container (the container to which the reaction mixture (b) extracted from the reaction container (b) is supplied, also referred to as a receiving container) by a known method.
- an inert gas such as nitrogen gas
- pressurization of the reaction mixture (b) by the vapor pressure of the reaction mixture (b), or the like can be used.
- the pump to be used is uniquely determined because the properties and supply conditions of the reaction mixture (b) are more suitable.
- pumps classified into positive displacement pumps and turbo pumps can be exemplified.
- the positive displacement pump a rotary pump is preferable, and more specifically, a gear pump is preferable.
- the turbo pump a centrifugal pump is preferable, and more specifically, a canned motor pump or a magnet pump, which is a kind of spiral pump, is preferable.
- the reaction mixture (b) contains a metal halide as a by-product.
- the metal halide precipitates insoluble, and the reaction mixture ( b) may become a slurry. Accordingly, when such a by-product metal halide precipitates, the reaction mixture (b) is sufficiently stirred in the reaction vessel to increase the uniformity when the reaction mixture (b) is withdrawn. It is preferable to disperse the particles uniformly.
- a pump is used for extracting the reaction mixture (b) from which by-product metal halide precipitates, it is preferable to use a pump having a mechanical seal structure among the above pumps. It is preferable to use a motor pump.
- the pressure in the reaction vessel exceeds the normal pressure.
- the same pump as described above can be used.
- a slurry seal type canned motor pump can be particularly preferably used.
- the reaction mixture (b) can be stably extracted with high uniformity, and the inside of the reaction vessel can be increased to a pressure exceeding the normal pressure.
- a reaction vessel containing the reaction mixture (b) is provided with a circulation line passing through the pump and a branch line branching from the circulation line via a valve.
- a method of extracting an arbitrary amount of the reaction mixture (b) from the reaction vessel while adjusting the flow rate of the branch line by controlling the valve opening of the branch line can also be preferably employed. That is, the reaction vessel is provided with a circulation line that is connected to the reaction vessel and circulates at least part of the reaction mixture (b) between the reaction vessel and the reaction vessel using the pump, and the reaction mixture ( A part of b) may be supplied into the reaction vessel.
- the uniformity of the slurry-like reaction mixture (b) containing a precipitation component such as a metal halide is more easily maintained even in the line, and the uniformity at the time of extraction is also increased.
- the reaction vessel is connected to the supply vessel of the raw material mixture (a) and / or the receiving vessel to which the extracted reaction mixture (b) is supplied through a pressure equalization line to equalize the pressure. It is also preferable to do.
- the pressure equalization line refers to a gas flow path that connects both containers in order to uniformly control the pressure in each container.
- the pressure equalization line does not substantially allow the mixture in each container to flow. In this case, the liquid transfer between the containers becomes smooth, and the operation (A) and the operation (B) can be easily controlled. Known methods can be applied to connect the respective containers.
- reaction mixture (b) extracted from the reaction vessel can be transferred to a receiving vessel, which is another vessel, through a pipe and recovered.
- a receiving vessel which is another vessel, through a pipe and recovered.
- an operation (D) for further heating the reaction mixture (b) may be performed to obtain the reaction mixture (c).
- the concentration of the unreacted sulfidizing agent in the reaction mixture (b) can vary depending on the operations (A) and (B). It is preferably always maintained at 30% or less, more preferably 20% or less, further preferably 10% or less, particularly preferably 5% or less, and preferably 3% or less with respect to the concentration of the sulfidizing agent in the mixture (a). Particularly preferred.
- the concentration of the unreacted sulfiding agent in the reaction mixture (b) is completely consumed, the concentration of the unreacted sulfiding agent is 0% with respect to the concentration of the sulfiding agent in the raw material mixture (a). Although it can be said that it is a typical state, it is often 0.1% or more as the lower limit in carrying out the actual reaction.
- the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture (b) may vary depending on the operations (A) and (B), but in the raw material mixture (a)
- the concentration of the dihalogenated aromatic compound is preferably always maintained at 30% or less, more preferably 20% or less, further preferably 10% or less, particularly preferably 5% or less, and particularly preferably 3% or less.
- the concentration of the unreacted dihalogenated aromatic compound is 0 with respect to the concentration of the sulfidizing agent in the raw material mixture (a). %, Which is an ideal state, but is often 0.1% or more as the lower limit for the actual reaction.
- the sulfur component of the unreacted sulfidizing agent contained per kilogram of the reaction mixture (b) is 0.15 mol or less.
- the sulfur component of the unreacted sulfidizing agent contained per kilogram of the reaction mixture (b) is 0.15 mol or less.
- it is 0.10 mol or less, 0.05 mol or less is further more preferable, 0.025 mol or less is especially preferable, and 0.015 mol or less is still more preferable.
- the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture (b) the arylene unit of the unreacted dihalogenated aromatic compound contained per kilogram of the reaction mixture (b) is 0.15 mol or less.
- the concentration of the unreacted sulfidizing agent and dihalogenated aromatic compound in the reaction mixture (b) is 0.10 mol or less, 0.05 mol or less is further more preferable, 0.025 mol or less is especially preferable, and 0.015 mol or less is still more preferable.
- the concentration of the unreacted sulfiding agent and dihalogenated aromatic compound in the reaction mixture (b) can vary depending on the operation (A) and the operation (B) as described above, but the method and control thereof are adjusted. Therefore, it can be maintained within the above preferable range.
- the operation (A) and the operation (B) are carried out by using the same feed amount of the raw material mixture (a) in the operation (A) and the extraction amount of the reaction mixture (b) in the operation (B).
- the unreacted sulfidizing agent and dihalogenated aromatic compound in the reaction mixture (b) are used in the steady state. It becomes possible to make the density
- the feed amount of the raw material mixture (a) in the operation (A) and the method of adjusting the extraction amount of the reaction mixture (b) in operation (B) can be illustrated.
- the concentration of the unreacted sulfidizing agent and dihalogenated aromatic compound in the reaction mixture (b) is 30% or less of the concentration of the sulfidizing agent in the raw material mixture (a), and the reaction mixture (b)
- the sulfur component of the unreacted sulfiding agent and the arylene unit of the dihalogenated aromatic compound contained in each kilogram at 0.15 mol or less, the production rate of cyclic PAS in the reaction mixture (b) is It tends to improve more easily. This is presumed to be due to the fact that the monomer concentration was kept low, resulting in pseudo-dilution conditions, and the selectivity of the cyclization reaction was improved.
- the concentration of the sulfidizing agent in the reaction mixture is determined by using, for example, an ion chromatography technique equipped with an electrical conductivity detector or an electrochemical detector. It can be calculated by quantifying the amount of.
- an ion chromatography technique equipped with an electrical conductivity detector or an electrochemical detector. It can be calculated by quantifying the amount of.
- hydrogen peroxide solution is added to the sample to oxidize sulfide ions contained in the sample, and then analysis using an electrical conductivity detector
- a method for calculating the amount of sulfate ions generated by oxidation of sulfide ions can be exemplified, and the concentration of the sulfidizing agent in the reaction mixture can be calculated from the calculated amount of sulfate ions.
- the concentration of the dihalogenated aromatic compound in the reaction mixture is determined by, for example, quantifying the amount of the dihalogenated aromatic compound in the reaction mixture using a gas chromatography technique. It is possible to calculate.
- an operation (D) for further heating the extracted reaction mixture (b) may be performed, and in this case, the reaction mixture (c) is obtained.
- this operation is aimed at consuming the unreacted raw material in the extracted reaction mixture (b), and the reaction which the said raw material consumes substantially completely
- Conditions are preferable, for example, a method in which heating is continued for 0.1 to 10 hours can be exemplified, heating is preferably continued for 0.1 to 3 hours, or the heating temperature is raised within a preferable range described later. Etc. can be exemplified.
- the raw material mixture (a) is supplied into the reaction vessel containing the reaction mixture (b) as described above (operation (A)), and the reaction vessel is heated. (Operation (C))
- the reaction is carried out, and the temperature in this reaction is preferably higher than the reflux temperature of the reaction mixture (b) under normal pressure.
- This desirable temperature cannot be uniquely determined because it varies depending on the kind and amount of the sulfidizing agent, dihalogenated aromatic compound and organic polar solvent used in the reaction, but is usually 120 ° C. or higher, preferably 180 ° C. or higher.
- it is 220 degreeC or more, More preferably, it can be 225 degreeC or more.
- the reaction consumption of the sulfidizing agent and dihalogenated aromatic compound, which are raw material components proceeds rapidly to produce cyclic PAS and linear PAS, and the reaction tends to proceed in a short time.
- the normal pressure is a pressure in the vicinity of the standard state of the atmosphere, and the standard state of the atmosphere is an atmospheric pressure condition in which the temperature is about 25 ° C. and the absolute pressure is about 101 kPa.
- the reflux temperature is the temperature at which the liquid component of the reaction mixture repeats boiling and condensation.
- the reaction vessel examples thereof include a method of setting the internal pressure to a pressure exceeding the normal pressure and a method of using the reaction vessel as a sealed vessel.
- the pressure in the reaction vessel containing the reaction mixture (b) is not particularly limited, and the pressure is determined by the raw materials constituting the reaction mixture in the reaction vessel, the composition thereof, and Since it varies depending on the reaction temperature and the like, it cannot be uniquely defined, but a preferable lower limit of pressure is 0.05 MPa or more, more preferably 0.3 MPa or more in gauge pressure.
- the lower limit of the preferable pressure at such a reaction temperature is 0.25 MPa or more, more preferably 0. 3 MPa or more can be illustrated.
- a preferable upper limit of pressure 10 MPa or less, More preferably, 5 MPa or less can be illustrated.
- the time required to cause the linear polyarylene sulfide, the sulfidizing agent and the dihalogenated aromatic compound to react with each other tends to be shortened.
- the extracted reaction mixture (b) can be transferred to another container through a pipe and collected, and for the purpose of reducing the change in the composition and state of the reaction mixture (b) at that time, You may adjust the pressure difference between the said another container.
- the gauge pressure is a relative pressure based on the atmospheric pressure, and is equivalent to a pressure difference obtained by subtracting the atmospheric pressure from the absolute pressure.
- the solid and soluble components present in the reaction mixture at a temperature sufficient to dissolve the cyclic PAS and linear PAS in the reaction mixture, preferably above 200 ° C., more preferably above 230 ° C. Separation by solid-liquid separation to recover solution components containing at least cyclic PAS, linear PAS, and organic polar solvent, and operations such as distillation of a part or most of the organic polar solvent from this solution component as necessary
- the cyclic PAS is mixed with an organic polar solvent having low solubility in the PAS component and preferably in contact with a solvent having a solubility in the by-product salt, if necessary, under heating.
- Solvents that are poorly soluble in the PAS component and miscible with the organic polar solvent, preferably soluble in the by-product salt, are generally relatively polar solvents.
- the preferred solvent varies depending on the type of organic polar solvent and by-product salt used, and thus cannot be limited.For example, water, alcohols represented by methanol, ethanol, propanol, isopropanol, butanol, and hexanol, and acetone are representative. Ketones, and acetates typified by ethyl acetate and butyl acetate. From the viewpoints of availability and economy, water, methanol and acetone are preferable, and water is particularly preferable.
- the PAS component can be recovered as a mixture of cyclic PAS and linear PAS using a known solid-liquid separation method.
- the solid-liquid separation method include separation by filtration, centrifugation, and decantation. Note that a series of these treatments can be repeated several times as necessary, which further reduces the amount of organic polar solvent and by-product salt contained in the mixed solid of cyclic PAS and linear PAS. Tend to.
- a method of treatment with the above-mentioned solvent there is a method of mixing a solvent and a reaction mixture, and it is possible to appropriately stir or heat as necessary.
- a solvent there is no restriction
- limiting in particular in the temperature at the time of processing by a solvent 20 degreeC or more is preferable and 50 degreeC or more is still more preferable.
- 220 degrees C or less is preferable and 200 degrees C or less is still more preferable.
- by-product salt can be easily removed, and the treatment can be performed at a relatively low pressure, which is preferable.
- water is preferably distilled water or deionized water.
- Solvents include formic acid, acetic acid, propionic acid, butyric acid, chloroacetic acid, dichloroacetic acid, acrylic acid, crotonic acid, benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid as required It is also possible to use an aqueous solution containing an organic acidic compound and its alkali metal salt, alkaline earth metal salt, inorganic acidic compound such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid, silicic acid and the like and a compound selected from ammonium ions. When the mixed solid of cyclic PAS and linear PAS obtained after this treatment contains the solvent used for the treatment, it is possible to remove the solvent by drying or the like as necessary.
- cyclic PAS is recovered as a mixture with linear PAS (hereinafter also referred to as PAS mixture).
- PAS mixture a mixture with linear PAS
- a separation method using the difference in solubility between cyclic PAS and linear PAS, more specifically, high solubility in cyclic PAS An example is a method of obtaining cyclic PAS as a solvent-soluble component by bringing a solvent having poor solubility in linear PAS into contact with a PAS mixture under heating as necessary under conditions for dissolving cyclic PAS.
- the molecular weight of linear PAS is difficult to dissolve in a solvent capable of dissolving cyclic PAS, which will be described later, preferably substantially.
- the molecular weight is preferably such that it does not dissolve.
- the weight average molecular weight can be 2,500 or more, preferably 5,000 or more, and more preferably 10,000 or more.
