JPH0280432A - Production of polyphenylene sulfide - Google Patents
Production of polyphenylene sulfideInfo
- Publication number
- JPH0280432A JPH0280432A JP63231468A JP23146888A JPH0280432A JP H0280432 A JPH0280432 A JP H0280432A JP 63231468 A JP63231468 A JP 63231468A JP 23146888 A JP23146888 A JP 23146888A JP H0280432 A JPH0280432 A JP H0280432A
- Authority
- JP
- Japan
- Prior art keywords
- sodium sulfide
- aqueous solution
- naoh
- soln
- concn
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims description 30
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 65
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 150000003857 carboxamides Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 88
- 239000007787 solid Substances 0.000 abstract description 20
- 239000012535 impurity Substances 0.000 abstract description 6
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 abstract description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001408 amides Chemical class 0.000 abstract 2
- 239000011734 sodium Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 17
- 239000002994 raw material Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 241001274216 Naso Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- YJIBHPVNTVUEPU-UHFFFAOYSA-N thorium(iv) sulfide Chemical compound S=[Th]=S YJIBHPVNTVUEPU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ポリフェニレンスルフィド（以下、ＰＰＳと
略記）の製造方法に関し、さらに詳しくは、ＰＰＳの製
造原料である硫化ナトリウムを特定濃度の水溶液として
使用することにより、重合操作を簡便かつ容易にして生
産性を向上させ、安定した高品質のＰＰＳを製造する方
法に関する。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing polyphenylene sulfide (hereinafter abbreviated as PPS). By using the present invention, it is possible to simplify and facilitate polymerization operations, improve productivity, and to produce stable, high-quality PPS.
（従来の技術）
ＰＰＳの代表的な製造方法は、Ｎ−メチルピロリドン等
の有機アミド溶媒中で、ｐ−ジクロルベンゼンに代表さ
れるジハロ芳香族化合物と硫化ナトリウムを反応させる
方法である（特公昭５２−１２２４０号公報、特開昭６
１−７３３２号公報など）。(Prior art) A typical method for producing PPS is a method in which a dihaloaromatic compound represented by p-dichlorobenzene and sodium sulfide are reacted in an organic amide solvent such as N-methylpyrrolidone. Publication No. 52-12240, Japanese Unexamined Patent Publication No. 6
1-7332, etc.).
この場合、原料の硫化ナトリウムとして、通常、Ｎａｇ
Ｓ ’ ９８２０結晶（ＮａｚＳ濃度３２．５重量％
）、Ｎａ１Ｓ−らＨｔＯ結晶（Ｎａ、Ｓ濃度４６．４重
量％）、またはＮ ａ ｚ Ｓ濃度が約６０重量％の固
結体などの固体状態のものが使用されている。その理由
は、これらの固体状態の硫化ナトリウムが工業的に生産
されており、それらの入手が容易だからである。In this case, the raw material sodium sulfide is usually Nag
S' 9820 crystal (NazS concentration 32.5% by weight)
), Na1S-et-HtO crystals (Na, S concentration: 46.4% by weight), or solids with a Na z S concentration of about 60% by weight are used. The reason is that these solid state sodium sulfides are produced industrially and are easily available.
しかしながら、これら工業製品としての固体状硫化ナト
リウムは、いずれも均一な組成をもつものではない。However, these solid sodium sulfide industrial products do not all have a uniform composition.
例えば、Ｎａ２Ｓ・５Ｈ２０結晶は晶析によって製造さ
れるが、硫化ナトリウムは水に溶解し易いため結晶の分
離に際し、通常、母液の洗浄除去は行ない得ず母液を付
着させたまま乾燥し製品とする。したがって、結晶の大
小により母液の付着量が異なり、かつ母液の組成は結晶
の組成とは異なったものである。For example, Na2S/5H20 crystals are produced by crystallization, but since sodium sulfide is easily dissolved in water, when separating the crystals, the mother liquor is usually not washed away and the product is dried with the mother liquor still attached. . Therefore, the amount of adhered mother liquor differs depending on the size of the crystal, and the composition of the mother liquor is different from that of the crystal.
