WO2020009481A1 - Procédé de préparation de poly(sulfure d'arylène) - Google Patents

Procédé de préparation de poly(sulfure d'arylène) Download PDF

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WO2020009481A1
WO2020009481A1 PCT/KR2019/008167 KR2019008167W WO2020009481A1 WO 2020009481 A1 WO2020009481 A1 WO 2020009481A1 KR 2019008167 W KR2019008167 W KR 2019008167W WO 2020009481 A1 WO2020009481 A1 WO 2020009481A1
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polyarylene sulfide
equivalents
alkali metal
reactor
reaction
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Korean (ko)
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정권수
한중진
박은주
류현욱
김한솔
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020190079236A external-priority patent/KR102251404B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to CN201980028341.0A priority Critical patent/CN112041373B/zh
Priority to US17/047,341 priority patent/US11414521B2/en
Priority to EP19831164.9A priority patent/EP3766921B1/fr
Priority to JP2020560792A priority patent/JP7191344B2/ja
Publication of WO2020009481A1 publication Critical patent/WO2020009481A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0259—Preparatory processes metal hydrogensulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/025—Preparatory processes
    • C08G75/0254—Preparatory processes using metal sulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0277—Post-polymerisation treatment
    • C08G75/0281—Recovery or purification

Definitions

  • the present invention relates to a method for producing a polyarylene sulfide having excellent strength, heat resistance, flame retardancy, and processability in processing a molded article with improved yield.
  • Polyarylene sulfide which is represented by polyphenylene sulfide (PPS)
  • PPS polyphenylene sulfide
  • PPS resin since the fluidity is good, it is advantageous to use it as a compound by kneading with filler or reinforcing agent such as glass fiber.
  • PAS is prepared by polymerizing a sulfur source and a dihalogenated aromatic compound under polymerization conditions in the presence of an amide compound such as N-methyl pyrrolidone (NMP), and optionally a molecular weight modifier such as an alkali metal salt is further used.
  • NMP N-methyl pyrrolidone
  • a molecular weight modifier such as an alkali metal salt
  • Japanese Patent No.5623277 includes a step of adding an aromatic compound such as a dihalo aromatic compound and a trihalo aromatic compound to a liquid phase in a polymerization reaction system after a phase separation polymerization process, and cooling the liquid phase. I win a prize in high yield ( ) PAS manufacturing method for obtaining PAS is described. As such a method for producing PAS, a method capable of further improving the yield for obtaining PAS has been desired.
  • the present invention uses the equivalent ratio of the dihalogenated aromatic compound to the sulfur compound in a predetermined range, and optimizes the dehydration reaction and the polymerization process conditions to react the polyarylene sulfide showing excellent strength, heat resistance, flame retardancy, and workability. It is intended to provide a process for producing in yields.
  • a dihalogenated aromatic compound and an amide compound are added to the reactor containing the said sulfur source, and it superposes
  • the dihalogenated aromatic compound is provided at a ratio of 1.04 to 1.08 equivalents based on 1 equivalent of the hydrosulfide of the alkali metal, thereby providing a method for producing polyarylene sulfide.
  • the polyarylene sulfide may be produced in a yield of 85% or more, and may have a melt viscosity of 20 Pa ⁇ S to 150 Pa ⁇ S.
  • the present invention by using the equivalence ratio of the dihalogenated aromatic compound to the sulfur compound in a predetermined range and optimizing and reacting the dehydration reaction and polymerization process conditions, it has excellent strength, heat resistance, flame retardancy, and workability. There is an excellent effect that can be produced in a high yield of polyarylene sulfide.
  • Example 1 is a simplified view of a process for preparing the polyarylene sulfide of Example 1 according to an embodiment of the present invention.
  • first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another component.
  • the dehydration for producing a sulfur source is carried out in the presence of an organic acid salt of an alkali metal, and at the same time the equivalent ratio of the dihalogenated aromatic compound to the sulfur compound is used in a predetermined range.
  • the method for producing the polyarylene sulfide is a dehydration reaction of an alkali metal hydrosulfide and an alkali metal hydroxide at a temperature of from 185 ° C to 205 ° C in a mixed solvent of water and an amide compound in the presence of an organic acid salt of an alkali metal.