- the solvent used for separation of cyclic PAS and linear PAS is not particularly limited as long as it can dissolve cyclic PAS, but cyclic PAS dissolves but linear PAS dissolves in the environment where the dissolution is performed.
- a difficult solvent is preferable, and a solvent that does not substantially dissolve linear PAS is more preferable.
- the pressure of the reaction system when the PAS mixture is brought into contact with the solvent is preferably normal pressure or slight pressure, and particularly preferably normal pressure.
- Such a pressure reaction system has the advantage that the components of the reactor for constructing it are inexpensive. From this point of view, it is desirable that the reaction system pressure avoid pressurizing conditions that require an expensive pressure vessel.
- solvents to be used those which do not substantially cause undesirable side reactions such as decomposition and crosslinking of the PAS component are preferable.
- examples of a preferable solvent when the operation of bringing the PAS mixture into contact with the solvent is performed under atmospheric pressure reflux conditions include hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, cyclopentane, benzene, toluene, and xylene.
- Halogen solvents such as chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene, and 2,6-dichlorotoluene, ether solvents such as diethyl ether, tetrahydrofuran, and diisopropyl ether
- polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, trimethyl phosphoric acid, N, N-dimethylimidazolidinone, and methyl ethyl ketone.
- the non-oxidizing atmosphere is an atmosphere having a gas phase oxygen concentration of 5% by volume or less, preferably 2% by volume or less, more preferably substantially free of oxygen, that is, an inert gas such as nitrogen, helium, or argon.
- an inert gas such as nitrogen, helium, or argon.
- a nitrogen atmosphere is preferable in terms of economy and ease of handling.
- the temperature at which the PAS mixture is brought into contact with the solvent is not particularly limited. Generally, the higher the temperature, the more the dissolution of the cyclic PAS in the solvent tends to be promoted. However, when the molecular weight of the linear PAS is low, the dissolution of the linear PAS Also tend to be promoted. When the molecular weight of the linear PAS is the above-described preferred molecular weight, the difference in solubility with the cyclic PAS increases, so that even if the PAS mixture is contacted with the solvent at a high temperature, the cyclic PAS and the linear PAS are increased. Tends to be suitably separated.
- the upper limit temperature is preferably set to the reflux condition temperature under the atmospheric pressure of the solvent to be used.
- the specific temperature range in which the PAS mixture is brought into contact with the solvent may be, for example, 20 ° C. or higher, preferably 30 ° C. or higher, when the above-described preferable solvent is used.
- 150 degrees C or less Preferably 100 degrees C or less can be illustrated.
- the time for which the PAS mixture is brought into contact with the solvent varies depending on the type of solvent used, the temperature, etc., and therefore cannot be uniquely limited. For example, it can be exemplified by 1 minute to 50 hours. In such a range, the cyclic PAS is dissolved in the solvent. Tend to be sufficient.
- the method of bringing the PAS mixture into contact with the solvent is not particularly limited as long as a known general method is used.
- the PAS mixture and the solvent are mixed, and if necessary, the solution part is recovered after being stirred.
- Any method can be used, such as a method of dissolving cyclic PAS in a solvent simultaneously with showering a solvent in the PAS mixture on the filter, or a method based on the principle of Soxhlet extraction.
- the amount of the solvent used when the PAS mixture and the solvent are brought into contact with each other is not particularly limited. When the bath ratio is in such a range, the PAS mixture and the solvent are easily mixed uniformly, and the cyclic PAS tends to be sufficiently dissolved in the solvent.
- a larger bath ratio is advantageous for dissolving cyclic PAS in a solvent, but if it is too large, no further effect can be expected, and conversely an economic disadvantage due to an increase in the amount of solvent used may occur. is there.
- the Soxhlet extraction method in principle, provides an effect similar to that obtained when the contact of the PAS mixture and the solvent is repeated, and in this case, a sufficient effect can often be obtained with a small bath ratio.
- the solution part is recovered using a known solid-liquid separation method. It is preferable. Examples of the solid-liquid separation method include separation by filtration, centrifugation, and decantation. By removing the solvent from the solution thus separated, the cyclic PAS can be recovered. On the other hand, for the solid component, when the cyclic PAS still remains, it is possible to obtain the cyclic PAS with higher yield by repeating contact with the solvent and recovery of the solution again. Further, when almost no cyclic PAS remains, it can be suitably recycled as a high-purity linear PAS by removing the residual solvent.
- the removal of the solvent can be exemplified by, for example, a method in which the above solution is heated and treated at a normal pressure or lower, or a solvent removal using a film. From the viewpoint of obtaining cyclic polyarylene sulfide more efficiently and efficiently, a method of removing the solvent by heating the above solution at normal pressure or lower is preferable.
- the solution containing cyclic PAS obtained as described above may contain a solid depending on the temperature. In this case, the solid belongs to the cyclic polyarylene sulfide mixture.
- the solvent it is desirable to recover together with components soluble in the solvent at the time of removal, so that cyclic PAS can be obtained with good yield.
- the temperature at which the solvent is removed by heating depends on the characteristics of the solvent used, it cannot be uniquely limited, but it can usually be 20 ° C. or higher, preferably 40 ° C. or higher. Moreover, it can be 150 degrees C or less, Preferably it is 120 degrees C or less.
- the pressure for removing the solvent is preferably normal pressure or lower, which makes it possible to remove the solvent at a lower temperature.
- the reaction mixture obtained in the embodiment of the present invention includes cyclic PAS, linear PAS, and organic polar solvent, and other components such as unreacted sulfidizing agent, dihalogenated aromatic compound, water, by-product salt, etc. As described above, may be included.
- cyclic PAS tends to be dissolved in an organic polar solvent over a wide temperature range.
- linear PAS differs greatly in dissolution behavior from cyclic PAS. Specifically, most of the linear PAS tends to exist as a solid in the reaction mixture in a temperature range of 200 ° C. or lower.
- cyclic PAS and linear PAS can be separated by simple solid-liquid separation.
- the upper limit of the specific temperature range in which cyclic PAS and linear PAS can be separated by such solid-liquid separation can be exemplified by 200 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 120 ° C. or lower.
- 10 degreeC or more can be illustrated, 20 degreeC or more is preferable, 50 degreeC or more is more preferable, and 80 degreeC or more is still more preferable.
- the linear PAS contained in the reaction mixture tends to exist as a solid content, and the above-described preferred weight average molecular weight linear PAS tends to be a solid content under these conditions.
- cyclic PAS in the reaction mixture has a strong tendency to be soluble in an organic polar solvent, and in particular, cyclic PAS in the preferred range in which the number of repeating units m of cyclic PAS is as described above is Strong tendency to dissolve in organic polar solvents.
- the viscosity of the reaction mixture tends to be low, the solid-liquid separation operation is easy, and the separation between the solid component and the solution component tends to be excellent.
- the solution component obtained by solid-liquid separation of the reaction mixture described above includes cyclic PAS.
- the method for removing the organic polar solvent include a method of removing by distillation, a method of contacting with a second solvent miscible with the organic polar solvent, and the like.
- a method of heating the filtrate component to preferably 20 to 250 ° C., more preferably 40 to 200 ° C., further preferably 100 to 200 ° C., and still more preferably 120 to 200 ° C.
- the non-oxidizing atmosphere refers to an atmosphere in which the oxygen concentration in the gas phase is 5% by volume or less, preferably 2% by volume or less, and more preferably contains substantially no oxygen, ie, nitrogen, helium, argon or the like. This indicates an active gas atmosphere, and among these, a nitrogen atmosphere is particularly preferred from the viewpoint of economy and ease of handling.
- a specific method for obtaining cyclic PAS by solvent replacement of the filtrate component with a second solvent is to contact the second solvent in which cyclic PAS does not substantially dissolve or is difficult to dissolve.
- a method for recovering a solid component containing cyclic PAS can be exemplified.
- As a more specific method of contacting with the second solvent it is possible to exemplify adopting a method shown in (8) described later.
- the cyclic polyarylene sulfide thus obtained has a sufficiently high purity and can be suitably used for various applications. However, the post-treatment described below is further applied to make it more desirable. High purity cyclic PAS can be obtained.
- the cyclic PAS obtained by the operations up to (7) above may contain impurity components contained in the PAS mixture depending on the characteristics of the solvent used.
- impurity components contained in the PAS mixture depending on the characteristics of the solvent used.
- a second solvent that dissolves the impurities but does not substantially dissolve the cyclic PAS or hardly dissolves the cyclic PAS, Often it can be selectively removed.
- the reaction system pressure when the cyclic PAS mixture or the filtrate component obtained in the above (7-2) is contacted with the second solvent is preferably normal pressure or slight pressure, and particularly preferably normal pressure.
- Such a pressure reaction system has the advantage that the members for constructing it are inexpensive. From this point of view, it is desirable that the reaction system pressure avoid pressurizing conditions that require an expensive pressure vessel.
- the preferred solvent as the second solvent those which do not substantially cause undesirable side reactions such as decomposition and crosslinking of cyclic PAS are preferable.
- Carboxylic acid ester solvents such as Le, and water can be exemplified.
- methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, pentane, hexane, heptane, octane, cyclohexane, cyclopentane, acetone, methyl acetate, ethyl acetate, and water are preferred.
- Methanol, ethanol, propanol , Ethylene glycol, pentane, hexane, heptane, octane, cyclohexane, acetone, ethyl acetate, and water are particularly preferred.
- These solvents can be used as one kind or a mixture of two or more kinds.
- the temperature at which the cyclic PAS is brought into contact with the second solvent is not particularly limited, but the upper limit temperature is preferably set to the reflux condition temperature under normal pressure of the second solvent to be used.
- the preferred second solvent described above for example, 20 to 100 ° C. can be exemplified as a preferable temperature range, and more preferably 25 to 80 ° C. can be exemplified.
- the time for which the cyclic PAS is brought into contact with the second solvent varies depending on the type of solvent used, the temperature, etc., and therefore cannot be uniquely limited, but examples include 1 minute to 50 hours. Within such a time range, the impurities in the cyclic PAS tend to be sufficiently dissolved in the second solvent.
- a method for bringing the cyclic PAS into contact with the second solvent a method in which the solid cyclic PAS and the second solvent are mixed by stirring as necessary, and the cyclic PAS solid on various filters is mixed with the second solvent.
- the method of dissolving the impurities in the second solvent at the same time of showering the solvent, the method of using Soxhlet extraction using the second solvent, and the cyclic PAS slurry containing the solution-like cyclic PAS or the solvent as the second solvent For example, a method in which cyclic PAS is deposited in the presence of a second solvent by contacting them can be used.
- the method of bringing a cyclic PAS slurry containing a solvent into contact with a second solvent is an effective method because the cyclic PAS obtained after the operation has a high purity.
- the solid-liquid separation method include separation by filtration, centrifugation, and decantation. If impurities still remain in the cyclic PAS obtained after the solid-liquid separation, the cyclic PAS and the second solvent can be contacted again to further remove the impurities.
- cyclic PAS having a single m is obtained as a single crystal, it has an extremely high melting temperature.
- cyclic PAS is easy to obtain a mixture having different m. It is characterized by a low melting temperature of PAS. This expresses an excellent feature that, for example, the heating temperature when the cyclic PAS is melted and used can be lowered.
- Resin composition blended with cyclic PAS of embodiment of the present invention can be blended with various resins and used.
- the resin composition blended with the above has a strong tendency to exhibit excellent fluidity at the time of melt processing, and tends to be excellent in retention stability.
- Such improved properties, particularly fluidity express the characteristics of excellent melt processability even when the heating temperature during melt processing of the resin composition is low, so that extrusion molding of injection molded products, fibers, films, etc. This is a great merit in that it improves the melt processability when processed into a product.
- the cyclic PAS of embodiment of this invention is 0.1 weight part or more with respect to 100 weight part of various resin, Preferably it is 0.8.
- blending 5 parts by weight or more it is possible to obtain a remarkable improvement in characteristics.
- the resin composition may further contain a fibrous and / or non-fibrous filler.
- the blending amount can be 0.5 parts by weight or more, preferably 1 part by weight or more with respect to 100 parts by weight of the various resins. Moreover, it can be 400 weight part or less, Preferably it is 300 weight part or less, More preferably, it is 200 weight part or less, More preferably, it is 100 weight part or less.
- the kind of filler any filler such as fibrous, plate-like, powdery, and granular can be used.
- these fillers include layered silicates such as glass fiber, talc, wollastonite, montmorillonite, and synthetic mica, and glass fiber is particularly preferable.
- the type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like.
- said filler can also be used in combination of 2 or more types.
- said filler used for embodiment of this invention processes the surface with a well-known coupling agent (For example, a silane coupling agent, a titanate coupling agent, etc.) and other surface treatment agents. It can also be used.
- the glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.
- the resin composition in order to maintain the thermal stability of the resin composition, it is possible to include one or more heat-resistant agents selected from phenolic and phosphorus compounds in the resin composition.
- the blending amount of the heat-resistant agent is preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more with respect to 100 parts by weight of the various resins, from the viewpoint of the heat resistance improvement effect. From the viewpoint of gas components generated during molding, it is preferably 5 parts by weight or less, particularly 1 part by weight or less with respect to 100 parts by weight of the various resins.
- the resin composition includes the following compounds, that is, coupling agents such as organic titanate compounds and organic borane compounds, polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organic phosphorus compounds.
