WO2019059593A1 - Procédé de préparation de sulfure de polyarylène - Google Patents

Procédé de préparation de sulfure de polyarylène Download PDF

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Publication number
WO2019059593A1
WO2019059593A1 PCT/KR2018/010862 KR2018010862W WO2019059593A1 WO 2019059593 A1 WO2019059593 A1 WO 2019059593A1 KR 2018010862 W KR2018010862 W KR 2018010862W WO 2019059593 A1 WO2019059593 A1 WO 2019059593A1
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WO
WIPO (PCT)
Prior art keywords
alkali metal
polyarylene sulfide
water
equivalent
sulfur
Prior art date
Application number
PCT/KR2018/010862
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English (en)
Korean (ko)
Inventor
김한솔
한중진
박은주
류현욱
정권수
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from KR1020180108349A external-priority patent/KR102088007B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/491,132 priority Critical patent/US11274183B2/en
Priority to EP18859916.1A priority patent/EP3569637B1/fr
Priority to JP2019547479A priority patent/JP6794000B2/ja
Priority to CN201880018737.2A priority patent/CN110446741B/zh
Publication of WO2019059593A1 publication Critical patent/WO2019059593A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—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
    • C08G75/0277—Post-polymerisation treatment
    • C08G75/0281—Recovery or purification

Definitions

  • PAS Polyarylene sulfide
  • PPS polyphenylene sul fi de
  • NMP N-methylpyrrolidone
  • a molecular weight modifier such as an alkali metal salt is further used do.
  • the reaction product obtained as a result of such polymerization reaction includes an aqueous phase and an organic phase, and the produced PAS is dissolved mainly in the organic phase. Accordingly, a process for separating the generated PAS is further performed. A method of cooling the crude product and precipitating the PAS is used.
  • polyphenylene sulfide uses a sulfur source for the polymerization, and the sulfur source uses NaSH and NaOH to generate Na 2 S and proceeds with PPS polymerization.
  • NaSH and NaOH uses NaSH and NaOH to generate Na 2 S and proceeds with PPS polymerization.
  • NaCl is produced as a by-product.
  • a large amount of NaCl caused corrosion problems such as semi-waning period, and the method of treating excess NaCl contained in the semi-waning period became a problem.
  • a hydrosulfide of an alkali metal, a hydroxide of an alkali metal and an alkali metal salt are repelled in the presence of water and an amide compound in the presence of an organic neat salt of an alkali metal and dehydrated to obtain a sulfide of an alkali metal,
  • Producing a source of sulfur comprising a fugitive solvent comprises the steps of: And
  • the alkali metal salt comprises sodium chloride, potassium chloride, rubidium chloride or heptachloride.
  • an alkaline metal salt such as NaCl produced as a polymerization by-product of the polyarylene sulfide is added to the above sulfur
  • the polyarylene sulfide having a thermal property equivalent to or higher than that of the conventional polyarylene sulfide can be produced.
  • the present invention has a better yield compared with the conventional method, and the main polymerization by-product (NaCl) is recycled to the sulfur source production process without being discarded, which is economical.
  • FIG. 1 is a schematic view showing a process for producing polyarylene sulfide of Example 1 of the present invention.
  • Fig. 2 is a schematic view showing a process for producing polyarylene sulfide of Comparative Example 1.
  • the main by-product is used in the preparation of a sulfur source in the production of polyarylene sulfide by polymerization reaction of a sulfur source and a dihalogenated aromatic compound in a solvent of water and an amide compound. Therefore, in the present invention, it is possible to relatively reduce the amount of the hydroxide of the alkali metal as the starting material for producing the sulfur source and to reduce the amount of the polyarylene sulfide
  • the present invention provides a production method which can be easily produced.
  • the method of producing polyarylene sulfide of the present invention can economically recycle by-products without additional cost required for the treatment of by-products because the main by-products are used.
  • the process for preparing the polyarylene sulfide of the present invention can improve the yield and increase the yield of the final product. Specifically, according to one embodiment of the present invention,
  • Hydroxides of alkali metals, hydroxides of alkali metals and alkali metal salts are repelled in the presence of water and an amide-based compound in the presence of an organic acid salt of an alkali metal, and then dehydrated to obtain sulfides of alkali metals and salts of amides
  • alkali metal salt comprises sodium chloride, potassium chloride, rubidium chloride, or chlorhexidine.
  • the present invention will be described in detail in order to facilitate understanding of the present invention.
  • the first step described above is the step of preparing a sulfur source.