また、約６０重量％の固結体は同一組成の融液を冷却し
て製造されるが、後記するようにこのものはＮａｇ Ｓ
・５Ｈｉ ＯとＮａａＳ”ＨｚＯとの混合物である。In addition, a solid of about 60% by weight is produced by cooling a melt of the same composition, but as described later, this is Nag S
- It is a mixture of 5Hi O and NaaS"HzO.
ので、冷却時に均一に固化せず、初期に固化したものは
６０重量％より高濃度であり、後期には６０重量％より
低濃度となる。Therefore, it does not solidify uniformly during cooling, and the concentration in the early stage is higher than 60% by weight, and in the later stage, the concentration is lower than 60% by weight.
以上のような理由で、工業用硫化ナトリウムの正確な濃
度分析はその不均一性のため極めて困難である。For the above reasons, accurate concentration analysis of industrial sodium sulfide is extremely difficult due to its heterogeneity.
さらに、ＰＰＳを工業的規模で大量生産する場合、原料
の硫化ナトリウムを固体状態のものとして使用すること
は、必ずしも好ましいことではない。なぜならば、大量
の硫化ナトリウムを貯蔵、移送あるいは計量する場合、
固体状態であるが故の取扱の困難さが付きまとうからで
ある。Furthermore, when mass producing PPS on an industrial scale, it is not necessarily preferable to use sodium sulfide as a raw material in a solid state. This is because when storing, transporting or weighing large amounts of sodium sulfide,
This is because it is difficult to handle because it is in a solid state.
例えば、硫化ナトリウムは、空気酸化を受は易く、その
結果、Ｎａ１ＳＯ＊やＮａ１ＳＯ＊、Ｎ ａ ｚ Ｓ
ｘ等の酸化物を生成し、これらの酸化物がＰＰＳの重合
反応を阻害する要因となる。空気酸化を防ぐためには、
窒素ガスなどの不活性ガスでシールを行なう必要がある
が、硫化ナトリウムが固体状態のものであれば、完全に
不活性ガスでシールすることには困難が多い。For example, sodium sulfide is susceptible to air oxidation, resulting in formation of NaSO*, NaSO*, NazS
This produces oxides such as x, and these oxides become a factor that inhibits the polymerization reaction of PPS. To prevent atmospheric oxidation,
It is necessary to seal with an inert gas such as nitrogen gas, but if sodium sulfide is in a solid state, it is difficult to completely seal with an inert gas.
また、固体状態の硫化ナトリウムは、輸送中および貯蔵
中の自重による圧密固結や移送中の破砕粉化によるライ
ン閉塞および計ｊ１Ｍ差等を生じ易い。In addition, sodium sulfide in a solid state is likely to cause compaction due to its own weight during transportation and storage, line blockage due to crushing and pulverization during transportation, and a total j1M difference.
また、固体物質の取扱い時には、異物が混入することが
あり、しかも−旦混入した異物を固体状態のままで除去
することは極めて困難である。Further, when handling solid substances, foreign substances may be mixed in, and it is extremely difficult to remove foreign substances that have been mixed in in a solid state.
さらに、結晶水としての水分を含む固体状態の硫化ナト
リウム（含水硫化ナトリウム）をＰＰＳ製造用の原料と
して使用する場合には、重合缶内で有機アミド溶媒とと
もに加熱して脱水し、水分量を硫化ナトリウムに対し０
．３〜５モル比程度に減らして後、ジへロ芳香族化合物
と反応させるのが一般的である。その理由は、ＰＰＳの
重合に際し、特に重合初期には、硫化ナトリウム１モル
当り５モルを越える水分が存在すると、重合途中のポリ
マーの分解や重合速度の低下を引き起こすからである。Furthermore, when solid sodium sulfide containing water as crystal water (hydrated sodium sulfide) is used as a raw material for PPS production, it is dehydrated by heating with an organic amide solvent in a polymerization reactor to reduce the water content by sulfurization. 0 for sodium
．． It is common to reduce the molar ratio to about 3 to 5 and then react with a diheroaromatic compound. The reason for this is that during the polymerization of PPS, especially in the initial stage of polymerization, if more than 5 mol of water exists per 1 mol of sodium sulfide, this will cause decomposition of the polymer during polymerization and a decrease in the polymerization rate.