- Plasticizers such as base compounds, crystal nucleating agents such as talc, kaolin, organophosphorus compounds, and polyether ether ketone, metal soaps such as montanic acid waxes, lithium stearate, and aluminum stearate, ethylenediamine, stearin Release agents such as acid and sebacic acid heavy compound and silicone compounds, anti-coloring agents such as hypophosphite, other lubricants, anti-ultraviolet agents, coloring agents, flame retardants, foaming agents, etc.
- the usual additives can be blended. All of the above compounds tend to exhibit their effects effectively when added in an amount of less than 20 parts by weight, preferably 10 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the various resins.
- the method for producing the resin composition comprising the cyclic PAS as described above is not particularly limited.
- the cyclic PAS, various resins, and other fillers and various additives as necessary may be added in advance.
- a method of melting and kneading with a generally known melt mixer such as a single-screw or twin-screw extruder, Banbury mixer, kneader, mixing roll or the like at a melting point of various resins and cyclic PAS, or a resin composition material
- a method of removing the solvent after mixing in the medium is used.
- cyclic PAS is a simple substance of the cyclic PAS, that is, when m of the formula (A) is a single one, or when a mixture of different m is used having a high crystallinity and a high melting point.
- the crystallization is suppressed and the amorphous material is supplied to the melt mixer, or the premelter is set to a melting point or higher of the cyclic PAS, and only the cyclic PAS is melted in the premelter and melt-mixed as a melt.
- a method of supplying to the machine can be adopted.
- the crystalline resin include polyolefin resins such as polyethylene resin, polypropylene resin, and syndiotactic polystyrene, polyvinyl alcohol resin, polyvinylidene chloride resin, polyester resin, polyamide resin, polyacetal resin, polyphenylene sulfide. Resins, polyetheretherketone resins, polyetherketone resins, polyketone resins, polyimide resins and copolymers thereof may be used, and one or more of them may be used in combination. Of these, polyphenylene sulfide resins, polyamide resins, and polyester resins are preferred in terms of heat resistance, moldability, fluidity, and mechanical properties.
- a polyester resin is preferable from the viewpoint of transparency of the obtained molded product.
- a crystalline resin is used as the various resins, there is a tendency to improve the crystallization characteristics in addition to the improvement in fluidity described above.
- polyphenylene sulfide resin is particularly preferable to use as various resins. In this case, it is said that the improvement of the crystallinity and the effect of these effects are significantly suppressed in the injection molding as well as the fluidity. Features tend to develop easily.
- the amorphous resin is not particularly limited as long as it is an amorphous resin that can be melt-molded.
- the glass transition temperature is preferably 50 ° C. or higher, and is 60 ° C. or higher. Is more preferable, it is more preferable that it is 70 degreeC or more, and it is especially preferable that it is 80 degreeC or more.
- the upper limit of the glass transition temperature is not particularly limited, but is preferably 300 ° C. or less, more preferably 280 ° C. or less from the viewpoint of moldability. In the embodiment of the present invention, the glass transition temperature of the amorphous resin is increased under the temperature increase condition of 20 ° C./min from 30 ° C.
- amorphous resin examples include amorphous nylon resin, polycarbonate (PC) resin, polyarylate resin, ABS resin, poly (meth) acrylate resin, poly (meth) acrylate copolymer, polysulfone resin, And at least one selected from polyethersulfone resins, and may be used alone or in combination of two or more.
- polycarbonate (PC) resin having particularly high transparency
- ABS resins transparent ABS resin, polyarylate resin, poly (meth) acrylate resin, poly (meth) acrylate copolymer, and polyether A sulfone resin
- an amorphous resin excellent in transparency as various resins in addition to the improvement in fluidity at the time of melt processing described above, it is possible to express the feature that high transparency can be maintained.
- a cyclic PAS having a different m in the formula (A) as the cyclic PAS.
- a single cyclic PAS that is, a single m of the formula (A)
- such a cyclic PAS tends to have a high melting point.
- the cyclic PAS having a different m in the formula (A) has a melting temperature, although it does not sufficiently melt and disperse in the kneading and tends to become aggregates in the resin or to decrease transparency. This tends to be low, which is effective in improving the uniformity during melt-kneading.
- the resin composition obtained by blending cyclic PAS with various resins obtained above can be molded by any known method such as injection molding, extrusion molding, blow molding, press molding, and spinning. It can be processed into products and used.
- the molded product can be used as an injection molded product, an extrusion molded product, a blow molded product, a film, a sheet, and a fiber.
- the various molded articles thus obtained can be used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, household goods and sanitary goods.
- the said resin composition and a molded article consisting thereof can be recycled.
- a resin composition obtained by pulverizing a resin composition and a molded product comprising the resin composition, preferably in a powder form, and then adding additives as necessary, can be used in the same manner as the resin composition described above. It can also be a molded product.
- the cyclic PAS recovered by the embodiment of the present invention has excellent characteristics as described in the above section (9). It can be suitably used as a prepolymer for obtaining a body.
- the prepolymer may be a cyclic PAS obtained by the cyclic PAS recovery method of the embodiment of the present invention alone, or may contain a predetermined amount of other components.
- the component other than the cyclic PAS is particularly preferably a PAS component such as a linear PAS or a PAS having a branched structure.
- a polyarylene sulfide prepolymer that contains at least the cyclic PAS of the embodiment of the present invention and can be converted into a high degree of polymerization by the method exemplified below is sometimes referred to as a PAS prepolymer.
- the conversion of the cyclic PAS to a high degree of polymerization may be performed under the condition that a high molecular weight product is produced from the cyclic PAS as a raw material.
- the cyclic PAS produced by the cyclic PAS production method according to the embodiment of the present invention may be used.
- a preferable method is a method in which the PAS prepolymer is heated and converted to a high degree of polymerization.
- the heating temperature is preferably a temperature at which the PAS prepolymer melts and is not particularly limited as long as it is such temperature conditions. When the heating temperature is lower than the melt solution temperature of the PAS prepolymer, a long time tends to be required to obtain a PAS having a high molecular weight.
- the temperature at which the PAS prepolymer melts varies depending on the composition and molecular weight of the PAS prepolymer and the environment during heating, it cannot be uniquely indicated.
- the PAS prepolymer is a differential scanning calorimeter. It is possible to grasp the melting solution temperature by analyzing with. If the heating temperature is too high, undesirable side reactions such as cross-linking reactions and decomposition reactions between PAS prepolymers, between PASs generated by heating, and between PAS and PAS prepolymers generated by heating are likely to occur. In some cases, the characteristics of the obtained PAS may deteriorate. Therefore, it is desirable to avoid a temperature at which such an undesirable side reaction is remarkably generated.
- the heating temperature at which the manifestation of such undesirable side reactions can be suppressed examples include 180 ° C. or higher, preferably 200 ° C. or higher, and more preferably 250 ° C. or higher.
- 400 degreeC or less can be illustrated as said heating temperature, Preferably it is 380 degrees C or less, More preferably, it is 360 degrees C or less.
- the temperature may be higher than 400 ° C., and a temperature range of 450 ° C. or lower, preferably 420 ° C. or lower can be selected. In this case, there is an advantage that the conversion to a high molecular weight can be performed in a very short time.
- the time for performing the heating cannot be uniformly defined because it varies depending on various properties such as the content and m number of the cyclic PAS in the PAS prepolymer to be used and the molecular weight, and the conditions such as the temperature of the heating. It is preferable to set so that the undesirable side reaction does not occur as much as possible.
- Examples of the heating time include 0.05 hours or more, and preferably 0.1 hours or more. Moreover, 100 hours or less can be illustrated, 20 hours or less are preferable and 10 hours or less are more preferable.
- the heating time is less than 0.05 hours, the conversion of the PAS prepolymer to PAS tends to be insufficient.
- the heating time exceeds 100 hours there is a tendency not only to increase the possibility of adverse effects due to undesirable side reactions on the properties of the PAS to be obtained, but also to cause economic disadvantages. There is a case.
- the PAS prepolymer when converted to a high degree of polymerization by heating, various catalyst components that promote the conversion can be used.
- a catalyst component include ionic compounds and compounds having radical generating ability.
- the ionic compound include thiophenol sodium salt and lithium salt, and sulfur alkali metal salt.
- produces a sulfur radical by heating can be illustrated, for example, More specifically, the compound containing a disulfide bond can be illustrated.
- the catalyst component is usually taken into PAS, and the obtained PAS often contains the catalyst component.
- the amount of alkali metal in the reaction system containing the PAS prepolymer and the catalyst component is 100 ppm or less, preferably 50 ppm or less, more preferably Is 30 ppm or less, more preferably 10 ppm or less, and the weight of sulfur atoms constituting the disulfide group is less than 1% by weight, preferably less than 0.5% by weight, based on the weight of all sulfur atoms in the reaction system. It is preferable to adjust the addition amount of the catalyst component so that it is more preferably less than 0.3% by weight, and still more preferably less than 0.1% by weight.
- the conversion of the PAS prepolymer to a high degree of polymerization by heating is usually performed in the absence of a solvent, but can also be performed in the presence of a solvent.
- the solvent is not particularly limited as long as it does not substantially cause undesirable side reactions such as inhibition of conversion of the PAS prepolymer to a high degree of polymerization by heating and decomposition or crosslinking of the produced PAS.
- nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide
- sulfoxide and sulfone solvents such as dimethylsulfoxide and dimethylsulfone
- ketones such as acetone, methyl ethyl ketone, diethyl ketone, and acetophenone
- ether solvents such as dimethyl ether, dipropyl ether, and tetrahydrofuran
- halogen solvents such as chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane, tetrachloroethane, and chlorobenzene
- methanol, ethanol, propanol Butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, and polyethylene glycol Or alcohol phenol based solvents, benzene, toluene, and the like aromatic hydro
- Conversion of the PAS prepolymer to a high degree of polymerization by heating may be performed in a mold for producing a molded product, as well as by a method using a normal polymerization reaction apparatus, an extruder or melt kneading.
- Any apparatus provided with a heating mechanism such as using a machine can be used without particular limitation, and known methods such as a batch method and a continuous method can be employed.
- the atmosphere when the PAS prepolymer is converted to a high degree of polymerization by heating is preferably a non-oxidizing atmosphere, and is preferably performed under reduced pressure.
- the atmosphere in the reaction system is once changed to a non-oxidizing atmosphere and then the reduced pressure conditions.
- the non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with the PAS component is 5% by volume or less, preferably 2% by volume or less, and more preferably contains substantially no oxygen, that is, nitrogen, helium, argon, etc.
- the inert gas atmosphere Among these, a nitrogen atmosphere is particularly preferable from the viewpoints of economy and ease of handling.
- the reduced pressure condition means that the reaction system is lower than the atmospheric pressure, and the upper limit is preferably 50 kPa or less, more preferably 20 kPa or less, and even more preferably 10 kPa or less.
- An example of the lower limit is 0.1 kPa or more, and 0.2 kPa or more is more preferable.
- the pressure reduction condition exceeds the preferable upper limit, an undesirable side reaction such as a crosslinking reaction tends to occur.
- the pressure reduction condition is less than the preferred lower limit, the cyclic polyarylene sulfide having a low molecular weight contained in the PAS prepolymer tends to be volatilized depending on the reaction temperature.
- the conversion of the PAS prepolymer to a high degree of polymerization can be performed in the presence of a fibrous substance.
- the fibrous substance is a fine thread-like substance, and an arbitrary substance having a structure elongated like a natural fiber is preferable.
- a composite material structure composed of PAS and the fibrous substance can be easily prepared. Since such a structure is reinforced by a fibrous material, it tends to have superior mechanical properties, for example, compared to the case of PAS alone.
- reinforcing fibers made of long fibers which makes it possible to highly strengthen PAS.
- the resin and the fibrous substance tend to become poorer due to the high viscosity when the resin is melted.
- composite materials cannot be produced or expected mechanical properties do not appear.
- wetting is the physical state of the fluid material and the solid substrate so that substantially no air or other gas is trapped between the fluid material such as a molten resin and the solid substrate such as a fibrous compound. Means there is good and maintained contact. The lower the viscosity of the fluid material, the better the wetting with the fibrous material.
- the PAS prepolymer of the embodiment of the present invention has good wettability with a fibrous material because its viscosity when melted is significantly lower than that of a general thermoplastic resin, for example, PAS produced by a conventionally known method. It is easy to become. After the PAS prepolymer and the fibrous material form good wetting, the PAS prepolymer is converted into a high polymerization degree according to the method for producing a PAS of the embodiment of the present invention. A composite material structure in which (polyarylene sulfide) forms good wetting can be easily obtained.
- the fibrous fiber is preferably a reinforcing fiber composed of long fibers
- the reinforcing fiber used in the embodiment of the present invention is not particularly limited.
- examples thereof include fibers having good heat resistance and tensile strength used as reinforcing fibers.
- examples of the reinforcing fiber include glass fiber, carbon fiber, graphite fiber, aramid fiber, silicon carbide fiber, alumina fiber, and boron fiber.
- carbon fiber and graphite fiber which have good specific strength and specific elastic modulus and have a great contribution to weight reduction, can be exemplified as the best.
- any type of carbon fiber or graphite fiber can be used depending on the application, but high strength and high elongation with a tensile strength of 450 kgf / mm 2 and a tensile elongation of 1.6% or more. Carbon fiber is most suitable.
- the length is preferably 5 cm or more. In the range of this length, it becomes easy to sufficiently develop the strength of the reinforcing fiber as a composite material. Carbon fibers and graphite fibers may be used in combination with other reinforcing fibers.