  • performing a dehydration to produce a sulfur source comprising a sulfide of an alkali metal and a mixed solvent of water and an amide compound;
  • adding a dihalogenated aromatic compound and an amide compound to a reactor including the sulfur source, polymerizing the reaction at a temperature of 225 ° C. or higher to 245 ° C. or lower, and then raising the temperature to 250 ° C. or higher to 260 ° C. or lower to polymerize.
  • the dehydration liquid is removed during the dehydration (dehydration) using an alkali metal hydrosulfide, etc. to prepare a polyarylene sulfide, about 15% ( v / v) to about 35% (v / v), wherein the dihalogenated aromatic compound is reacted with an alkali metal in a polymerization reaction in which the sulfur source prepared through the dehydration is reacted with the dihalogenated aromatic compound. And about 1.04 equivalents or more and about 1.08 equivalents or less based on 1 equivalent of hydrosulfide.
  • the present invention can significantly increase the yield of the resulting polyarylene sulfide by adding the dihalogenated aromatic compound in a predetermined content range and simultaneously performing the dehydration process and the polymerization process under optimized conditions.
  • it is possible to easily prepare a polyarylene sulfide showing the thermal properties of the final polymer product is equal or more than the conventional.
  • the production method of the polyarylene sulfide of the present invention is also improved in yield, it is possible to increase the output of the final product.
  • the first step described above is to prepare a sulfur source.
  • the sulfur source is prepared by dehydration of an alkali metal hydrosulfide and an alkali metal hydroxide in a mixed solvent of water and an amide compound in the presence of an organic acid salt of the alkali metal.
  • the sulfur source may include a mixed solvent of water and an amide compound remaining after the dehydration reaction together with the sulfide of the alkali metal produced by the reaction of an alkali metal hydrosulfide with an alkali metal hydroxide.
  • polyarylene sulfide having excellent yield is prepared through polymerization using the sulfur source, the dihalogenated aromatic compound, and the amide compound.
  • the sulfide of the alkali metal may be determined according to the type of hydrosulfide of the alkali metal used in the reaction, and specific examples thereof include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, or cesium sulfide, and any one of these Mixtures of two or more may be included.
  • alkali metal hydrosulfide In preparing the sulfur source by the reaction of the alkali metal hydroxide with the hydroxide of the alkali metal, specific examples of the alkali metal hydrosulfide that may be used include lithium sulfide, sodium hydrogen sulfide, potassium hydrogen sulfide, rubidium hydrogen sulfide or cesium hydrogen sulfide. have. Any one or a mixture of two or more of these may be used, and anhydrides or hydrates thereof may also be used.
  • hydroxide of the alkali metal examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and the like, and any one or a mixture of two or more thereof may be used.
  • the alkali metal hydroxide may be used in an equivalent ratio of about 0.90 to about 2.0, more specifically about 1.0 to about 1.5, and more specifically about 1.0 to about 1.1, based on 1 equivalent of the alkali metal hydrosulfide. have.
  • the equivalent weight means a molar equivalent weight (eq / mol).
  • an organic acid salt of an alkali metal is added, which promotes a polymerization reaction as a polymerization aid to increase the degree of polymerization of polyarylene sulfide in a short time.
  • the organic acid salt of the alkali metal may be lithium acetate, sodium acetate, or the like, and any one or a mixture of two or more thereof may be used.
  • the organic acid salt of the alkali metal is generally about 0.01 or more, or about 0.05 or more, or about 0.1 or more, to 1 equivalent of the hydrosulfide of the alkali metal in terms of producing a high yield of melt viscosity suitable for use in general. Or in an equivalent ratio of at least about 0.18, or at least about 0.23.
  • the organic acid salt of the alkali metal is a factor of increase in manufacturing cost when used in an excessive amount in terms of a polymerization aid acting as a catalyst, preferably about 1.0 or less, or about 0.8 or less, or about 0.6 or less, or about 0.5 or less Or equivalent ratios of about 0.45 or less.