一方、硫化ナトリウム（Ｎａｇ Ｓ）１モル当りの水分
量が０．３モル以下となると、硫化ナトリウムが有機ア
ミド溶媒に溶解しなくなり、高重合度のポリマーを得る
ことが困難となる。ところが、含水硫化ナトリウムを有
機アミド溶媒中で加熱して水分を蒸発除去する際に、Ｈ
ａｓガスが硫化ナトリウムから平衡的に解離して揮敗し
、その結果、Ｎ ａ ／ Ｓ比（モル比、以下同様）が
原料のＮ ａ ／ Ｓ比より若干高めとなる６そこで、
原料の硫化ナトリウムとして、例えばＮ ａ ｚ Ｓ・
５ＨｚＯの単一結晶、すなわちＮ ａ ／ Ｓ比が２の
ものを使用しても、実際の重合条件下ではＮ ａ ／
Ｓ比は２より大きい２．０５程度の値となる。On the other hand, when the water content per mole of sodium sulfide (Nag S) is 0.3 mole or less, sodium sulfide becomes insoluble in the organic amide solvent, making it difficult to obtain a polymer with a high degree of polymerization. However, when heating hydrated sodium sulfide in an organic amide solvent to evaporate water, H
As gas dissociates from sodium sulfide in an equilibrium manner and volatilizes, and as a result, the Na/S ratio (molar ratio, hereinafter the same) becomes slightly higher than the Na/S ratio of the raw material6.Therefore,
As the raw material sodium sulfide, for example, N a z S.
Even if a single crystal of 5 HzO, i.e. with a Na/S ratio of 2, is used, under actual polymerization conditions the Na/S ratio is
The S ratio has a value of about 2.05, which is larger than 2.
したがって、原料として用いる硫化ナトリウムは、脱水
時のＮ ａ ／ Ｓ比の上昇を考慮した上で重合時のＮ
ａ ／ Ｓ比が一定の範囲内になるように調節する必
要がある。しかしながら、このような調節は、Ｎａｇ
Ｓ ・９Ｈ＊ ＯやＮ ａｔ Ｓ ・５ Ｈｚ Ｏの単
一結晶では非常に困難である。Therefore, the sodium sulfide used as a raw material has a high N a / S ratio during polymerization, taking into account the increase in the N a /S ratio during dehydration.
It is necessary to adjust the a/S ratio so that it falls within a certain range. However, such regulation is
This is extremely difficult with a single crystal of S .9H*O or N at S .5 Hz O.
Ｎａｇ Ｓ−９Ｈｘ ＯやＮａｇ Ｓ ・５Ｈｉ Ｏの
単一結晶に、Ｎａ０Ｈ（Ｎａ／Ｓ比＝ ｏａ ）やＮａ
ＨＳ（Ｎａ／Ｓ比＝１ ） 、 Ｈｚ Ｓ （Ｎ ａ／
Ｓ比＝０）を添加してＮ ａ ／ Ｓ比をコントロー
ルすることも考えられるが、操作が煩雑となり、また、
得られるポリマーの物性が最初からＮ ａ ／ Ｓ比を
調節した硫化ナトリウムを使用して得たものと比べ、溶
融粘度が低い等、劣ることが多い。Na0H (Na/S ratio = oa) and Na
HS (Na/S ratio = 1), Hz S (Na/
It is also possible to control the Na/S ratio by adding S ratio = 0), but the operation would be complicated, and
The physical properties of the resulting polymer are often inferior to those obtained using sodium sulfide whose Na/S ratio is adjusted from the beginning, such as a lower melt viscosity.
したがって、ＰＰＳの製造においては、最初からＮ ａ
／ Ｓ比を適正な範囲に調節した硫化ナトリラムを原
料として用いることが好ましい。Therefore, in the production of PPS, Na
It is preferable to use sodium sulfide with the S ratio adjusted to an appropriate range as the raw material.