- sequence of a reinforced fiber are not limited, For example, even if it is a single direction, a random direction, a sheet form, a mat form, a textile form, and a braid form, it can be used. In particular, for applications that require high specific strength and specific elastic modulus, an array in which reinforcing fibers are aligned in a single direction is most suitable. Arrangements are also suitable for embodiments of the present invention.
- the conversion of the PAS prepolymer to a high degree of polymerization can be performed in the presence of a filler.
- the filler include non-fibrous glass, non-fibrous carbon, and inorganic fillers such as calcium carbonate, titanium oxide, and alumina.
- each component separated by HPLC is determined by liquid chromatography / mass spectrometry (LC-MS) and by matrix-assisted laser desorption / ionization of the fraction in preparative liquid chromatography (preparative LC).
- the analysis was performed by mass spectrometry (MALDI-MS), analysis by nuclear magnetic resonance spectroscopy (NMR), and infrared spectroscopy (IR measurement).
- MALDI-MS mass spectrometry
- NMR nuclear magnetic resonance spectroscopy
- IR measurement infrared spectroscopy
- Apparatus HIC-20 Asper made by Shimadzu Corporation
- Detector Electrical conductivity detector (suppressor)
- Eluent 4.0 mM sodium bicarbonate / 1.0 mM aqueous sodium carbonate flow rate: 1.0 mL / min
- Injection volume 50 microliters
- Column temperature 30 ° C.
- FIG. 1 is an explanatory view schematically showing the outline of the configuration of the reaction apparatus 10 used in this example.
- the reactor 10 includes containers (I), (II), (III) and (IV).
- the container (I) the water-containing sulfiding agent is dehydrated.
- the sulfidizing agent dehydrated in the container (I) is sent to the container (II) via the flow path 20.
- the raw material mixture (a) is prepared by mixing the sent sulfidizing agent and other raw material components.
- the container (II) is provided with a circulation line 42 for circulating the raw material mixture (a) between the container (II) and the container (II).
- the circulation line 42 includes a pump which is a slurry seal type canned motor pump, and the raw material mixture (a) circulates by the driving force of the pump.
- a branch line 22 is connected to the circulation line 42 via a valve, and the raw material mixture (a) is supplied from the container (II) to the container (III) via the circulation line 42 and the branch line 22. .
- the amount of the raw material mixture (a) supplied from the container (II) to the container (III) can be adjusted by adjusting the opening of the valve.
- the supplied raw material mixture (a) can be heated and reacted, and the internal pressure can be a pressure exceeding the normal pressure. In this way, the reaction mixture (b) is adjusted by heating the raw material mixture (a).
- the container (III) is provided with a circulation line 44 for circulating the reaction mixture (b) between the container (III) and the container (III).
- the circulation line 44 includes a pump that is a slurry seal type canned motor pump, and the reaction mixture (b) circulates by the driving force of the pump.
- a branch line 24 is connected to the circulation line 44 via a valve, and the reaction mixture (b) is supplied from the vessel (III) to the vessel (IV) via the circulation line 44 and the branch line 24. .
- the amount of the reaction mixture (b) supplied from the container (III) to the container (IV) can be adjusted by adjusting the opening of the valve. Since the branch line 24 is provided with a cooling mechanism (not shown), the high-temperature reaction mixture (b) can be cooled and recovered in the container (IV).
- the container (III) corresponds to a “reaction container” in the claims of the present application
- the container (II) corresponds to a “supply container”
- the container (IV) corresponds to a “receiving container”.
- the distillate in the dehydration operation was analyzed by gas chromatography, the distillate contained 0.15 kg (0.15 liter) of NMP, and the container (I) contained 24.9 kg (24.2 kg) of NMP. Liter) was found to remain.
- the hydrogen sulfide scattered from the reaction system through the dehydration process was 2.5 mol, and the sodium sulfide was reduced by 2.5 mol and the sodium hydroxide increased by 2.5 mol due to the hydrogen sulfide scattering. It will be done.
- the mixture from which water was removed by the above dehydration operation was placed in a 300 liter vessel (II) made of SUS316 equipped with a stirrer, and 221 kg (216 liters) of NMP and 18.4 kg of p-dichlorobenzene (p-DCB) were obtained. (125 mol) was further added to obtain a raw material mixture (a-1). Therefore, the substrate concentration of the sulfur component represented by the amount of the organic polar solvent in the raw material mixture (a-1) was 1.96 liters per mol of the sulfur component. Moreover, the substrate concentration of the arylene unit represented by the amount of the organic polar solvent was 1.92 liters per mole of the arylene unit. The amount of the arylene unit in the raw material mixture (a-1) was 1.02 mol per mol of the sulfur component. In the container (II), the internal temperature was maintained at 140 ° C. while stirring the raw material mixture (a-1).
- ⁇ Preparation of initial reaction mixture 40 kg of the raw material mixture (a-1) prepared in the container (II) was supplied to a 70 liter container (III) made of SUS316 equipped with a stirrer, sealed under nitrogen, and the internal temperature was raised to 250 ° C. The initial reaction was carried out for 2 hours to obtain an initial reaction mixture. The pressure of the container (III) after the initial reaction was 0.4 MPa. As a result of sampling and analyzing the initial reaction mixture, the concentration of the unreacted sulfiding agent in the initial reaction mixture, that is, the unreacted sulfiding agent contained per kilogram of the initial reaction mixture was 0.022 mol. .
- the ratio of the sulfidizing agent concentration of the initial reaction mixture to the sulfidizing agent concentration of the raw material mixture (a-1) was 5%. Further, the concentration of the unreacted dihalogenated aromatic compound in the initial reaction mixture, that is, the unreacted dihalogenated aromatic compound contained in 1 kg of the initial reaction mixture was 0.027 mol. The ratio of the dihalogenated aromatic compound concentration of the initial reaction mixture to the dihalogenated aromatic compound concentration of the raw material mixture (a-1) was 6%. The production rate of cyclic PPS was 14%. Since there are no volatile components and additional components in this reaction, there is no change in the weight of the initial reaction mixture, and it can be considered that the substrate concentration can be kept the same as the raw material mixture (a-1).
- the raw material mixture (a-1) is transferred from the container (II) at a rate of 20 kg / hour while maintaining the internal temperature of the container (III) at 250 ° C. It was continuously supplied using a canned motor pump (operation A).
- the reaction mixture (b) is continuously withdrawn from the container (III) at a rate of 20 kg / hour using a slurry seal type canned motor pump (operation B), cooled to 200 ° C. or less in the pipe, and received. It transferred to the container (IV) which is a container, and obtained the mixture containing cyclic PPS. This operation was continued for 10 hours.
- the pressure in the container (III) was constant at 0.4 MPa.
- the container (II) there was no addition of components or evaporation of components other than the supply of the raw material mixture (a-1).
- the container (III) there was no addition of components or evaporation of components other than the supply of the raw material mixture (a-1) and the extraction of the reaction mixture (b). Therefore, it can be considered that the substrate concentration in the reaction mixture (b) in the vessel (III) is the same as that in the initial reaction mixture and kept constant.
- the liquid level of the container (III) was constant, it can be said that the amount of the reaction mixture (b) was also constant.
- the reaction mixture (b) was sampled and analyzed from the container (III). After 5 hours, the concentration of the unreacted sulfiding agent in the reaction mixture (b), that is, the unreacted sulfiding agent contained per kilogram of the reaction mixture (b) was 0.009 mol. The ratio of the sulfidizing agent concentration of the reaction mixture (b) to the sulfidizing agent concentration of the raw material mixture (a-1) was 2%. Further, the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture (b), that is, the unreacted dihalogenated aromatic compound contained per 1 kg of the reaction mixture (b) was 0.014 mol.
- the ratio of the dihalogenated aromatic compound concentration of the reaction mixture (b) to the dihalogenated aromatic compound concentration of the raw material mixture (a-1) was 3%.
- the production rate of cyclic PPS was 16%.
- the concentration of the unreacted sulfidizing agent in the reaction mixture (b) that is, the unreacted sulfidizing agent contained per kilogram of the reaction mixture (b) was 0.009 mol.
- the ratio of the sulfidizing agent concentration of the reaction mixture (b) to the sulfidizing agent concentration of the raw material mixture (a-1) was 2%.
- the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture (b), that is, the unreacted dihalogenated aromatic compound contained per 1 kg of the reaction mixture (b) was 0.014 mol.
- the ratio of the dihalogenated aromatic compound concentration of the reaction mixture (b) to the dihalogenated aromatic compound concentration of the raw material mixture (a-1) was 3%.
- the production rate of cyclic PPS was 17%.
- the ratio of the sulfidizing agent concentration of the reaction mixture to the sulfiding agent concentration of the raw material mixture (a-1) was 5%. Further, the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture, that is, the unreacted dihalogenated aromatic compound contained per kilogram of the reaction mixture was 0.027 mol. The ratio of the dihalogenated aromatic compound concentration of the reaction mixture to the dihalogenated aromatic compound concentration of the raw material mixture (a-1) was 6%. The production rate of cyclic PPS was 14%. Since there are no volatile components and additional components in this reaction, there is no change in the weight of the reaction mixture, and it can be considered that the substrate concentration can be kept the same as the raw material mixture (a-1).
- Example 1 the same raw material mixture (a-1) as in Example 1 was used, and the reaction time was 2 hours, which was the same as the average residence time in the synthesis of cyclic PAS in Example 1, but the production of cyclic PPS The rate was found to be lower than in Example 1.
- the effect of the present invention in which the production rate of cyclic polyarylene sulfide is improved by continuously performing the operation A and the operation B with respect to the batch system was shown. .
- a SUS 10 liter reaction vessel equipped with a stirrer and a rectifying column was charged with 2.46 kg of a 48 wt% aqueous solution of sodium hydrosulfide (1.18 kg as sodium hydrosulfide, 21.1 mol), and a 48 wt% aqueous solution of sodium hydroxide 1 .84 kg (0.88 kg as sodium hydroxide, 22.1 mol) and 4.43 kg (4.32 liters) of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised to 205 ° C. through nitrogen gas, followed by dehydration. Went.
- the reaction mixture obtained above that is, the reaction mixture containing at least cyclic PPS, linear PPS, NMP and NaCl as a by-product salt, is solid-liquid separated by a centrifugal dehydrator, and this operation is performed to obtain a solid content in a wet state.
- the obtained wet solid was sufficiently washed with warm water and then dried to obtain 1.54 kg of a dry solid.
- Example 2 Here, the result of producing a cyclic PAS by preparing a raw material mixture (a) containing a linear polyarylene sulfide in addition to a sulfidizing agent, a dihalogenated aromatic compound and an organic polar solvent is shown.
- the substrate concentration represented by the amount of the organic polar solvent in the raw material mixture (a-2) was 1.96 liters per mole of sulfur component.
- the substrate concentration of the arylene unit represented by the amount of the organic polar solvent was 1.92 liters per mole of the arylene unit.
- the amount of the arylene unit in the raw material mixture (a-2) was 1.02 mol per mol of the sulfur component.
- the internal temperature was maintained at 140 ° C. while stirring the raw material mixture (a-2).
- the pressure of the container (III) after the initial reaction was 0.3 MPa.
- the concentration of the unreacted sulfiding agent in the initial reaction mixture that is, the unreacted sulfidizing agent contained in 1 kg of the initial reaction mixture was 0.005 mol. .
- the ratio of the sulfidizing agent concentration of the initial reaction mixture to the sulfiding agent concentration of the raw material mixture (a-2) was 5%. Further, the concentration of the unreacted dihalogenated aromatic compound in the initial reaction mixture, that is, the unreacted dihalogenated aromatic compound contained per kilogram of the initial reaction mixture was 0.009 mol. The ratio of the dihalogenated aromatic compound concentration of the initial reaction mixture to the dihalogenated aromatic compound concentration of the raw material mixture (a-2) was 9%. The production rate of cyclic PPS was 12%. Since there are no volatile components and additional components during this reaction, there is no change in the weight of the initial reaction mixture, and it can be considered that the substrate concentration can be maintained the same as the raw material mixture (a-2).
- the raw material mixture (a-2) is transferred from the container (II) at a rate of 20 kg / hour while maintaining the internal temperature of the container (III) at 250 ° C. It was continuously supplied using a canned motor pump (operation A).
- the reaction mixture (b) is continuously withdrawn from the vessel (III) at a rate of 20 kg / hour using a slurry seal type canned motor pump (operation B), cooled to 200 ° C. or lower in the pipe, and received. It transferred to the container (IV) which is a container, and obtained the mixture containing cyclic PPS. This operation was continued for 10 hours.
- the pressure in the container (III) was constant at 0.3 MPa.
- the container (II) there was no addition of components or evaporation of components other than the supply of the raw material mixture (a-2).
- the container (III) there was no addition of components or evaporation of components other than the supply of the raw material mixture (a-2) and the extraction of the reaction mixture (b). Therefore, it can be considered that the substrate concentration in the reaction mixture (b) in the vessel (III) is the same as that in the initial reaction mixture and kept constant.
- the liquid level of the container (III) was constant, it can be said that the amount of the reaction mixture (b) was also constant.