  • the reaction of the alkali metal hydrosulfide and the alkali metal hydroxide may be carried out in a mixed solvent of water and an amide compound, wherein specific examples of the amide compound are N, N-dimethylformamide or N, N Amide compounds such as dimethylacetamide; Pyrrolidone compounds such as N-methyl-2-pyrrolidone (NMP) or N-cyclohexyl-2-pyrrolidone; Caprolactam compounds such as N-methyl- ⁇ -caprolactam; Imidazolidinone compounds, such as 1,3-dialkyl-2-imidazolidinone; Urea compounds such as tetramethyl urea; Or phosphate amide compounds such as hexamethyl phosphate triamide, and the like, and any one or a mixture of two or more thereof may be used.
  • the amide compound are N, N-dimethylformamide or N, N Amide compounds such as dimethylacetamide
  • Pyrrolidone compounds such as N-methyl
  • the amide compound may be more specifically N-methyl-2-pyrrolidone (NMP) in consideration of the reaction efficiency and the effect of the cosolvent as a polymerization solvent in the polymerization for preparing polyarylene sulfide.
  • NMP N-methyl-2-pyrrolidone
  • the water may be used in an equivalent ratio of about 1 to about 8 equivalents to 1 equivalent of the amide compound, more specifically in an equivalent ratio of about 1.5 to about 5, and more specifically in an equivalent ratio of about 2.5 to about 4.5 Can be.
  • a reactant including an alkali metal hydrosulfide, an alkali metal hydroxide, and the like may generate sulfides of the alkali metal through dehydration.
  • the dehydration reaction is carried out at a temperature range of about 185 °C to about 205 °C, can be carried out by stirring at a speed of about 100 rpm to 500 rpm, more specifically at a speed of about 100 rpm to about 300 rpm have.
  • the dehydration reaction temperature is about 185 ° C.
  • the dehydration reaction temperature is about 205 It should be carried out below °C.
  • solvents such as water in the reactants may be removed by distillation, etc., and a part of the amide compound is discharged together with the water, and some sulfur contained in the sulfur source reacts with the water by heat during the dehydration process. It may be volatilized as hydrogen sulfide gas.
  • the hydroxide of the alkali metal of the same mole as the hydrogen sulfide may be produced.
  • the total volume of the entire mixture including the mixed solvent of water and the amide compound in the dehydration liquid generated during the dehydration reaction in the first step, i. Based on the amide compound is included from about 15% to about 35% (v / v).
  • the concentration of the amide compound should be maintained in the above-described range. Specifically, the concentration of the amide compound in the dehydration solution may be about 25% to about 35% (v / v), or about 28% to about 32% (v / v).
  • sulfur contained in the sulfur source remaining in the sulfur source that is, sulfur sulfide of the alkali metal introduced into the sulfur-containing reactant, and the like reacts with water to produce hydrogen sulfide and alkali metal hydroxide, and the produced hydrogen sulfide Since is volatilized, the amount of sulfur in the sulfur source remaining in the system after the dehydration process may be reduced by the hydrogen sulfide volatilized out of the system during the dehydration process.
  • the amount of sulfur remaining in the system after the dehydration process is a molar amount of sulfur contained in a sulfur source introduced as a reactant, that is, a sulfur-containing reactant of an alkali metal.
  • the amount is equal to minus the molar amount of hydrogen sulfide volatilized out of the system. Accordingly, it is necessary to quantify the amount of effective sulfur contained in the sulfur source remaining in the system after the dehydration process from the amount of hydrogen sulfide volatilized out of the system.
  • the water remaining in the system after the dehydration process is completed has a molar ratio of about 1.5 to about 3.5, more specifically about 1.6 to about 3.0, even more specifically about 1.8 to about 2.8 per mole of effective sulfur. May be performed until If the amount of water in the sulfur source is excessively reduced by the dehydration process, water may be adjusted by adding water prior to the polymerization process.
  • the sulfur source prepared by the reaction and dehydration of the alkali metal hydrosulfide and the alkali metal hydroxide and dehydration may include a mixed solvent of water and an amide compound together with the sulfide of the alkali metal,
  • the water may be included in a molar ratio of about 1.5 to about 3.5 specifically with respect to 1 mole of sulfur contained in the sulfur source.
  • the sulfur source may further comprise a hydroxide of an alkali metal produced by the reaction of sulfur and water.