しかしながら、従来汎用されている固体状態の硫化ナト
リウムでは、前記したような問題点があり、Ｎ ａ ／
Ｓ比を適正な範囲に調節することは困難である。However, solid state sodium sulfide, which has been widely used in the past, has the above-mentioned problems, and N a /
It is difficult to adjust the S ratio to an appropriate range.
このように、固体状態の硫化ナトリウムは、濃度測定の
ための試料採取、貯蔵、移送、計量、酸化防止等の取扱
上の問題があり、また、これらの問題点に起因してＰＰ
Ｓの溶融粘度の低下やロフトごとの溶融粘度のバラツキ
などが生じ、その解決が求められている。As described above, solid state sodium sulfide has problems in handling such as sample collection for concentration measurement, storage, transportation, weighing, and prevention of oxidation.
A decrease in the melt viscosity of S and variations in melt viscosity from loft to loft have occurred, and a solution is required.
（発明が解決しようとする課題）
本発明の目的は、ＰＰＳの製造方法において、前記した
従来技術の有する問題点を解決し、重合操作を簡便かつ
容易にして生産性を向上させ、安定した高品質のＰＰＳ
を製造する方法を提供することにある。(Problems to be Solved by the Invention) An object of the present invention is to solve the problems of the prior art described above, to simplify and facilitate the polymerization operation, to improve productivity, and to achieve stable high-performance polymerization in a method for producing PPS. Quality PPS
The purpose is to provide a method for manufacturing.
さらに、本発明の目的は、取扱が容易で、酸化防止や不
溶性不純物の除去が可能で、しかも適切なＮ ａ ／
Ｓ比とすることができる硫化すトリウム水溶液をＰＰＳ
製造用の原料として使用する方法を提供することにある
。Furthermore, it is an object of the present invention to be easy to handle, to be able to prevent oxidation and to remove insoluble impurities, and to have an appropriate Na/
Thorium sulfide aqueous solution that can be made into S ratio is PPS
The object of the present invention is to provide a method for use as a raw material for manufacturing.
本発明者らは鋭意研究した結果、ＰＰＳの製造原料であ
る硫化ナトリウムを高濃度の水溶液として製造し、水溶
液の状態で、濃度分析、貯蔵、移送、計量等を行ない、
重合用原料として重合缶に仕込むことにより前記目的を
達成できることを見出し、この知見に基づいて本発明を
完成するに至った。As a result of intensive research, the present inventors manufactured sodium sulfide, which is a raw material for PPS, as a highly concentrated aqueous solution, and performed concentration analysis, storage, transfer, measurement, etc. in the aqueous solution state.
It was discovered that the above object could be achieved by charging it as a raw material for polymerization into a polymerization can, and based on this knowledge, the present invention was completed.
（課題を解決するための手段）
すなわち、本発明によれば、有機アミド溶媒中で硫化ナ
トリウムとジハロ芳香族化合物とを反応させてＰＰＳを
製造する方法において、硫化ナトリウムを４６〜６０重
量％の水溶液として使用することを特徴とするポリフェ
ニレンスルフィドの製造方法が提供される。(Means for Solving the Problems) That is, according to the present invention, in a method for producing PPS by reacting sodium sulfide and a dihaloaromatic compound in an organic amide solvent, sodium sulfide is added in an amount of 46 to 60% by weight. A method for producing polyphenylene sulfide is provided, which is characterized in that it is used as an aqueous solution.
以下、本発明の構成について詳述する。Hereinafter, the configuration of the present invention will be explained in detail.
硫化ナトリウム（ＮａｚＳ）と水との状態図を第１図に
示す。A phase diagram of sodium sulfide (NazS) and water is shown in FIG.
第１図から、Ｎ ａ ｚ Ｓは、６０重量％以下の濃度
でのみ水溶液として存在し得ることが分かる。From FIG. 1 it can be seen that N a z S can exist as an aqueous solution only at concentrations below 60% by weight.