- the reaction mixture (b) was sampled and analyzed from the container (III). After 5 hours, the concentration of the unreacted sulfiding agent in the reaction mixture (b), that is, the unreacted sulfiding agent contained per kilogram of the reaction mixture (b) was 0.005 mol. The ratio of the sulfidizing agent concentration of the reaction mixture (b) to the sulfiding agent concentration of the raw material mixture (a-2) was 5%. Further, the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture (b), that is, the unreacted dihalogenated aromatic compound contained per 1 kg of the reaction mixture (b) was 0.009 mol.
- the ratio of the dihalogenated aromatic compound concentration of the reaction mixture (b) to the dihalogenated aromatic compound concentration of the raw material mixture (a-2) was 9%.
- the production rate of cyclic PPS was 14%.
- the concentration of the unreacted sulfidizing agent in the reaction mixture (b) that is, the unreacted sulfidizing agent contained per kilogram of the reaction mixture (b) was 0.004 mol.
- the ratio of the sulfidizing agent concentration in the reaction mixture (b) to the sulfidizing agent concentration in the raw material mixture (a-2) was 4%.
- the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture (b), that is, the unreacted dihalogenated aromatic compound contained per 1 kg of the reaction mixture (b) was 0.009 mol.
- the ratio of the dihalogenated aromatic compound concentration of the reaction mixture (b) to the dihalogenated aromatic compound concentration of the raw material mixture (a-2) was 9%.
- the production rate of cyclic PPS was 15%.
- cyclic PPS can be continuously obtained at a high production rate and a constant production rate, and cyclic PPS can be synthesized efficiently. I understood.
- the ratio of the sulfidizing agent concentration of the reaction mixture to the sulfidizing agent concentration of the raw material mixture (a-2) was 5%. Further, the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture, that is, the unreacted dihalogenated aromatic compound contained per kilogram of the reaction mixture was 0.009 mol. The ratio of the dihalogenated aromatic compound concentration of the reaction mixture to the dihalogenated aromatic compound concentration of the raw material mixture (a-2) was 9%. The production rate of cyclic PPS was 12%. Since there are no volatile components and additional components in this reaction, there is no change in the weight of the reaction mixture, and it can be considered that the substrate concentration can be kept the same as the raw material mixture (a-2).
- Example 2 the same raw material mixture (a-2) as in Example 2 was used, and the reaction time was 2 hours, which was the same as the average residence time in the synthesis of cyclic PAS in Example 2, but the formation of cyclic PPS The rate was found to be lower than in Example 2.
- the effect of the present invention in which the production rate of cyclic polyarylene sulfide is improved by continuously performing the operation A and the operation B with respect to the batch system was shown. .
- Example 3 an example in which the amount of the organic polar solvent in the raw material mixture (a) and the reaction mixture (b) is increased from that in Example 1, that is, the substrate concentration is low.
- the substrate concentration of the arylene unit represented by the amount of the organic polar solvent was 3.27 liters per mole of the arylene unit.
- the amount of the arylene unit in the raw material mixture (a-3) was 1.02 mol per mol of the sulfur component.
- the internal temperature was maintained at 140 ° C. while stirring the raw material mixture (a-3).
- the pressure of the container (III) after the initial reaction was 0.4 MPa.
- the concentration of the unreacted sulfiding agent in the initial reaction mixture that is, the unreacted sulfiding agent contained in 1 kg of the initial reaction mixture was 0.014 mol. .
- the ratio of the sulfidizing agent concentration of the initial reaction mixture to the sulfidizing agent concentration of the raw material mixture (a-3) was 5%. Further, the concentration of the unreacted dihalogenated aromatic compound in the initial reaction mixture, that is, the unreacted dihalogenated aromatic compound contained in 1 kg of the initial reaction mixture was 0.017 mol. The ratio of the dihalogenated aromatic compound concentration of the initial reaction mixture to the dihalogenated aromatic compound concentration of the raw material mixture (a-3) was 6%. The production rate of cyclic PPS was 18%. Since there are no volatile components and additional components in this reaction, there is no change in the weight of the initial reaction mixture, and it can be considered that the substrate concentration can be kept the same as the raw material mixture (a-3).
- the raw material mixture (a-3) is transferred from the container (II) at a rate of 20 kg / hour while maintaining the internal temperature of the container (III) at 250 ° C. It was continuously supplied using a canned motor pump (operation A).
- the reaction mixture (b) is continuously withdrawn from the vessel (III) at a rate of 20 kg / hour using a slurry seal type canned motor pump (operation B), cooled to 200 ° C. or lower in the pipe, and received. It transferred to the container (IV) which is a container, and obtained the mixture containing cyclic PPS. This operation was continued for 10 hours.
- the pressure in the container (III) was constant at 0.4 MPa.
- the container (II) there was no addition of components or evaporation of components other than the supply of the raw material mixture (a-3).
- the container (III) there was no addition of components or evaporation of components other than the supply of the raw material mixture (a-3) and the extraction of the reaction mixture (b). Therefore, it can be considered that the substrate concentration in the reaction mixture (b) in the vessel (III) is the same as that in the initial reaction mixture and kept constant.
- the liquid level of the container (III) was constant, it can be said that the amount of the reaction mixture (b) was also constant.
- the reaction mixture (b) was sampled and analyzed from the container (III). After 5 hours, the concentration of the unreacted sulfiding agent in the reaction mixture (b), that is, the unreacted sulfiding agent contained per kilogram of the reaction mixture (b) was 0.008 mol. The ratio of the sulfidizing agent concentration of the reaction mixture (b) to the sulfidizing agent concentration of the raw material mixture (a-3) was 3%. Further, the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture (b), that is, the unreacted dihalogenated aromatic compound contained per 1 kg of the reaction mixture (b) was 0.011 mol.
- the ratio of the dihalogenated aromatic compound concentration of the reaction mixture (b) to the dihalogenated aromatic compound concentration of the raw material mixture (a-3) was 4%.
- the production rate of cyclic PPS was 20%.
- the concentration of the unreacted sulfiding agent in the reaction mixture (b) that is, the unreacted sulfiding agent contained per kilogram of the reaction mixture (b) was 0.006 mol.
- the ratio of the sulfidizing agent concentration of the reaction mixture (b) to the sulfidizing agent concentration of the raw material mixture (a-3) was 2%.
- the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture (b), that is, the unreacted dihalogenated aromatic compound contained per 1 kg of the reaction mixture (b) was 0.008 mol.
- the ratio of the dihalogenated aromatic compound concentration of the reaction mixture (b) to the dihalogenated aromatic compound concentration of the raw material mixture (a-3) was 3%.
- the production rate of cyclic PPS was 21%.
- the ratio of the sulfidizing agent concentration of the reaction mixture to the sulfidizing agent concentration of the raw material mixture (a-3) was 5%. Further, the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture, that is, the unreacted dihalogenated aromatic compound contained per kilogram of the reaction mixture was 0.017 mol. The ratio of the dihalogenated aromatic compound concentration of the reaction mixture to the dihalogenated aromatic compound concentration of the raw material mixture (a-3) was 6%. The production rate of cyclic PPS was 18%. Since there are no volatile components and additional components during this reaction, there is no change in the weight of the reaction mixture, and it can be considered that the substrate concentration can be kept the same as the raw material mixture (a-3).
- Example 3 the same raw material mixture (a-3) as in Example 3 was used, and the reaction time was 2 hours, which was the same as the average residence time in the synthesis of the cyclic PAS in Example 3, but the formation of cyclic PPS The rate was found to be lower than in Example 3.
- the effect of the present invention that the production rate of cyclic polyarylene sulfide is improved by continuously performing the operation A and the operation B with respect to the batch system was shown. .
- Example 4 Here, an example is shown in which the amount of the organic polar solvent in the raw material mixture (a) and the reaction mixture (b) is lower than that in Example 1, that is, the substrate concentration is high.
- the substrate concentration of the arylene unit represented by the amount of the organic polar solvent was 1.40 liters per mol of the arylene unit.
- the amount of the arylene unit in the raw material mixture (a-4) was 1.02 mol per mol of the sulfur component.
- the internal temperature was maintained at 140 ° C. while stirring the raw material mixture (a-4).
- the pressure of the container (III) after the initial reaction was 0.4 MPa.
- the concentration of the unreacted sulfiding agent in the initial reaction mixture that is, the unreacted sulfidizing agent contained in 1 kg of the initial reaction mixture was 0.017 mol. .
- the ratio of the sulfiding agent concentration of the initial reaction mixture to the sulfiding agent concentration of the raw material mixture (a-4) was 3%. Further, the concentration of the unreacted dihalogenated aromatic compound in the initial reaction mixture, that is, the unreacted dihalogenated aromatic compound contained in 1 kg of the initial reaction mixture was 0.024 mol. The ratio of the dihalogenated aromatic compound concentration of the initial reaction mixture to the dihalogenated aromatic compound concentration of the raw material mixture (a-4) was 4%. The production rate of cyclic PPS was 10%. Since there are no volatile components and additional components in this reaction, there is no change in the weight of the initial reaction mixture, and it can be considered that the substrate concentration can be maintained the same as the raw material mixture (a-4).
- the raw material mixture (a-4) is transferred from the container (II) at a rate of 20 kg / hour while maintaining the internal temperature of the container (III) at 250 ° C. It was continuously supplied using a canned motor pump (operation A).
- the reaction mixture (b) is continuously withdrawn from the container (III) at a rate of 20 kg / hour using a slurry seal type canned motor pump (operation B), cooled to 200 ° C. or less in the pipe, and received. It transferred to the container (IV) which is a container, and obtained the mixture containing cyclic PPS. This operation was continued for 5 hours.
- the pressure in the container (III) was constant at 0.4 MPa.
- the container (II) there was no addition of components or evaporation of components other than the supply of the raw material mixture (a-4).
- the container (III) there was no addition of components or evaporation of components other than the supply of the raw material mixture (a-4) and the extraction of the reaction mixture (b). Therefore, it can be considered that the substrate concentration in the reaction mixture (b) in the vessel (III) is the same as that in the initial reaction mixture and kept constant.
- the liquid level of the container (III) was constant, it can be said that the amount of the reaction mixture (b) was also constant.
- the concentration of the unreacted sulfidizing agent in the reaction mixture (b), that is, the reaction mixture (b) 1 The unreacted sulfidizing agent contained per kilogram was 0.012 mol.
- the ratio of the sulfidizing agent concentration of the reaction mixture (b) to the sulfiding agent concentration of the raw material mixture (a-4) was 2%.
- the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture (b), that is, the unreacted dihalogenated aromatic compound contained in 1 kg of the reaction mixture (b) was 0.018 mol.
- the ratio of the dihalogenated aromatic compound concentration of the reaction mixture (b) to the dihalogenated aromatic compound concentration of the raw material mixture (a-4) was 3%.
- the production rate of cyclic PPS was 12%.
- the ratio of the sulfidizing agent concentration of the reaction mixture to the sulfidizing agent concentration of the raw material mixture (a-4) was 3%. Further, the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture, that is, the unreacted dihalogenated aromatic compound contained per kilogram of the reaction mixture was 0.024 mol. The ratio of the dihalogenated aromatic compound concentration of the reaction mixture to the dihalogenated aromatic compound concentration of the raw material mixture (a-4) was 4%. The production rate of cyclic PPS was 10%. Since there are no volatile components and additional components during this reaction, there is no change in the weight of the reaction mixture, and it can be considered that the substrate concentration can be maintained the same as the raw material mixture (a-4).
- Example 4 the same raw material mixture (a-4) as in Example 4 was used, and the reaction time was 2 hours, which was the same as the average residence time in the synthesis of cyclic PAS in Example 4, but the formation of cyclic PPS The rate was found to be low.
- the effect of the present invention in which the production rate of cyclic polyarylene sulfide is improved by continuously performing the operation A and the operation B with respect to the batch system was shown. .
- Example 5 Here, an example in which the amount of the raw material mixture (a) supplied in operation A and the amount of the reaction mixture (b) extracted in operation B is increased from that in Example 1, that is, the average residence time of the reaction mixture (b) is shortened.
- Example 5 In the same manner as in Example 1, except that the feed rate of the raw material mixture (a-1) and the extraction rate of the reaction mixture (b) in the synthesis of the cyclic PAS of Example 1 were changed from 20 kg / hour to 40 kg / hour, respectively. Operation (A) and operation (B) were continued for 5 hours. That is, in Example 5, the average residence time was 1 hour.
- the pressure in the container (III) was constant at 0.4 MPa.
- the container (II) there was no addition of components or evaporation of components other than the supply of the raw material mixture (a-1).
- the container (III) there was no addition of components or evaporation of components other than the supply of the raw material mixture (a-1) and the extraction of the reaction mixture (b). Therefore, it can be considered that the substrate concentration in the reaction mixture (b) in the vessel (III) is the same as that in the initial reaction mixture and kept constant.
- the liquid level of the container (III) was constant, it can be said that the amount of the reaction mixture (b) was also constant.
- the concentration of the unreacted sulfidizing agent in the reaction mixture (b), that is, the reaction mixture (b) 1 Unreacted sulfiding agent contained per kilogram was 0.049 mol.
- the ratio of the sulfidizing agent concentration of the reaction mixture (b) to the sulfiding agent concentration of the raw material mixture (a-1) was 11%.
- the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture (b), that is, the unreacted dihalogenated aromatic compound contained in 1 kg of the reaction mixture (b) was 0.059 mol.
- the ratio of the dihalogenated aromatic compound concentration of the reaction mixture (b) to the dihalogenated aromatic compound concentration of the raw material mixture (a-1) was 13%.