  • the sulfur source is prepared by reacting a hydrosulfide of an alkali metal, a hydroxide of an alkali metal and an alkali metal salt in a mixed solvent of water and an amide compound, followed by dehydration.
  • the source of sulfur may comprise water, amide-based compound coalescing solvents, which remain undiluted, along with sulfides of alkali metals produced by the reaction of a hydrosulfide of an alkali metal and a hydroxide of an alkali metal.
  • alkali metal salts such as NaCl generated as a by-product after polyarylene sulfide polymerization are recycled and used together in order to reduce the amount of alkali metal hydroxide such as NaOH used in the production of a sulfur source.
  • dehydration by replacing the NaOH with some NaCl may be decreased and the yield may be increased.
  • Phase separation occurs in the polyarylene sulfide during the polymerization between the water layer and the amide compound layer (NMP).
  • NaCl alkali metal salt
  • the specific gravity of water is reduced in the amide compound layer (NMP layer), and the polymerization reaction in the second step can be improved. Therefore, in the present invention, the polyarylene sulfide superior in the conventional yield can be produced through the polymerization using the sulfur source, the dihalogenated aromatic compound and the amide compound continuously.
  • the present invention can prevent the corrosion of the semi-woofers used in the polymerization of the polyarylene sulfide by the recycling of the alkali metal salt, and also can reduce the amount of the alkali metal hydroxide used in the production of the sulfur source relatively Can be reduced.
  • the present invention can reduce the waste treatment cost.
  • an alkali metal salt is produced as a polymerization by-product after the polymerization reaction, and the alkali metal salt may be recovered and supplied as the alkali metal salt of the first step. That is, the reactor of the first step includes a hydrosulfide of an alkali metal and a hydroxide of an alkali metal, and the alkali metal salt may be included in the reactor to proceed the reaction.
  • the process for producing the polyarylene sulfide of the present invention may be a continuous process, and the step of introducing the alkali metal salt may be a polymerization by-product obtained after producing the polyarylene sulfide.
  • the alkali metal salt may be a halogenated alkali metal salt as a main by-product produced after the reaction of the sulfur source and the di-halogenated aromatic compound in the polymerization process of the polyarylene sulfide.
  • the alkali phosphatide salt may comprise sodium chloride, potassium chloride, rhubarb chloride, or cesium chloride, and more preferably sodium chloride.
  • the alkali metal salt may be used in an amount of 0.15 to 1 equivalent or 0.2 to 0.5 equivalent based on 1 equivalent of the sulfur source. If the content of the alkali metal salt is less than 0.1 equivalent, the effect is reduced. If the amount is more than 10 equivalent, the salt exceeding the solubility remains.
  • the alkali metal sulfide may be determined depending on the type of the alkali metal hydrosulfide used in the alkali metal, and specific examples thereof include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, One or more conjugates may be included.
  • alkali metal hydrosulfide that can be used in the production of a sulfur source by the reaction between the alkali metal hydrosulfide and the alkali metal hydrosulfide include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrogen sulfide and cesium hydrogen sulfide . Any one or two or more of these may be used, and anhydrides or hydrates thereof may be used.
  • the alkali metal hydroxide examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Any one or two or more of these may be used.
  • the hydroxide of the alkali metal has an equivalent ratio of 0.90 to 2.0, more specifically an equivalence ratio of 1.0 to 1.5, more specifically 1.0 to 1, based on 1 equivalent of an alkali metal hydrosulfide. 1 < / RTI > On the other hand, in the present invention, the equivalent amount means the molar equivalent (eq / mo1).
  • an alkali metal organic acid salt which can increase the degree of polymerization of the polyarylene sulfide in a short period of time .
  • the alkali metal organic acid salt may be specifically lithium acetate, sodium acetate or the like, and any one or two or more of them may be used.
  • the organic acid salt of the alkali metal may be used in an equivalent ratio of 0.01 to 1.0, more specifically 0.01 to 0.8, and more particularly 0.5 to 0.5, based on 1 equivalent of the alkali metal hydrosulfide.
  • the reaction between the hydrosulfide of an alkali metal and the hydroxide of an alkali metal may be carried out in a mixed solvent of water and an amide compound.
  • the amide compound include N, N-dimethylformamide or N, N Amide compounds such as dimethylacetamide; Pyrrolidone compounds such as N-methyl-2-pyrrolidone (NMU) or N-cyclohexyl-2-pyrrolidone; Caprolactam compounds such as N-methyl-epsilon -caprolactam; Imidazolidinone compounds such as 1, 3-dialkyl-2-imidazolidinone; Urea compounds such as tetramethyl urea; Or phosphoric acid amide compounds such as tricalcium methylphosphoric triamide.