また、Ｎａｇ Ｓ・５Ｈｘ Ｏ（Ｎａｇ Ｓ濃度４６重
量％）は、極大融点９８℃を持ち、４６〜６０重量％の
濃度領域では、９８℃より低い温度で水溶液として存在
し、５５重量％で極小融点８６℃を持つことがわかる。In addition, Nag S・5Hx O (Nag S concentration 46% by weight) has a maximum melting point of 98°C, and in the concentration range of 46 to 60% by weight, it exists as an aqueous solution at a temperature lower than 98°C, and at 55% by weight it has a maximum melting point of 98°C. It can be seen that it has a melting point of 86°C.
本発明において硫化ナトリウム水溶液の濃度を４６〜６
０重量％とする理由は、前記のＮａｘＳの水に対する溶
解挙動に基づく。In the present invention, the concentration of the sodium sulfide aqueous solution is 46 to 6.
The reason for setting it to 0% by weight is based on the above-mentioned solubility behavior of NaxS in water.
硫化ナトリウムの濃度が高い程、ＰＰＳ製造時における
脱水工程での消費エネルギーを少な（することができ、
経済的であると同時に、脱水量が少なくてすむことは脱
水に伴うＨ，Ｓガスの揮散も少なく好ましい。また、固
形分の混在しない均質な溶液とすることにより、計量誤
差を極小に押えることができる。水溶液の保温温度も低
い方が経済的である。したがって、硫化ナトリウム水溶
液は、高濃度でかつ溶液として存在し得ろ温度が低い方
が好ましく、その観点から濃度が４６〜６０重量％、そ
の中でも５４〜５６重量％の範囲であることがより好ま
しい。The higher the concentration of sodium sulfide, the less energy is consumed in the dehydration process during PPS production.
It is economical, and at the same time, it is preferable that the amount of dehydration is small, since the volatilization of H and S gases accompanying dehydration is also small. In addition, by creating a homogeneous solution with no solid content, measurement errors can be kept to a minimum. It is more economical to keep the aqueous solution at a lower temperature. Therefore, it is preferable that the sodium sulfide aqueous solution has a high concentration and can exist as a solution at a low temperature. From this point of view, the concentration is preferably in the range of 46 to 60% by weight, and more preferably in the range of 54 to 56% by weight.
なお、Ｎａ／Ｓ比が２よりわずかにズしたもの、すなわ
ちＮ ａ ｘ Ｓ以外にＮａｐ）（やＮａＨＳをわずか
に含む硫化ナトリウム水溶液も、このような不飽和水溶
液として存在し得る。したがって、本発明の硫化ナトリ
ウム水溶液には、少量のＮａＯＨまたはＮａＨＳが含ま
れていてもよい。Note that an aqueous sodium sulfide solution with a Na/S ratio slightly higher than 2, that is, an aqueous solution of sodium sulfide containing a small amount of Nap (or NaHS) in addition to Na x S, can also exist as such an unsaturated aqueous solution. The aqueous sodium sulfide solution of the invention may contain a small amount of NaOH or NaHS.
４６〜６０重量％濃度の硫化ナトリウム水溶液を製造す
る方法としては、次のような各種の方法が挙げられる。As a method for producing a sodium sulfide aqueous solution having a concentration of 46 to 60% by weight, the following various methods can be mentioned.
（ａ）Ｎａｇ Ｓ ・９Ｈａ ＯあるいはＮ ａ ｘ
Ｓ ・５Ｈ，Ｏの結晶を加熱溶融して液体とし、これを
濃縮すると共に、ＮａＯＨまたはＮａＨＳを少量添加し
、重合時におけるＮ ａ ／ Ｓ比を当初の設定値に合
わせる。(a) Nag S ・9Ha O or Na x
The crystals of S.5H,O are heated and melted to make a liquid, which is concentrated, and a small amount of NaOH or NaHS is added to adjust the Na/S ratio during polymerization to the initially set value.
（ｂ）ＮａＨ３水溶液をＮａＯＨ水溶液で中和し、濃縮
する。(b) Neutralize the NaH3 aqueous solution with an NaOH aqueous solution and concentrate.
（ｃ）ＮａＯＨ水溶液を濃縮するとともにＨａｓガスを
吸収させる。(c) Concentrating the NaOH aqueous solution and absorbing Has gas.