- the production rate of cyclic PPS was 15%.
- the ratio of the sulfidizing agent concentration of the reaction mixture to the sulfidizing agent concentration of the raw material mixture (a-1) was 12%. Further, the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture, that is, the unreacted dihalogenated aromatic compound contained in 1 kg of the reaction mixture was 0.068 mol. The ratio of the dihalogenated aromatic compound concentration of the reaction mixture to the dihalogenated aromatic compound concentration of the raw material mixture (a-1) was 15%. The production rate of cyclic PPS was 13%. Since there are no volatile components and additional components in this reaction, there is no change in the weight of the reaction mixture, and it can be considered that the substrate concentration can be kept the same as the raw material mixture (a-1).
- Example 5 the same raw material mixture (a-1) as in Example 5 was used, and the reaction time was 1 hour, which was the same as the average residence time in the synthesis of cyclic PAS in Example 5, but formation of cyclic PPS The rate was found to be lower than in Example 1.
- the effect of the present invention that the production rate of cyclic polyarylene sulfide is improved by continuously performing the operation A and the operation B with respect to the batch system was shown. .
- Example 6 Here, the example which performed operation (D) which further heats the reaction mixture (b) extracted from the reaction container is shown.
- the above apparatus configuration is changed to the following configuration. That is, a container (V) having the same configuration as the container (III) is installed between the container (III) and the container (IV), and the slurry seal type cand is placed in the order of the container (III) and the container (V) container (IV). It was connected via a motor pump. In connecting the container (V) and the container (IV), a pipe having a cooling mechanism was installed between the slurry seal type canned motor pump and the container (V).
- Example 1 up to the container (III), the same operation as in Example 1 was performed to start the operation (A) and the operation (B), and the reaction mixture (b) extracted from the container (III)
- the reaction mixture (b) obtained in Example 1 was supplied and supplied to the vessel (V) heated to 250 ° C., and further heated at 250 ° C. (operation D) to obtain a reaction mixture (c), 20 kg / hour.
- the mixture was continuously extracted at a speed of, cooled to 200 ° C. or lower in the pipe, and transferred to the container (IV) to obtain a mixture containing cyclic PPS. This operation was continued for 10 hours.
- the reaction mixture (c) was sampled and analyzed from the container (V). As a result, the reaction mixture (c) was not analyzed in either 5 hours or 10 hours.
- the concentration of the sulfidizing agent in the reaction that is, the unreacted sulfidizing agent contained per kilogram of the reaction mixture (c) was 0.004 mol.
- the ratio of the sulfidizing agent concentration of the reaction mixture (c) to the sulfidizing agent concentration of the raw material mixture (a-1) was 1%.
- the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture (c), that is, the unreacted dihalogenated aromatic compound contained per 1 kg of the reaction mixture (c) was 0.009 mol.
- the ratio of the dihalogenated aromatic compound concentration of the reaction mixture (c) to the dihalogenated aromatic compound concentration of the raw material mixture (a-1) was 2%.
- the production rate of cyclic PPS was 18%.
- Example 7 Here, an example involving a change in substrate concentration is shown.
- 85.0 kg (82.9 liters) of NMP was put into the container (II).
- the raw material mixture (a-1) was diluted to obtain a raw material mixture (a-5). Therefore, the substrate concentration of the sulfur component represented by the organic polar solvent of the raw material mixture was 1.96 liters to 3.33 liters per mole of sulfur component.
- the substrate concentration of the arylene unit represented by the amount of the organic polar solvent in the raw material mixture was 1.92 liters to 3.26 liters per mole of the arylene units.
- the amount of the arylene unit relative to the sulfur component in the raw material mixture was not changed at 1.02 mol per mol of the sulfur component.
- the reaction mixture (b) As a result of sampling and analyzing the reaction mixture (b) from the container (III) 5 hours after the start of this operation (10 hours after starting the supply of the raw material mixture (a-1)), the reaction mixture (b The concentration of the unreacted sulfidizing agent in), that is, the unreacted sulfidizing agent contained per kilogram of the reaction mixture (b) was 0.005 mol. The ratio of the sulfidizing agent concentration of the reaction mixture (b) to the sulfiding agent concentration of the raw material mixture (a-5) was 2%.
- the concentration of the unreacted dihalogenated aromatic compound in the reaction mixture (b), that is, the unreacted dihalogenated aromatic compound contained per 1 kg of the reaction mixture (b) was 0.008 mol.
- the ratio of the dihalogenated aromatic compound concentration of the reaction mixture (b) to the dihalogenated aromatic compound concentration of the raw material mixture (a-5) was 3%.
- the production rate of cyclic PPS was 20%.
- Example 1 From the results of Example 1 and this example, it was found that when the substrate concentration is varied within the preferred range of the present invention, the yield of cyclic PPS also varies, but cyclic polyarylene sulfide can be synthesized efficiently.
- Example 8 Here, the preparation of the initial reaction mixture is not the batch type exemplified in Example 1, but an operation in which an organic polar solvent is introduced into the reaction vessel and the raw material mixture (a) is supplied into the reaction vessel; The example prepared by performing in parallel the operation which extracts a part of reaction mixture from a reaction container is shown.
- the raw material mixture (a-1) was continuously supplied to the container (III) at a rate of 10 kg / hour using a slurry seal type canned motor pump.
- the initial reaction mixture containing the reaction product is continuously extracted from the container (III) at a rate of 20 kg / hour using a slurry seal type canned motor pump, cooled to 200 ° C. or less in the pipe, Transferred to (IV).
- the operation of the initial reaction in which the feed of the raw material mixture (a-1) to the container (III) and the extraction of the initial reaction mixture from the container (III) were continuously continued for 12 hours.
- the concentration of unreacted sulfiding agent in the initial reaction mixture at the time point after 2 hours is 0.057 mol.
- the ratio of the sulfidizing agent concentration of the initial reaction mixture to the sulfiding agent concentration of the raw material mixture (a-1) was 13%.
- the concentration of unreacted dihalogenated aromatic compound in the initial reaction mixture, that is, the unreacted dihalogenated aromatic compound contained in 1 kg of the initial reaction mixture was 0.068 mol.
- the ratio of the dihalogenated aromatic compound concentration of the initial reaction mixture to the dihalogenated aromatic compound concentration of the raw material mixture (a-1) was 15%.
- the production rate of cyclic PPS was 9%.
- the concentration of the unreacted sulfiding agent in the initial reaction mixture that is, the unreacted sulfiding agent contained per kilogram of the initial reaction mixture was 0.018 mol.