  • the amide compound may be more specifically n-methyl-2-pyridone (NUMP), considering the antimony efficiency and the cosolvent effect as a polymerization solvent for polymerization for producing polyarylene sulfide.
  • the water may be used in an equivalent ratio of 1 to 8 per one equivalent of the amide compound, more specifically 1.5 to 5, more specifically 2.5 to 4.5 equivalents.
  • a sulfide of an alkali metal is precipitated in a solid phase in a water-insoluble solvent of an amide compound and the number of unreacted alkali metals Some of the sulfide may remain.
  • the molar ratio of the sulfur source may be selected from the group consisting of alkali Means the total molar ratio of the sulfide of the metal to the alkali metal hydrosulfide of the polyaniline.
  • an alkali metal salt may be contained as a by-product, which can be recovered and used continuously for the production of a sulfur source.
  • a dehydration process is performed.
  • the dehydration process can be carried out according to a method well known in the art, and the conditions thereof are not particularly limited.
  • the dehydration process can be carried out by stirring at a temperature of 130 to 205 ° C at a rate of 100 to 500 rpm.
  • the dewatering step may be performed by stirring at a temperature of 175 to 200 ° C at a speed of 100 to 300 rpm.
  • the sulfur contained in the sulfur source is counteracted with water to generate hydrogen sulfide and alkali metal hydroxide, and the generated hydrogen sulfide is volatilized.
  • the amount of sulfur in the sulfur source can be reduced.
  • the amount of sulfur remaining in the system after the dehydration process is equal to the molar amount of sulfur in the introduced sulfur source minus the molar amount of hydrogen sulfide vaporized out of the system . It is therefore necessary to quantify the amount of the effective sulfur contained in the sulfur source remaining in the system after the dehydration process from the amount of hydrogen sulfide vaporized out of the system.
  • the dehydration process may be carried out until the molar ratio of water to 1 mole of effective sulfur is 1 to 5, more specifically 1.5 to 4, and more specifically 2.0 to 3.5.
  • water can be added to adjust the water content before the polymerization process.
  • the sulfur source prepared by the reaction of a hydrosulfide of an alkali metal and a hydroxide of an alkali metal and dehydration as described above may contain, in addition to a sulfide of an alkali metal, a water and an amide- The water may be included in a molar ratio of from 2.5 to 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.
  • a di-halogenated aromatic compound to prepare polyarylene sulfide.
  • the dihalogenated aromatic compounds usable for the production of the polyarylene sulfide are compounds in which two hydrogen atoms in the aromatic ring are substituted with halogen atoms.
  • Specific examples thereof include 0-dihalobenzene, m-dihalobenzene, And any of them may be used as long as they can be used in combination with one or more of them, such as benzene, benzene, toluene, toluene, toluene, dihalonaphthalene, dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl ether, dihalodiphenylsulfone, dihalodiphenylsulfoxide or dihalodiphenylketone Or two or more impurities may be used.
  • the halogen atom may be fluorine, chlorine, bromine or iodine.
  • P-dichlorobenzene p-DCB
  • p-DCB P-dichlorobenzene
  • the di-halogenated aromatic compound may be added in an equivalent amount of 0.8 to 1.2.
  • the polyarylene sulfide having excellent physical properties can be prepared without the fear of lowering the melting point of the polyarylene sulfide to be produced and increasing the content of chlorine present in the polyarylene sulfide have. Considering that the improvement effect of the addition amount of the sulfur source and the dihalogenated aromatic compound is excellent, more specifically, the dihalogenated aromatic compound
  • the step of lowering the temperature of the reactor including the sulfur source to a temperature of 150 to 2 cxrc may be further included to prevent the vaporization of the di-halogenated aromatic compound.
  • the polymerization reaction of the sulfur source and the dihalogenated aromatic compound can be carried out as an aprotic polar organic solvent in a solvent of an amide compound stable to an alkali at a high temperature.
  • the amide-based compound is more preferably N-methyl-2-pyrrolidone (NMP) or N- Nucleic Acid-2-Pyridone And the like.
  • the amide compound added in the second step is a compound of water (H 2 O) with respect to the amide compound present in the polymerization solvent system May be added in such an amount that the molar ratio (molar ratio of water / amide compound) is 0.85 or more.