これらの方法のうち、原料の入手の難易、原料の純度等
を勘案して、いずれの方法を選択してもよいが、（ａ）
および（ｂ）は、高濃度のＮ ａ ｘ Ｓ溶液の濃縮に
際し耐蝕性の高い材料の容器を用いる必要があり、また
、蒸発水と共にＨ□Ｓガスが揮散するので、その処理を
必要とする等問題は多い。Among these methods, any method may be selected taking into account the difficulty of obtaining raw materials, the purity of raw materials, etc., but (a)
and (b), it is necessary to use a container made of a highly corrosion-resistant material when concentrating a high concentration Na There are many problems.
好ましい製造方法の一例として、次のような方法が挙げ
られる。An example of a preferred manufacturing method includes the following method.
■ 市販の４８〜５０重量％のＮａＯＨ水溶液を７３〜
７４重量％に濃縮する。第２図に示すように、工業的に
はこの濃度がＮａＯＨを水溶液として取扱える上限であ
る。■ Commercially available 48-50% by weight NaOH aqueous solution
Concentrate to 74% by weight. As shown in FIG. 2, this concentration is the upper limit at which NaOH can be handled as an aqueous solution industrially.
■ このＮａＯＨ水溶液を略二分し、一方にＨ，Ｓガス
を飽和になるまで吸収させ６３〜６４重量％のＮａＨＳ
水溶液とする。この際、使用するＨ、Ｓは、炭酸ガスや
ポリ硫化水素等の不純物を含まない高純度のものが好ま
しく、その製造方法の一例としては特開昭６３−１３９
００７号公報に記載の方法がある。■ Divide this NaOH aqueous solution into approximately two halves, and absorb H and S gases into one half until it becomes saturated.
Make an aqueous solution. At this time, the H and S used are preferably of high purity and do not contain impurities such as carbon dioxide gas or polyhydrogen sulfide.
There is a method described in Publication No. 007.
■ このＮａＨＳ水溶液に、前記７３〜７４重量％のＮ
ａＯＨ水溶液の残る一方を混合すると５４〜５５重量％
のＮａａ Ｓ水溶液となる。この際のＮａＨＳ水溶液と
ＮａＯＨ水溶液との混合比はほぼ等モルであるが、必要
に応じてその混合比をわずかに変化させることによりＮ
ａ ／ Ｓ比を自由に調節することができる。■ Add 73 to 74% by weight of N to this NaHS aqueous solution.
When the remaining aOH aqueous solution is mixed, it is 54 to 55% by weight.
This becomes an aqueous Naa S solution. At this time, the mixing ratio of the NaHS aqueous solution and the NaOH aqueous solution is approximately equimolar, but if necessary, by changing the mixing ratio slightly, the N
The a/S ratio can be adjusted freely.
このようにして製造したＮ ａ ｘ Ｓ水溶液中には、
不溶性の固体状不純物が存在することがある。例えば、
ＮａＯＨに由来するＮａＣβ、Ｎａｇ Ｃｏｗ 、Ｆｅ
、Ｃｒ、Ｎｉ等の重金属の硫化物、Ｎａ＊Ｓの空気酸化
により副生したＮａ２ＳＯｓ 、Ｎａｇ ｓ２０ｍ 、
さらに装置材料や系外より混入する異物等である。この
ような不溶性不純物は、得られるＰＰＳの物性に悪影響
を与えるので、遠心沈降などの固液分離により除去し、
清澄液として使用する。In the N a x S aqueous solution produced in this way,
Insoluble solid impurities may be present. for example,
NaCβ, Nag Cow, Fe derived from NaOH
, sulfides of heavy metals such as Cr and Ni, Na2SOs by-produced by air oxidation of Na*S, Nag s20m,
Furthermore, there are equipment materials and foreign substances that enter the system from outside the system. Such insoluble impurities adversely affect the physical properties of the resulting PPS, so they are removed by solid-liquid separation such as centrifugal sedimentation.
Use as a clear liquid.