  • the second step is a step of polymerizing the sulfur source with a dihalogenated aromatic compound to prepare polyarylene sulfide.
  • the dihalogenated aromatic compound usable for the preparation of the polyarylene sulfide is a compound in which two hydrogens in an aromatic ring are substituted with halogen atoms, and specific examples thereof include o-dihalobenzene, m-dihalobenzene, and p-dihal.
  • the halogen atom may be fluorine, chlorine, bromine or iodine.
  • p-DCB p-dichlorobenzene
  • the dihalogenated aromatic compound should be added at about 1.04 to about 1.08 equivalents based on 1 equivalent of the hydrosulfide of the alkali metal. When introduced in the above content range, it is possible to prepare a polyarylene sulfide having excellent physical properties without concern for the increase in the chlorine content present in the polyarylene sulfide to be produced.
  • the dihalogenated aromatic compound is about 1.04 to about 1.08 in order to take into account the superiority of the improvement effect by controlling the addition amount of the sulfur source and the dihalogenated aromatic compound, to control the melt viscosity and the total volatile organic compound, and to improve the yield. It should be put in equivalence.
  • the method may further include lowering the temperature of the reactor including the sulfur source to a temperature of less than about 200 ° C. to less than about 200 ° C. to prevent vaporization of the dihalogenated aromatic compound. have.
  • the polymerization of the sulfur source and the dihalogenated aromatic compound may be carried out in a solvent of an amide compound which is stable to alkali at high temperature as an aprotic polar organic solvent.
  • the amide compound may be N-methyl-2-pyrrolidone (NMP).
  • the amide compound added in the second step is a molar ratio of water (H 2 O) to the amide compound present in the polymerization system. (Molar ratio of water / amide compound) can be added in an amount such that it is about 0.85 or more.
  • the amide-based compound further added in the second step is about 1.0 equivalent to about 2.0 equivalents, or about 1.1 equivalents to about 1.85 equivalents, or about 1.1 equivalents to about 1.35, based on 1 equivalent of the hydrosulfide of the alkali metal. It can be added in equivalent weight.
  • the amide compound when performing the polymerization reaction in the second step, is added to the molar ratio of 2.5 to 4.0 with respect to 1 mol of sulfur. This corresponds to the content of the final amide compound present in the system during the second stage of the polymerization reaction, and is further added in the second stage and the remaining amide compound in the sulfur source obtained through the dehydration reaction in the first stage. It can be said that it is the total amount of an amide compound.
  • the final content of the amide compound present in the system during the polymerization step of the second step for example, from the total amount of the amide compound introduced in each of the first step and the second step proceeds to the dehydration solution of the first step It can confirm by subtracting the quantity of the outgoing amide compound, and acidifying.
  • additives for controlling the polymerization reaction or molecular weight such as a molecular weight adjusting agent, a crosslinking agent during the polymerization reaction may be further added in a content that does not lower the physical properties and production yield of the polyarylene sulfide to be finally prepared.
  • a prepolymer of polyarylene sulfide is reacted by reacting a halogenated aromatic compound with a sulfur compound. It is characterized in that it is carried out in a multi-step, including a shear polymerization process for producing a polymer) and a post-stage polymerization process for increasing the molecular weight and melt viscosity by using the prepolymer.
  • the polymerization reaction of the sulfur source and the dihalogenated aromatic compound is specifically a temperature higher than the temperature at the time of the first polymerization reaction continuously after the first polymerization reaction from about 225 ° C. or more to about 245 ° C. or less.
  • the secondary polymerization should be carried out from about 250 ° C. or higher to about 260 ° C. or lower.
  • the first polymerization reaction should be carried out in an aromatic compound in a temperature range of about 225 ° C. or more and about 245 ° C. or less in terms of conversion and yield improvement. Or less than or about 230 ° C. or higher and about 245 ° C. or lower.
  • the secondary polymerization reaction should be carried out at more than 250 °C in terms of maintaining the melt viscosity to a sufficient degree to effectively perform the injection molding, and to reduce the yield and melt viscosity decrease due to high temperature decomposition reaction due to excessive temperature rise In terms of prevention, it should be carried out below 260 °C.