  • the polymerization inhibitor such as the polymerization inhibitor, the cross-linking agent, and other additives for controlling the molecular weight may be further added in the range of not lowering the physical properties and production yield of the polyarylene sulfide to be finally produced.
  • the polymerization reaction of the sulfur source and the dihalogenated aromatic compound can be carried out at 200 to 300 ° C.
  • the second polymerization reaction is carried out continuously at a temperature higher than the temperature of the first polymerization reaction, specifically at 250 ° C to 300 ° C .
  • the resultant reaction products resulting from the polymerization reaction are separated into an aqueous phase and an organic phase, wherein the polyarylene sulfide, which is a polymerization reaction product, is dissolved in the organic phase. Accordingly, a process for precipitation and separation of the produced polyarylene sulfide can be selectively performed.
  • the precipitation of the polyarylene sulfide can be carried out by adding water to an ammonium salt at an equivalent ratio of 3 to 5 to 1 equivalent of sulfur and agitating it.
  • water is added in the above-mentioned content range, the plyarylene sulfide can be precipitated with excellent efficiency.
  • the precipitated polyarylene sulfide may be optionally further subjected to washing and filtration and drying steps according to a conventional method. According to the method for producing polyarylene sulfide according to one embodiment of the present invention as described above, Excellent polyarylene sulfide can be easily produced.
  • the present invention relates to a process for producing a polyarylene sulfide, which comprises recycling an alkaline metal salt as a polymerization by-product of the polyarylene sulfide to a dehydrating agent for producing the sulfur source, And the like can be produced with high yield.
  • the polyarylene sulfide produced by the above production method is produced at a yield of 80% or more, more specifically 83% or more, and has a melting melting temperature (T) of 270 to 300 ° C and a melting temperature of 180 to 250 ° C And may have a crystallization temperature (Tc).
  • the polyarylene sulfide may have a weight average molecular weight (Mw) of 10, 000 g / mol and 30,000 g / mol or less.
  • the polyarylene sulfide thus produced exhibits excellent fluidity and can exhibit enhanced flammability to fillers and reinforcing agents. As a result, it can be useful for the production of molds for replacing metals in automobiles, electric and electronic products or mechanical parts, especially in the manufacture of refillers and base plasters for automotive lamps which require excellent mechanical properties.
  • Polyphenylene sulfide was prepared in the content range shown in Table 1 below.
  • sodium sulphide Na 2 S
  • NaSH 70% sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • 0.44 equivalents of sodium acetate powder and 1.65 equivalents of N-methyl-2-pyrrolidone (NMP), 4.92 equivalents of deionized water (DI water) and 0.2 equivalents of NaCl was carried out.
  • the reaction was heated to 185 ° C for 1 hour and 40 minutes with stirring at 150 rpm and dehydrated. The temperature was then lowered to 165 [ deg.] C and 1.00 equivalents of para- Dichlorobenzene (p-DCB) and 1.35 equivalents of NMP were added to the reactor. The reaction mixture was heated to 230 ° C for 2 hours, heated again to 250 ° C, and reacted for 2 hours.
  • p-DCB para- Dichlorobenzene
  • Polyphenylene sulfide was prepared in the content range shown in Table 1 below.
  • sodium sulphide Na 2 S was prepared by mixing 1 equivalent of 70% sodium hydrogen sulfide (NaSH) and 0.86 equivalent of sodium hydroxide (NaOH) in the reactor according to the method shown in FIG. At this time, 0.2 equivalents of sodium acetate powder and 1.65 equivalents of N-methyl-2-pyrrolidone (NMP), 4.92 equivalents of DI water and 0.2 equivalents of NaCl (polymerization byproduct) The reaction was heated to 205 ° C for 1 hour and 40 minutes with stirring at 150 rpm and dehydrated.
  • NaSH 70% sodium hydrogen sulfide
  • NaOH sodium hydroxide
  • NMP N-methyl-2-pyrrolidone
  • DI water 0.2 equivalents of NaCl (polymerization byproduct)
  • Polyphenylene sulfide was prepared in the content range shown in Table 1 below.
  • the half "group was heated with stirring at 150rpm for 1 hour 40 minutes to 185 ° C, and after dehydration, and lowering the temperature to 165 ° C, 1 .00 equivalents of para-dichlorobenzene (DCB p-) and 1 .35 equivalents of NMP were added to the semi-funnel, which was then heated to 230 [ deg.] C for 2 hours, then further heated to 25 [deg.] C for another 2 hours.
  • DCB p- para-dichlorobenzene
  • Polyphenylene sulfide was prepared in the content range shown in Table 1 below.