本発明で使用する硫化ナトリウム水溶液は、蓋のある容
器に入れて保存や移送ができるため、密閉したり、窒素
ガスでシールすることが容易である。したがって、固形
状態のものに比べて、酸化防止が完全であり、計量に当
たっても、均質な液状であり、かつ、濃度管理を正確に
できるため、正確な計量を容易に行なうことができる。The aqueous sodium sulfide solution used in the present invention can be stored or transported in a container with a lid, so it can be easily sealed or sealed with nitrogen gas. Therefore, compared to a solid state, it is completely prevented from oxidation, and even when measured, it is a homogeneous liquid state, and the concentration can be controlled accurately, so that accurate measurement can be easily performed.
そして、硫化ナトリウム水溶液をＰＰＳ製造用原料とし
て使用すると、ロットごとのバラツキが少なく、一定粘
度のＰＰＳを製造することができる。When an aqueous sodium sulfide solution is used as a raw material for producing PPS, it is possible to produce PPS with a constant viscosity and less variation from lot to lot.
ここで、ＰＰＳの製造に際し、固体状態の硫化ナトリウ
ムと本発明で使用する特定濃度の硫化ナトリウム水溶液
との取扱の難易等を比較すると、第１表に示すとおりで
ある。Table 1 shows a comparison of the difficulty in handling solid sodium sulfide and the aqueous sodium sulfide solution at a specific concentration used in the present invention when producing PPS.
第 １
表
（以下余白）
傘ｌ：酸化防止用に使用する窒素ガスの使用置傘２：装
置単位重量当たりの比較
（実施例）
以下、本発明を参考例、実施例および比較例を挙げて具
体的に説明するが、本発明はこれら実施例のみに限定さ
れるものではない。Table 1 (blank below) Umbrella 1: Use of nitrogen gas used for oxidation prevention Umbrella 2: Comparison per unit weight of device (Example) The present invention will be described below with reference examples, examples, and comparative examples. Although a specific explanation will be given, the present invention is not limited to these Examples.
なお、硫化ナトリウムおよびその不純物の分析方法は、
ＪＩＳ Ｋ−１４３５に基づいて行なった。The analysis method for sodium sulfide and its impurities is as follows:
It was conducted based on JIS K-1435.
委］Ｌ母」１（硫化ナトリウム水溶液の調製）３００β
の撹拌機付チタン張り反応槽に２．５３ ｋｍｏ ｌの
７４．０重量％ＮａＯＨ水溶液を入れる。この液の融点
は６２℃であるので、液温な７０℃とした。Committee] L Mother'1 (Preparation of sodium sulfide aqueous solution) 300β
2.53 kmol of 74.0% by weight NaOH aqueous solution was placed in a titanium-lined reaction tank equipped with a stirrer. Since the melting point of this liquid is 62°C, the liquid temperature was set at 70°C.
この中に硫化水素ボンベよりＨ２Ｓガスを飽和になるま
で吹き込んだ。この間、液ｃＭが１１０℃を超えないよ
うに、反応槽を冷却しながら反応させた。この状態でＮ
ａ ／ Ｓ比は１．Ｏｌであった。H2S gas was blown into this from a hydrogen sulfide cylinder until it became saturated. During this time, the reaction was carried out while cooling the reaction tank so that the liquid cM did not exceed 110°C. In this state N
The a/S ratio is 1. It was an office worker.
次いで、２．４５ｋｍｏｌの７４．０重量％ＮａＯＨ水
溶液（液温７０℃）を加久て、Ｎ ａ ／ Ｓ比１．９
９の５５．１重量％硫化ナトリウム水溶ン夜を得た。Next, 2.45 kmol of 74.0 wt% NaOH aqueous solution (liquid temperature 70°C) was heated to give a Na/S ratio of 1.9.
A 55.1% by weight aqueous sodium sulfide solution of 9 was obtained.
この硫化ナトリウム水溶液は、透明な清澄液であったが
、不純物としてＮａｇ ＳＯｘが０．１５重量％、Ｎａ
ｇ Ｓｔ Ｏｘが０．０６重量％存在していた。This aqueous sodium sulfide solution was a clear, clear liquid, but contained 0.15% by weight of Nag SOx and Na
g St Ox was present at 0.06% by weight.