  • the secondary polymerization may be performed at a temperature higher than about 5 ° C. to about 35 ° C., specifically about 5 ° C. to about 32 ° C., or about 20 ° C. to about 30 ° C. It can be carried out at a high temperature.
  • the reaction product produced as a result of the polymerization reaction is separated into an aqueous phase and an organic phase, wherein polyarylene sulfide as a polymerization reactant is dissolved in the organic phase. Accordingly, the process for the precipitation and separation of the polyarylene sulfide prepared may be optionally further performed.
  • the precipitation of the polyarylene sulfide may be performed by adding water to the reaction mixture in a ratio of 3 to 5 equivalents to 1 equivalent of sulfur and cooling.
  • water is added in the above content range, polyarylene sulfide can be precipitated with excellent efficiency.
  • the precipitated polyarylene sulfide may then optionally be further subjected to washing and filtration drying processes in accordance with conventional methods.
  • polyarylene sulfide Specific examples of the polyarylene sulfide may be referred to the following examples.
  • the manufacturing method of the polyarylene sulfide is not limited to the contents described herein, and the manufacturing method may further employ a step generally employed in the art to which the present invention pertains, Step (s) may be modified by conventionally changeable step (s).
  • the polyarylene sulfide produced by the above production method is produced in a yield of about 85% or more, or about 85.5% or more, and is about 20 Pa.S to 150 Pa.S, or about 22 Pa.S to 130. Pa.S, or about 25 Pa.S to 120 Pa.S, or about 40 Pa.S to 120 Pa.S.
  • the melt viscosity of the polyarylene sulfide is too low, the polymer repeating unit is shortened, so that the content of the end group, Cl, etc. is increased, and thus, the mechanical strength may be lowered. desirable.
  • the molding conditions may be changed in order to facilitate the molding during injection molding, so about 150 Pa ⁇ S or less is preferable. That is, the polyarylene sulfide may be maintained in the above-described range because the melt viscosity is too small, the mechanical strength is insufficient, and when the polyarylene sulfide is too large, the fluidity during melt molding of the resin composition is poor and the molding operation becomes difficult.
  • the polyarylene sulfide may have a melting melting temperature (Tm) of about 270 ° C to about 300 ° C, and a crystallization temperature (Tc) of about 180 ° C to 250 ° C.
  • Tm melting melting temperature
  • Tc crystallization temperature
  • the melting point (Tm) and crystallization temperature (Tc) of the polyarylene sulfide may be measured using a differential scanning calorimeter (DSC) device (TA instrument, TA Q2000), and a measuring method thereof Is well known in the art and a detailed description thereof will be omitted.
  • DSC differential scanning calorimeter
  • the polyarylene sulfide may have a weight average molecular weight (Mw) of more than about 10000 g / mol to about 30000 g / mol or less.
  • the weight average molecular weight (Mw) of the polyarylene sulfide can be measured using gel permeation chromatography (GPC), for example, using a Waters PL-GPC220 instrument as a gel permeation chromatography (GPC) apparatus, Polymer Laboratories PLgel MIX-B can be measured using a 300mm length column, the measuring method is well known in the art and a detailed description thereof will be omitted.
  • GPC gel permeation chromatography
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na 2 S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 0.44 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 195 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the measured NMP concentration (v / v%) in the dehydration liquid that was removed to the outside while performing the dehydration reaction was 30.2% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 1.82.
  • the washed polyphenylene sulfide was recovered by drying in a vacuum oven at 150 ° C. for 8 hours.
  • the yield of polyphenylene sulfide recovered at this time was 85.8%, and the viscosity was 73.8 Pa ⁇ S.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na2S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 0.44 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 205 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the measured NMP concentration (v / v%) in the dehydration liquid which was removed to the outside while performing the dehydration reaction was 30.6% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 1.85.
  • the washed polyphenylene sulfide was recovered by drying in a vacuum oven at 150 ° C. for 8 hours.
  • the yield of polyphenylene sulfide recovered at this time was 86.4%, and the viscosity was 58.0 Pa ⁇ S.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na2S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 0.44 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 205 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the measured NMP concentration (v / v%) in the dehydration liquid that was removed to the outside while performing the dehydration reaction was 30.9% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 1.81.