  • Polyphenylene sulfide was prepared in the same manner as in Comparative Example 1 except that 0.1 equivalent of LiCl was added in the dehydration reaction and 0.33 equivalent of NaOAc was added. At this time, since LiCl was not generated during the polymerization, a separate material other than the polymerization by-product was added to the L iCl.
  • Example 1 is superior in polymerization yield as compared with the case where LiCl of Comparative Example 2 is used.
  • Comparative Example 2 is not a material generated after polymerization even when an alkali metal salt is added, and its content range is lower than that of the present invention, so that the polymerization yield is very low.
  • Example 1 of the present invention In contrast, the melting temperature and the crystallinity range of silver halide in Example 1 of the present invention were comparable to those of Comparative Examples 1 and 2, and thus it was confirmed that the physical properties of the polymer showing similar thermal properties were easily produced economically .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

La présente invention peut fournir un procédé de préparation d'un sulfure de polyarylène, le procédé étant économique et produisant un excellent rendement étant donné qu'un sel de métal alcalin, tel que NaCl, qui est un sous-produit de polymérisation principal du sulfure de polyarylène, peut être réutilisé dans une réaction de déshydratation préparant une source d'alimentation en soufre.
PCT/KR2018/010862 2017-09-20 2018-09-14 Procédé de préparation de sulfure de polyarylène WO2019059593A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/491,132 US11274183B2 (en) 2017-09-20 2018-09-14 Method of preparing polyarylene sulfide
EP18859916.1A EP3569637B1 (fr) 2017-09-20 2018-09-14 Procédé de préparation de sulfure de polyarylène
JP2019547479A JP6794000B2 (ja) 2017-09-20 2018-09-14 ポリアリーレンスルフィドの製造方法
CN201880018737.2A CN110446741B (zh) 2017-09-20 2018-09-14 制备聚芳硫醚的方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170121475 2017-09-20
KR10-2017-0121475 2017-09-20
KR1020180108349A KR102088007B1 (ko) 2017-09-20 2018-09-11 폴리아릴렌 설파이드의 제조방법
KR10-2018-0108349 2018-09-11

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0215312A1 (fr) * 1985-08-20 1987-03-25 Idemitsu Petrochemical Co. Ltd. Procédé de préparation de poly(sulfures d'arylène)
EP0226909A2 (fr) * 1985-12-18 1987-07-01 Tosoh Corporation Procédé pour préparer un polyarylène sulfure
EP0302218A1 (fr) * 1987-06-30 1989-02-08 Idemitsu Petrochemical Co. Ltd. Procédé pour la préparation de polyarylène sulfide
US5635587A (en) * 1993-12-16 1997-06-03 Idemitsu Petrochemical Co., Ltd. Process for manufacturing polyarylene sulfide
JP2010106179A (ja) * 2008-10-31 2010-05-13 Toray Ind Inc ポリアリーレンスルフィド樹脂の製造方法
KR20110086702A (ko) * 2008-11-21 2011-07-29 디아이씨 가부시끼가이샤 폴리아릴렌설피드 수지의 제조 방법
KR101711182B1 (ko) * 2012-12-26 2017-02-28 저지앙 엔에이치유 스페셜 머티어리얼스 컴퍼니 리미티드 피버 그레이드 폴리페닐렌 설파이드 수지의 합성 방법

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0215312A1 (fr) * 1985-08-20 1987-03-25 Idemitsu Petrochemical Co. Ltd. Procédé de préparation de poly(sulfures d'arylène)
EP0226909A2 (fr) * 1985-12-18 1987-07-01 Tosoh Corporation Procédé pour préparer un polyarylène sulfure
EP0302218A1 (fr) * 1987-06-30 1989-02-08 Idemitsu Petrochemical Co. Ltd. Procédé pour la préparation de polyarylène sulfide
US5635587A (en) * 1993-12-16 1997-06-03 Idemitsu Petrochemical Co., Ltd. Process for manufacturing polyarylene sulfide
JP2010106179A (ja) * 2008-10-31 2010-05-13 Toray Ind Inc ポリアリーレンスルフィド樹脂の製造方法
KR20110086702A (ko) * 2008-11-21 2011-07-29 디아이씨 가부시끼가이샤 폴리아릴렌설피드 수지의 제조 방법
KR101711182B1 (ko) * 2012-12-26 2017-02-28 저지앙 엔에이치유 스페셜 머티어리얼스 컴퍼니 리미티드 피버 그레이드 폴리페닐렌 설파이드 수지의 합성 방법

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