- the ratio of the sulfidizing agent concentration of the initial reaction mixture to the sulfidizing agent concentration of the raw material mixture (a-1) was 4%.
- the concentration of the unreacted dihalogenated aromatic compound in the initial reaction mixture was 0.023 mol.
- the ratio of the dihalogenated aromatic compound concentration of the initial reaction mixture to the dihalogenated aromatic compound concentration of the raw material mixture (a-1) was 5%.
- the production rate of cyclic PPS reached 15%, and the composition was the same as that of the initial reaction mixture of Example 1.
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Abstract
Description
特に、本発明の方法を採用することにより、環式ポリアリーレンスルフィドを高生成率で得ることができる。
本発明の実施形態で用いられるスルフィド化剤とは、ジハロゲン化芳香族化合物にスルフィド結合を導入できるもの、およびアリーレンスルフィド結合に作用してアリーレンチオラートを生成するものであればよい。スルフィド化剤としては、例えばアルカリ金属硫化物、アルカリ金属水硫化物、および硫化水素が挙げられる。
本発明の実施形態で使用されるジハロゲン化芳香族化合物とは、芳香環の二価基であるアリーレン基と、2つのハロゲノ基とを有する芳香族化合物である。ジハロゲン化芳香族化合物1モルは、アリーレン単位1モルとハロゲノ基2モルを有している。たとえば、アリーレン基としてベンゼン環の二価基であるフェニレン基を有すると共に2つのハロゲノ基を有する化合物として、p-ジクロロベンゼン、o-ジクロロベンゼン、m-ジクロロベンゼン、p-ジブロモベンゼン、o-ジブロモベンゼン、m-ジブロモベンゼン、1-ブロモ-4-クロロベンゼン、および1-ブロモ-3-クロロベンゼンなどのジハロゲン化ベンゼンを挙げることができる。さらに、ジハロゲン化芳香族化合物としては、1-メトキシ-2,5-ジクロロベンゼン、1-メチル-2,5-ジクロロベンゼン、1,4-ジメチル-2,5-ジクロロベンゼン、1,3-ジメチル-2,5-ジクロロベンゼン、および3,5-ジクロロ安息香酸などのハロゲン基以外の置換基をも含む化合物を挙げることができる。なかでも、p-ジクロロベンゼンに代表されるp-ジハロゲン化ベンゼンを主成分にするジハロゲン化芳香族化合物が好ましい。特に好ましくは、p-ジクロロベンゼンを80~100モル%含むものであり、さらに好ましくは90~100モル%含むものである。また、環式ポリアリーレンスルフィド(以下、環式PASとも呼ぶ)共重合体を得るために異なる2種以上のジハロゲン化芳香族化合物を組み合わせて用いることも可能である。
本発明の実施形態の環式PASの製造においては、反応溶媒として有機極性溶媒を用いるが、なかでも有機アミド溶媒を用いるのが好ましい。具体例としては、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、N-シクロヘキシル-2-ピロリドンなどのN-アルキルピロリドン類、N-メチル-ε-カプロラクタムなどのカプロラクタム類、1,3-ジメチル-2-イミダゾリジノン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、ヘキサメチルリン酸トリアミドなどに代表されるアプロチック有機溶媒、及びこれらの混合物などが、反応の安定性が高いために好ましく使用される。これらのなかでもN-メチル-2-ピロリドン、1,3-ジメチル-2-イミダゾリジノンが好ましく用いられる。
本発明の実施形態における環式ポリアリーレンスルフィドとは、式-(Ar-S)-の繰り返し単位を主要構成単位とする環式化合物であり、好ましくは当該繰り返し単位を80モル%以上含有する下記一般式(A)のごとき化合物が例示できる。
本発明の実施形態における線状ポリアリーレンスルフィド(以下、線状PASと略する場合もある)とは、式、-(Ar-S)-の繰り返し単位を主要構成単位とする好ましくは当該繰り返し単位を80モル%以上含有する線状のホモポリマーまたは線状のコポリマーである。Arとしては前記の式(B)~式(M)などであらわされる単位などがあるが、なかでも式(B)が特に好ましい。
本発明の実施形態では、少なくともスルフィド化剤、ジハロゲン化芳香族化合物および有機極性溶媒を含む原料混合物を加熱して反応させて環式ポリアリーレンスルフィドを製造する方法において、原料混合物(a)から生じる反応生成物を含む反応容器内の反応混合物(b)へ原料混合物(a)を供給する操作(A)と、同反応容器内の反応混合物(b)の一部を反応容器から抜き出す操作(B)と、前記反応容器内を加熱する操作(C)とを、継続的に行うことが特徴であり、これにより高生成率で一定品質の環式ポリアリーレンスルフィドを継続して得られることから高い生産性の実現が可能である。以下、本発明の実施形態に係る基質濃度、原料混合物(a)、反応混合物(b)、操作(A)および操作(B)、およびその他の実施形態について順に詳述する。
本願明細書において基質濃度とは、以下に詳述するとおり、原料混合物(a)または反応混合物(b)(以下、合わせて反応混合物等とも表記する)中の硫黄成分およびアリーレン単位のそれぞれの量(モル数)と有機極性溶媒の量との関係により表される。つまり、本願明細書において、硫黄成分の基質濃度とは、反応混合物等中の硫黄成分当たりの有機極性溶媒量をいい、アリーレン単位の基質濃度とは、反応混合物等中のアリーレン単位当たりの有機極性溶媒量をいう。
本発明の実施形態における原料混合物(a)は、原料成分としてスルフィド化剤、ジハロゲン化芳香族化合物および有機極性溶媒を必須成分とする。原料混合物(a)は、更に線状PASを含んでいてもよく、また、前記必須成分以外に、反応を著しく阻害しない第三成分や、反応を加速する効果を有する第三成分を加えることも可能である。原料混合物(a)の組成は反応容器内に供給された時点での全原料成分の組成を基準とし、供給した原料成分全体をもって原料混合物(a)と見なす。
本発明の実施形態の環式PASの製造方法における反応混合物(b)とは、前記の原料混合物(a)を加熱して反応させて得られる少なくとも環式PAS、線状PAS、金属ハロゲン化物および有機極性溶媒を含む反応容器内の反応混合物のことをいう。本発明の実施形態では、反応混合物(b)に対し継続的に原料混合物(a)を追加して反応させるため、反応混合物(b)はスルフィド化剤および/またはジハロゲン化芳香族化合物を含んでいてもよい。また、前記の通り反応混合物(b)の基質濃度は一定に維持するが、反応混合物(b)の成分組成は変動しうるものであり、常に一定とは限らない。
本発明の実施形態の環式PASの製造おいては、前記の原料混合物(a)から生じる反応混合物(b)を含む反応容器内に原料混合物(a)を供給する操作(A)と、同反応容器内の反応混合物(b)の一部を反応容器から抜き出す操作(B)と、前記反応容器内を加熱する操作(C)とを、それぞれ継続的に行う。これら操作(A)および操作(B)は、継続的に反応混合物(b)が得られればいかなる方法を適用してもよい。なお、ここで言う継続的とは、双方の操作を連続的に継続する構成のみならず、少なくとも一方の操作を断続的に継続する構成、例えば双方の操作を交互に継続的に行なう態様も含む。
本発明の実施形態において反応混合物(b)中の未反応のスルフィド化剤の濃度は、前記の操作(A)および操作(B)によって変動しうるが、原料混合物(a)中のスルフィド化剤の濃度に対し、常に30%以下に維持することが好ましく、20%以下がより好ましく、10%以下がさらに好ましく、5%以下がとりわけ好ましく、3%以下が殊更好ましい。また、反応混合物(b)中のスルフィド化剤が完全消費した場合には、未反応のスルフィド化剤の濃度は、原料混合物(a)中のスルフィド化剤の濃度に対して0%となり、理想的な状態と言えるが、実際反応を行う上での下限としては0.1%以上であることが多い。
本発明の実施形態の環式PASの製造においては、前記した反応により得られた反応混合物から環式PASを分離回収することも可能である。反応により得られた反応混合物には環式PAS、線状PAS及び有機極性溶媒が含まれ、その他の成分として未反応のスルフィド化剤、ジハロゲン化芳香族化合物、水、あるいは副生塩などが含まれる場合もある。
この様な反応混合物からPAS成分を回収する方法に特に制限は無く、例えば必要に応じて有機極性溶媒の一部もしくは大部分を蒸留等の操作により除去した後に、PAS成分に対する溶解性が低く且つ有機極性溶媒と混和し、好ましくは副生塩に対して溶解性を有する溶剤と必要に応じて加熱下で接触させて、環式PASを線状PASとの混合固体としてPAS成分を回収する方法が例示できる。あるいは、反応混合物中の環式PASおよび線状PASが溶解するに足る温度、好ましくは200℃を超える温度、より好ましくは230℃以上の温度において反応混合物中に存在する固形成分と可溶成分を固液分離により分離して、少なくとも環式PAS、線状PASおよび有機極性溶媒を含む溶液成分を回収し、この溶液成分から必要に応じて有機極性溶媒の一部もしくは大部分を蒸留等の操作により除去した後に、PAS成分に対する溶解性が低く且つ有機極性溶媒と混和し、好ましくは副生塩に対して溶解性を有する溶剤と必要に応じて加熱下で接触させて、環式PASを線状PASとの混合固体としてPAS成分を回収する方法が例示できる。PAS成分に対する溶解性が低く且つ有機極性溶媒と混和し、好ましくは副生塩に対して溶解性を有する溶剤は、一般に比較的極性の高い溶剤である。用いた有機極性溶媒や副生塩の種類により好ましい溶剤は異なるので限定はできないが、例えば水や、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、およびヘキサノールに代表されるアルコール類や、アセトンに代表されるケトン類、並びに、酢酸エチルおよび酢酸ブチルなどに代表される酢酸エステル類が例示できる。入手性、経済性の観点から、水、メタノール及びアセトンが好ましく、水が特に好ましい。
上記には環式PASの回収方法として、まず環式PASと線状PASを含むPAS混合物を得た後にこの混合物から環式PASを回収する方法について例示したが、回収方法はこれに限定されるものではない。環式PAS回収方法として別の具体例を以下に示す。
かくして得られた環式ポリアリーレンスルフィドは十分に高純度であり、各種用途に好適に用いることができるが、さらに以下に述べる後処理を付加的に施すことによってよりいっそう純度の高い環式PASを得ることが可能である。
上記のようにして環式PASとして得られたポリアリーレンスルフィドは、通常、環式PASを50重量%以上、好ましくは70重量%以上、より好ましくは80重量%以上含む純度の高いものであり、一般的に得られる線状のPASとは異なる特性を有する工業的にも利用価値の高いものである。また、本発明の実施形態の製造方法により得られる環式PASは前記式(A)におけるmが単一ではなく、m=4~50の異なるmを有する前記式(A)が得られやすいという特徴を有する。ここで好ましいmの範囲は4~25,より好ましくは4~20である。mがこの範囲であれば、後述するようにPASポリマー(高重合度体)を得るための原料として用いる場合に重合反応が進行しやすく、高分子量体が得られやすくなる傾向にある。この理由は現時点判然とはしないが、この範囲の環式PASは分子が環式であるがために生じる結合のゆがみが大きく、重合時に高分子量化が起こりやすいためと推測している。
本発明の実施形態で得られた環式PASを各種樹脂に配合して用いることも可能であり、このような環式PASを配合した樹脂組成物は、溶融加工時にすぐれた流動性を発現する傾向が強く、また滞留安定性にも優れる傾向にある。この様な特性、特に流動性の向上は、樹脂組成物を溶融加工する際の加熱温度が低くても溶融加工性に優れるという特徴を発現するため、射出成形品や繊維、フィルム等の押出成形品に加工する際の溶融加工性の向上をもたらす点で大きなメリットとなる。環式PASを配合した際にこの様な特性の向上が発現する理由は定かではないが、環式PASの構造の特異性、すなわち環状構造であるために通常の線状化合物と比較してコンパクトな構造をとりやすいため、マトリックスである各種樹脂との絡み合いが少なくなりやすいこと、各種樹脂に対して可塑剤として作用すること、またマトリックス樹脂どうしの絡み合い抑制にも奏効するためと推測している。
本発明の実施形態によって回収される環式PASは、前記(9)項に述べたごとき優れた特性を有するので、PASポリマーすなわち高重合度体を得る際のプレポリマーとして好適に用いることが可能である。プレポリマーとしては、本発明の実施形態の環式PASの回収方法で得られる環式PAS単独でもよいし、所定量の他の成分を含むものでも差し障り無い。ただし、環式PAS以外の成分を含む場合は、環式PAS以外の成分が、線状PASや分岐構造を有するPASなど、PAS成分であることが特に好ましい。少なくとも本発明の実施形態の環式PASを含み、以下に例示する方法により高重合度体へ変換可能なものがポリアリーレンスルフィドプレポリマーであり、以下PASプレポリマーと称する場合もある。
環式ポリフェニレンスルフィド化合物の生成率の測定は、HPLCを用いた定性定量分析によって行なった。HPLCの測定条件を以下に示す。
カラム:関東化学社製 Mightysil RP-18 GP150-4.6(5μm)
検出器:フォトダイオードアレイ検出器(波長270nm)
反応混合物中のスルフィド化剤の定量(水硫化ナトリウムの定量)は、イオンクロマトグラフィーを用いて以下の条件にて実施した。
カラム:島津製作所製 Shim-packIC-SA2(250mm×4.6mmID)
検出器:電気伝導度検出器(サプレッサ)
溶離液:4.0mM炭酸水素ナトリウム/1.0mM炭酸ナトリウム水溶液
流速:1.0mL/分
注入量:50マイクロリットル
カラム温度:30℃。
反応生成物を含む反応混合物中のジハロゲン化芳香族化合物の定量(p-ジクロロベンゼンの定量)は、ガスクロマトグラフィーを用いて以下の条件にて実施した。
カラム:J&W社製 DB-5 0.32mm×30m(0.25μm)
キャリアーガス:ヘリウム
検出器:水素炎イオン化検出器(FID)。
原料として用いる線状ポリフェニレンスルフィドの重量平均分子量は下記条件にて測定し、標準ポリスチレン換算として求めた。
カラム:Shodex UT806M×2
カラム温度:210℃
移動相:1-クロロナフタレン
検出器:示差屈折率検出器
検出器温度:210℃
図1は、本実施例で使用した反応装置10の構成の概要を模式的に表わす説明図である。反応装置10は、容器(I)、(II)、(III)および(IV)を備える。容器(I)では、水分を含むスルフィド化剤の脱水を行う。容器(I)で脱水したスルフィド化剤は、流路20を介して容器(II)へ送られる。
<原料混合物(a-1)の調製>
攪拌機および精留塔を具備したSUS316製70リットルの容器(I)に水硫化ナトリウム48重量%水溶液を14.6kg(水硫化ナトリウムとして7.0kg、125モル)、水酸化ナトリウム48重量%水溶液10.9kg(水酸化ナトリウムとして5.2kg、131モル)、N-メチル-2-ピロリドン(NMP)25.0kg(24.4リットル)を仕込み、窒素ガスを通じながら205℃まで徐々に昇温し脱水操作を行った。脱水操作での留出液をガスクロマトグラフィーで分析したところ留出液にはNMPが0.15kg(0.15リットル)含まれており、容器(I)にNMPが24.9kg(24.2リットル)残存していることがわかった。なお、脱水工程を通して反応系から飛散した硫化水素は2.5モルであり、硫化水素の飛散により容器(I)から水硫化ナトリウムが2.5モル減少し、水酸化ナトリウムが2.5モル増加したことになる。