  • the washed polyphenylene sulfide was recovered by drying in a vacuum oven at 150 ° C. for 8 hours.
  • the yield of polyphenylene sulfide recovered at this time was 85.0%, and the viscosity was 65.1 Pa.S.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na2S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 0.44 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 185 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the measured NMP concentration (v / v%) in the dehydration liquid that was removed to the outside while performing the dehydration reaction was 31.0% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 2.30.
  • the washed polyphenylene sulfide was recovered by drying in a vacuum oven at 150 ° C. for 8 hours.
  • the yield of polyphenylene sulfide recovered at this time was 91.6%, and the viscosity was 46.4 Pa ⁇ S.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na2S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 0.44 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 195 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the NMP concentration (v / v%) measured in the dehydration liquid which was removed to the outside while performing the dehydration reaction was 29.9% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 1.92.
  • the washed polyphenylene sulfide was recovered by drying in a vacuum oven at 150 ° C. for 8 hours.
  • the yield of polyphenylene sulfide recovered at this time was 87.8%, and the viscosity was 27.3 Pa ⁇ S.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na 2 S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 0.44 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 185 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the measured NMP concentration (v / v%) in the dehydration liquid that was removed to the outside while performing the dehydration reaction was 29.7% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 2.09.
  • the washed polyphenylene sulfide was recovered by drying in a vacuum oven at 150 ° C. for 8 hours.
  • the yield of polyphenylene sulfide recovered at this time was 79.6%, and the viscosity was 56.4 Pa ⁇ S.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na 2 S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 0.44 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 180 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the NMP concentration (v / v%) measured in the dehydration liquid which was removed to the outside while performing the dehydration reaction was 31.2% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 2.38.
  • the washed polyphenylene sulfide was recovered by drying in a vacuum oven at 150 ° C. for 8 hours.
  • the yield of polyphenylene sulfide recovered at this time was 77.7%, and the viscosity was 61.1 Pa ⁇ S.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na2S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 0.44 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 180 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the measured NMP concentration (v / v%) in the dehydration liquid that was removed to the outside while performing the dehydration reaction was 30.4% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 2.44.
  • the washed polyphenylene sulfide was recovered by drying in a vacuum oven at 150 ° C. for 8 hours.
  • the yield of polyphenylene sulfide recovered at this time was 69.4%, and the viscosity was 220.3 Pa ⁇ S.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na2S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 0.44 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 215 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the measured NMP concentration (v / v%) in the dehydration liquid that was removed to the outside while performing the dehydration reaction was 35.0% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 2.13.
  • the washed polyphenylene sulfide was recovered by drying in a vacuum oven at 150 ° C. for 8 hours.
  • the yield of polyphenylene sulfide recovered at this time was 74.8%, and the viscosity was 62.3 Pa ⁇ S.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na2S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 0.44 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 185 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the measured NMP concentration (v / v%) in the dehydration liquid that was removed to the outside while performing the dehydration reaction was 28.9% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 2.21.
  • the washed polyphenylene sulfide was recovered by drying in a vacuum oven at 150 ° C. for 8 hours.
  • the yield of polyphenylene sulfide recovered at this time was 83.2%, and the viscosity was 9.8 Pa.S.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na2S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 0.20 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 210 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the measured NMP concentration (v / v%) in the dehydration liquid that was removed to the outside while performing the dehydration reaction was 28.6% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 1.82.
  • the washed polyphenylene sulfide was recovered by drying in a vacuum oven at 150 ° C. for 8 hours.
  • the yield of polyphenylene sulfide recovered at this time was 68.0%, and the viscosity was 6.1 Pa.S.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na2S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 0.20 equivalents of sodium acetate (CH 3 COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 205 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the measured NMP concentration (v / v%) in the dehydration liquid that was removed to the outside while performing the dehydration reaction was 28.9% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 1.72.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na2S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time 0.44 equivalents of sodium acetate (CH3COONa) powder, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 185 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the measured NMP concentration (v / v%) in the dehydration liquid that was removed to the outside while performing the dehydration reaction was 30.2% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 2.26.