攪拌機を具備したSUS316製70リットルの容器(III)に、容器(II)で調製した原料混合物(a-1)を40kg供給し、窒素下に密封し、内温を250℃まで昇温した後、2時間保持して初期反応を行ない、初期反応混合物を得た。初期反応後の容器(III)の圧力は0.4MPaであった。初期反応混合物をサンプリングして分析した結果、初期反応混合物における未反応のスルフィド化剤の濃度、すなわち、初期反応混合物1キログラム当たりに含まれる未反応のスルフィド化剤は、0.022モルであった。原料混合物(a-1)のスルフィド化剤濃度に対する初期反応混合物のスルフィド化剤濃度の比は、5%であった。また、初期反応混合物における未反応のジハロゲン化芳香族化合物の濃度、すなわち、初期反応混合物1キログラム当たりに含まれる未反応のジハロゲン化芳香族化合物は、0.027モルであった。原料混合物(a-1)のジハロゲン化芳香族化合物濃度に対する初期反応混合物のジハロゲン化芳香族化合物濃度の比は、6%であった。また、環式PPSの生成率は14%であった。本反応中の揮散成分および追加成分はないことから初期反応混合物の重量変化はなく、基質濃度は原料混合物(a-1)と同一に維持できたと見なせる。
上記の初期反応混合物を含む容器(III)に、容器(III)の内温を250℃に保持したまま、容器(II)から原料混合物(a-1)を20kg/時間の速度でスラリーシール型キャンドモータポンプを使用して連続的に供給した(操作A)。また同時に、容器(III)から反応混合物(b)を20kg/時間の速度でスラリーシール型キャンドモータポンプを使用して連続的に抜き出し(操作B)、配管内で200℃以下に冷却し、受け容器である容器(IV)に移送して環式PPSを含む混合物を得た。本操作を10時間継続した。
ここでは原料混合物(a)の供給(操作A)および反応混合物(b)の抜き出し(操作B)を行わず、回分式にて環式PASを合成した例を示す。
ここでは従来技術による線状ポリアリーレンスルフィドの製造、すなわちスルフィド化剤とジハロゲン化芳香族化合物とをスルフィド化剤の硫黄成分1モルに対して1.25リットル以上の有機極性溶媒中を用いて、加熱して反応させて得られる反応混合物を固液分離に処することで環式ポリアリーレンスルフィドと線状ポリアリーレンスルフィドの分離を行い得られる溶媒を含む固形分を、さらに水洗して線状ポリアリーレンスルフィドを製造した例を示す。
この様にして得られた固体を分析した結果、赤外分光分析(装置;島津社製FTIR-8100A)における吸収スペクトルより線状のポリフェニレンスルフィドであることがわかった。また重量平均分子量は10,000であった。
ここではスルフィド化剤及びジハロゲン化芳香族化合物および有機極性溶媒に加え、線状ポリアリーレンスルフィドを含む原料混合物(a)を調製して環式PASの製造を行った結果を示す。
実施例1と同様にして脱水操作を行った後、攪拌機を具備したSUS316製300リットルの容器(II)に先の脱水操作で水を除いた混合物の5分の1(水硫化ナトリウムとして1.4kg(24.5モル)、NMPとして5.0kg(4.8リットル))を入れ、さらに参考例1で調製した線状PPSを10.6kg(硫黄成分およびアリーレン成分として98.0モル)、NMPを241kg(235リットル)、p-ジクロロベンゼン(p-DCB)3.9kg(26.5モル)を追添加して、原料混合物(a-2)とした。したがって、原料混合物(a-2)の有機極性溶媒量で表す基質濃度は、硫黄成分1モル当たり1.96リットルであった。また、有機極性溶媒量で表すアリーレン単位の基質濃度は、アリーレン単位1モル当たり1.92リットルであった。また、原料混合物(a-2)中のアリーレン単位量は、硫黄成分1モル当たり1.02モルとなった。容器(II)では、原料混合物(a-2)を撹拌しながら内温を140℃で保持した。
攪拌機を具備したSUS316製70リットルの容器(III)に上記で調製した原料混合物(a-2)を40kg供給し、窒素下に密封し、内温を250℃まで昇温した後、2時間保持して初期反応を行ない、初期反応混合物を得た。初期反応後の容器(III)の圧力は0.3MPaであった。初期反応混合物をサンプリングして分析した結果、初期反応混合物における未反応のスルフィド化剤の濃度、すなわち、初期反応混合物1キログラム当たりに含まれる未反応のスルフィド化剤は、0.005モルであった。原料混合物(a-2)のスルフィド化剤濃度に対する初期反応混合物のスルフィド化剤濃度の比は、5%であった。また、初期反応混合物における未反応のジハロゲン化芳香族化合物の濃度、すなわち、初期反応混合物1キログラム当たりに含まれる未反応のジハロゲン化芳香族化合物は、0.009モルであった。原料混合物(a-2)のジハロゲン化芳香族化合物濃度に対する初期反応混合物のジハロゲン化芳香族化合物濃度の比は、9%であった。また、環式PPSの生成率は12%であった。本反応中の揮散成分および追加成分はないことから初期反応混合物の重量変化はなく、基質濃度は原料混合物(a-2)と同一に維持できたと見なせる。
上記の初期反応混合物を含む容器(III)に、容器(III)の内温を250℃に保持したまま、容器(II)から原料混合物(a-2)を20kg/時間の速度でスラリーシール型キャンドモータポンプを使用して連続的に供給した(操作A)。また同時に、容器(III)から反応混合物(b)を20kg/時間の速度でスラリーシール型キャンドモータポンプを使用して連続的に抜き出し(操作B)、配管内で200℃以下に冷却し、受け容器である容器(IV)に移送して環式PPSを含む混合物を得た。本操作を10時間継続した。
ここでは原料混合物(a)の供給(操作A)および反応混合物(b)の抜き出し(操作B)を行わず、回分式にて環式PASを合成した例を示す。
ここでは原料混合物(a)および反応混合物(b)の有機極性溶媒量を実施例1よりも増加した、すなわち基質濃度が低い例を示す。
実施例1と同様にして脱水操作を行った後、攪拌機を具備したSUS316製300リットルの容器(II)に先の脱水操作で水を除いた混合物を入れ、NMPを395kg(385リットル)、p-ジクロロベンゼン(p-DCB)18.4kg(125モル)を追添加して、原料混合物(a-3)とした。したがって、原料混合物(a-3)の有機極性溶媒量で表す硫黄成分の基質濃度は、硫黄成分1モル当たり3.34リットルであった。また、有機極性溶媒量で表すアリーレン単位の基質濃度は、アリーレン単位1モル当たり3.27リットルであった。また、原料混合物(a-3)中のアリーレン単位量は、硫黄成分1モル当たり1.02モルとなった。容器(II)では、原料混合物(a-3)を撹拌しながら内温を140℃で保持した。
攪拌機を具備したSUS316製70リットルの容器(III)に上記で調製した原料混合物(a-3)を40kg供給し、窒素下に密封し、内温を250℃まで昇温した後、2時間保持して初期反応を行ない、初期反応混合物を得た。初期反応後の容器(III)の圧力は0.4MPaであった。初期反応混合物をサンプリングして分析した結果、初期反応混合物における未反応のスルフィド化剤の濃度、すなわち、初期反応混合物1キログラム当たりに含まれる未反応のスルフィド化剤は、0.014モルであった。原料混合物(a-3)のスルフィド化剤濃度に対する初期反応混合物のスルフィド化剤濃度の比は、5%であった。また、初期反応混合物における未反応のジハロゲン化芳香族化合物の濃度、すなわち、初期反応混合物1キログラム当たりに含まれる未反応のジハロゲン化芳香族化合物は、0.017モルであった。原料混合物(a-3)のジハロゲン化芳香族化合物濃度に対する初期反応混合物のジハロゲン化芳香族化合物濃度の比は、6%であった。また、環式PPSの生成率は18%であった。本反応中の揮散成分および追加成分はないことから初期反応混合物の重量変化はなく、基質濃度は原料混合物(a-3)と同一に維持できたと見なせる。
上記の初期反応混合物を含む容器(III)に、容器(III)の内温を250℃に保持したまま、容器(II)から原料混合物(a-3)を20kg/時間の速度でスラリーシール型キャンドモータポンプを使用して連続的に供給した(操作A)。また同時に、容器(III)から反応混合物(b)を20kg/時間の速度でスラリーシール型キャンドモータポンプを使用して連続的に抜き出し(操作B)、配管内で200℃以下に冷却し、受け容器である容器(IV)に移送して環式PPSを含む混合物を得た。本操作を10時間継続した。
ここでは原料混合物(a)の供給(操作A)および反応混合物(b)の抜き出し(操作B)を行わず、回分式にて環式PASを合成した例を示す。
ここでは原料混合物(a)および反応混合物(b)の有機極性溶媒量を実施例1よりも低減した、すなわち基質濃度が高い例を示す。
実施例1と同様にして脱水操作を行った後、攪拌機を具備したSUS316製300リットルの容器(II)に先の脱水操作で水を除いた混合物を入れ、NMPを155kg(151リットル)、p-ジクロロベンゼン(p-DCB)18.4kg(125モル)を追添加して、原料混合物(a-4)とした。したがって、原料混合物(a-4)の有機極性溶媒量で表す基質濃度は、硫黄成分1モル当たり1.43リットルであった。また、有機極性溶媒量で表すアリーレン単位の基質濃度はアリーレン単位の基質濃度は、アリーレン単位1モル当たり1.40リットルであった。また、原料混合物(a-4)中のアリーレン単位量は、硫黄成分1モル当たり1.02モルとなった。容器(II)では、原料混合物(a-4)を撹拌しながら内温を140℃で保持した。
攪拌機を具備したSUS316製70リットルの容器(III)に上記で調製した原料混合物(a-4)を40kg供給し、窒素下に密封し、内温を250℃まで昇温した後、2時間保持して初期反応を行ない、初期反応混合物を得た。初期反応後の容器(III)の圧力は0.4MPaであった。初期反応混合物をサンプリングして分析した結果、初期反応混合物における未反応のスルフィド化剤の濃度、すなわち、初期反応混合物1キログラム当たりに含まれる未反応のスルフィド化剤は、0.017モルであった。原料混合物(a-4)のスルフィド化剤濃度に対する初期反応混合物のスルフィド化剤濃度の比は、3%であった。また、初期反応混合物における未反応のジハロゲン化芳香族化合物の濃度、すなわち、初期反応混合物1キログラム当たりに含まれる未反応のジハロゲン化芳香族化合物は、0.024モルであった。原料混合物(a-4)のジハロゲン化芳香族化合物濃度に対する初期反応混合物のジハロゲン化芳香族化合物濃度の比は、4%であった。また、環式PPSの生成率は10%であった。本反応中の揮散成分および追加成分はないことから初期反応混合物の重量変化はなく、基質濃度は原料混合物(a-4)と同一に維持できたと見なせる。
上記の初期反応混合物を含む容器(III)に、容器(III)の内温を250℃に保持したまま、容器(II)から原料混合物(a-4)を20kg/時間の速度でスラリーシール型キャンドモータポンプを使用して連続的に供給した(操作A)。また同時に、容器(III)から反応混合物(b)を20kg/時間の速度でスラリーシール型キャンドモータポンプを使用して連続的に抜き出し(操作B)、配管内で200℃以下に冷却し、受け容器である容器(IV)に移送して環式PPSを含む混合物を得た。本操作を5時間継続した。
ここでは原料混合物(a)の供給(操作A)および反応混合物(b)の抜き出し(操作B)を行わず回分式にて環式PASを合成した例を示す。
ここでは操作Aで供給する原料混合物(a)および操作Bで抜き出す反応混合物(b)の量を実施例1より増加、すなわち反応混合物(b)の平均滞留時間を短縮した例を示す。
ここでは原料混合物(a)の供給(操作A)および反応混合物(b)の抜き出し(操作B)を行わず、回分式にて環式PASを合成した例を示す。
ここでは反応容器から抜き出した反応混合物(b)をさらに加熱する操作(D)を行った例を示す。
ここでは基質濃度の変動を伴う例を示す。
図1に示した装置を用いて、実施例1と同様にして操作(A)および操作(B)を5時間行った後、容器(II)にNMPを85.0kg(82.9リットル)を一挙に添加し、原料混合物(a-1)を希釈し、原料混合物(a-5)とした。したがって、原料混合物の有機極性溶媒で表す硫黄成分の基質濃度は、硫黄成分1モル当たり1.96リットルから3.33リットルとなった。また、原料混合物の有機極性溶媒量で表わすアリーレン単位の基質濃度は、アリーレン単位1モル当たり1.92リットルから3.26リットルとなった。原料混合物中の硫黄成分に対するアリーレン単位量は、硫黄成分1モル当たり1.02モルで変化なかった。
ここでは初期反応混合物の調製を実施例1で例示した回分式ではなく、反応容器に有機極性溶媒を導入し、同反応容器内に原料混合物(a)を供給する操作と、同反応容器内の反応混合物の一部を反応容器から抜き出す操作を並行して行うことで調製した例を示す。
攪拌機を具備したSUS316製70リットルの容器(III)にNMPを20kg供給し、窒素下に密封し、内温を250℃まで昇温した後、実施例1と同様に容器(II)で調製した原料混合物(a-1)を、10kg/時間の速度でスラリーシール型キャンドモータポンプを使用して連続的に容器(III)に供給した。また同時に、容器(III)から、反応生成物を含む初期反応混合物を20kg/時間の速度でスラリーシール型キャンドモータポンプを使用して連続的に抜き出し、配管内で200℃以下に冷却し、容器(IV)に移送した。容器(III)への原料混合物(a-1)の供給および容器(III)からの初期反応混合物の抜き出しを連続して行なう初期反応の操作を、12時間継続した。
20…流路
22…分岐ライン
24…分岐ライン
42…循環ライン
44…循環ライン
Claims (16)
- 少なくともスルフィド化剤、ジハロゲン化芳香族化合物および有機極性溶媒を含む原料混合物(a)を加熱して反応させて、環式ポリアリーレンスルフィドを製造する方法であって、
原料混合物(a)から生じた反応生成物を含む反応容器内の反応混合物(b)へ原料混合物(a)を供給する操作(A)と、前記反応容器内の反応混合物(b)の一部を前記反応容器から抜き出す操作(B)と、前記反応容器内を加熱する操作(C)とを、それぞれ継続的に行う環式ポリアリーレンスルフィドの製造方法。 - 前記反応混合物(b)中の有機極性溶媒がスルフィド化剤の硫黄原子1モルに対して1.25リットル以上、50リットル以下である請求項1に記載の環式ポリアリーレンスルフィドの製造方法。
- 前記反応容器内の反応混合物(b)中の硫黄成分量およびアリーレン単位量のそれぞれと、有機極性溶媒量との関係を一定に維持する請求項1または2のいずれかに記載の環式ポリアリーレンスルフィドの製造方法。
- 前記操作(A)および前記操作(B)を同時に行う請求項1から3のいずれか1項に記載の環式ポリアリーレンスルフィドの製造方法。
- 前記操作(A)および前記操作(B)を連続的に行う請求項1から4のいずれか1項に記載の環式ポリアリーレンスルフィドの製造方法。
- 前記反応容器内の反応混合物(b)の量を一定に維持する請求項1から5のいずれか1項に記載の環式ポリアリーレンスルフィドの製造方法。
- 前記反応容器内の反応混合物(b)中の未反応のスルフィド化剤およびジハロゲン化芳香族化合物の濃度をそれぞれ、前記原料混合物(a)中のスルフィド化剤およびジハロゲン化芳香族化合物の各濃度の30%以下に維持し、かつ、前記反応混合物(b)1キログラム当たりに含まれる未反応のスルフィド化剤およびジハロゲン化芳香族化合物を、それぞれ0.15モル以下に維持する請求項1から6のいずれか1項に記載の環式ポリアリーレンスルフィドの製造方法。
- 前記操作(B)によって前記反応容器から抜き出した反応混合物(b)を加熱する操作(D)をさらに行なう請求項1から7のいずれか1項に記載の環式ポリアリーレンスルフィドの製造方法。
- 前記操作(C)における加熱を常圧における還流温度を超える温度で行う請求項1から8のいずれか1項に記載の環式ポリアリーレンスルフィドの製造方法。
- 前記ジハロゲン化芳香族化合物がジクロロベンゼンである請求項1から9のいずれか1項に記載の環式ポリアリーレンスルフィドの製造方法。
- 前記スルフィド化剤がアルカリ金属硫化物である請求項1から10のいずれか1項に記載の環式ポリアリーレンスルフィドの製造方法。
- 前記原料混合物(a)は線状ポリアリーレンスルフィドを含む請求項1から11のいずれか1項に記載の環式ポリアリーレンスルフィドの製造方法。
- 予め前記原料混合物(a)を回分式で反応させて前記反応混合物(b)を得た後に、前記操作(A)および前記操作(B)を開始する請求項1から12のいずれか1項に記載の環式ポリアリーレンスルフィドの製造方法。
- 前記操作(B)において遠心ポンプを使用して前記反応混合物(b)の抜き出し量を調整する請求項1~13のいずれか1項に記載の環式ポリアリーレンスルフィドの製造方法。
- 前記反応容器には、該反応容器に接続されてポンプを用いて前記反応容器との間で前記反応混合物(b)を循環させる循環ラインが設けられており、前記操作(B)では、前記循環ラインを介して前記反応容器から前記反応混合物(b)を抜き出す請求項1~14のいずれか1項に記載の環式ポリアリーレンスルフィドの製造方法。
- 前記反応容器が、該反応容器に接続されて前記操作(A)で前記反応容器に前記原料混合物(a)を供給する供給容器、および/または前記反応容器に接続されて前記操作(B)で前記反応容器から抜き出した前記反応混合物(b)が供給される受け容器と、均圧ラインで連結されて均圧化されている請求項1~15のいずれか1項に記載の環式ポリアリーレンスルフィドの製造方法。
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