  • the washed polyphenylene sulfide was recovered by drying in a vacuum oven at 150 ° C. for 8 hours.
  • the yield of polyphenylene sulfide recovered at this time was 74.6%, and the viscosity was 38.3 Pa ⁇ S.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na2S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 1.65 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 185 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source. At this time, the NMP concentration (v / v%) measured in the dehydration liquid which was removed to the outside while performing the dehydration reaction was 30.0% as measured by gas chromatography. In addition, the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 1.50.
  • the washed polyphenylene sulfide was recovered by drying in a vacuum oven at 150 ° C. for 8 hours.
  • the yield of polyphenylene sulfide recovered at this time was 64.8%, and the viscosity was 5.4 Pa ⁇ S.
  • first step a dehydration reaction (first step) and a polymerization reaction (second step) were performed according to the method as shown in FIG. 1.
  • Sodium sulfide (Na2S) was prepared by mixing 1.00 equivalents of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) in a reactor. At this time, 0.44 equivalents of sodium acetate (CH3COONa) powder, 4.00 equivalents of N-methyl-2-pyrrolidone (NMP) and 4.72 equivalents of distilled water were added to the reactor. The reactor was heated to 185 ° C. for 1 hour with stirring at 150 rpm to carry out a dehydration reaction, and the remaining mixture obtained after the dehydration reaction was obtained as a sulfur source.
  • NaSH sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • the measured NMP concentration (v / v%) in the dehydration liquid that was removed to the outside while performing the dehydration reaction was 53.0% as measured by gas chromatography.
  • the molar ratio of H 2 O / S in the remaining mixture obtained as the sulfur source was calculated to be 1.64.
  • Comparative Example 7 and Comparative Example 10 did not produce polyphenylene sulfide (PPS) particles, so the physical property evaluation itself was impossible.
  • the dihalogenated aromatic compound was introduced at an optimum ratio of 1.04 to 1.08 equivalent to the hydrosulfide of the alkali metal, and at the same time, the dehydration reaction and the second step
  • the polyarylene sulfides having a melt viscosity of 27.3 Pa.S to 73.8 Pa.S could be effectively produced with a high yield of 85% or more.

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Abstract

La présente invention concerne un procédé de préparation de poly(sulfure d'arylène), le rapport équivalent d'un composé aromatique déhalogéné à un composé soufré étant utilisé dans une plage prédéfinie et à la fois une réaction de déshydratation et un processus de polymérisation étant effectués dans des conditions optimales, de sorte qu'un poly(sulfure d'arylène) ayant des propriétés équivalentes ou supérieures par comparaison avec ceux existants peut être préparé avec un rendement de polymérisation élevé.
PCT/KR2019/008167 2018-07-03 2019-07-03 Procédé de préparation de poly(sulfure d'arylène) Ceased WO2020009481A1 (fr)

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CN201980028341.0A CN112041373B (zh) 2018-07-03 2019-07-03 聚亚芳基硫醚的制备方法
US17/047,341 US11414521B2 (en) 2018-07-03 2019-07-03 Preparation method of polyarylene sulfide
EP19831164.9A EP3766921B1 (fr) 2018-07-03 2019-07-03 Procédé de préparation de poly(sulfure d'arylène)
JP2020560792A JP7191344B2 (ja) 2018-07-03 2019-07-03 ポリアリーレンスルフィドの製造方法

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CN115260496A (zh) * 2022-07-27 2022-11-01 浙江新和成特种材料有限公司 聚亚芳基硫醚树脂的制造工艺及其产品和应用

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CN111286027A (zh) * 2020-02-13 2020-06-16 四川明道和化学新材料有限公司 低共价结合氯的聚苯硫醚的生产方法
CN111286027B (zh) * 2020-02-13 2022-06-10 四川明道和化学新材料有限公司 低共价结合氯的聚苯硫醚的生产方法
CN115260496A (zh) * 2022-07-27 2022-11-01 浙江新和成特种材料有限公司 聚亚芳基硫醚树脂的制造工艺及其产品和应用
CN115260496B (zh) * 2022-07-27 2024-03-29 浙江新和成特种材料有限公司 聚亚芳基硫醚树脂的制造工艺及其产品和应用

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