この硫化ナトリウム水溶液を反・応槽に入れたままで９
０℃で、２ケ月間、窒素ガスによるシール下に保存した
が、酸化物の増加は認められなかった。If this sodium sulfide aqueous solution is left in the reaction tank,
Although it was stored at 0° C. for 2 months under a nitrogen gas seal, no increase in oxides was observed.
１互■ユ（固体状態の硫化ナトリウムの保存）含水結晶
硫化ナトリウム（はぼＮａ２Ｓ・５ＨｚＯに相当）を１
トン入りコンテナバック中に温度２５〜３５℃、湿度７
０〜８０％の状態で２ケ月間保存したところ、第２表に
示すような変化が見られた。1 reciprocal (preservation of solid state sodium sulfide) 1 hydrated crystalline sodium sulfide (equivalent to Na2S・5HzO)
Temperature 25-35℃, humidity 7 in container bag with tons
When stored for 2 months at 0-80%, changes as shown in Table 2 were observed.
（以下余白）
第２表
および （ｐｐｓの製造）
硫化ナトリウム水溶液と市販の含水結晶硫化ナトリウム
とを対比するため、以下の方法によりＰｐｓを製造した
。(Margin below) Table 2 and (Manufacture of pps) In order to compare the sodium sulfide aqueous solution and commercially available hydrous crystalline sodium sulfide, Pps was manufactured by the following method.
（実施例１）
参考例１で得られた硫化ナトリウム水溶液（９０℃）を
３５４．１ ｋｇ （２，５０ｋｍｏ ｌ）およびＮ−
メチルピロリドン（以下、ＮＭＰと略記）ｌｏｏｏｋｇ
をチタン張りオートクレーブに仕込み、約２０３℃まで
昇温しで水を９６ｋｇを留出させた。(Example 1) 354.1 kg (2,50 kmol) of the sodium sulfide aqueous solution (90°C) obtained in Reference Example 1 and N-
Methylpyrrolidone (hereinafter abbreviated as NMP) loookg
was placed in a titanium-lined autoclave, heated to approximately 203°C, and 96 kg of water was distilled out.
次いで、ｐ−ジクロルベンゼン（７０℃、液状）３７１
ｋｇを仕込んだ、硫化ナトリウム水溶液、ＮＭＰ、ｐ−
ジクロルベンゼンは、いずれも積算流量計（タービン式
流量計）・を用いて計量した。このものをさらに２２０
℃で５時間反応させた後、脱イオン水６１．８ｋｇを追
加した。そして２５５℃で５時間重合させた。Next, p-dichlorobenzene (70°C, liquid) 371
kg of sodium sulfide aqueous solution, NMP, p-
Dichlorobenzene was measured using an integrating flowmeter (turbine flowmeter). 220 more of this stuff
After reacting for 5 hours at °C, 61.8 kg of deionized water was added. Then, polymerization was carried out at 255°C for 5 hours.
反応液を目間０．１ｍｍのスクリーンで篩分けし、粒状
ポリマーだけを分離し、アセトン洗浄、次いで脱イオン
水洗浄して、洗浄ポリマーを得た。The reaction solution was sieved through a screen with a mesh size of 0.1 mm to separate only the granular polymer, which was washed with acetone and then with deionized water to obtain a washed polymer.
洗浄ポリマーを２重量％塩化アンモニウム水溶液に浸漬
し、４０℃で３０分間処理し、脱イオン水で水洗後、乾
燥してＰＰＳを得た。The washed polymer was immersed in a 2% by weight aqueous ammonium chloride solution, treated at 40° C. for 30 minutes, washed with deionized water, and dried to obtain PPS.
以上の操作を１０回繰返し各々得られたポリマーの溶融
粘度（３１０℃、剪断速度２００５ｅｃ−’）を測定し
たところ１５５０〜１８５０ボイズであり、平均値は１
７００ボイズであった。The above operation was repeated 10 times and the melt viscosity (310°C, shear rate 2005 ec-') of each obtained polymer was measured and found to be 1550 to 1850 voids, with an average value of 1
It was 700 voices.
（比較例１）
参考例２の含水結晶硫化ナトリウム（保存前のもの）を
用いて実施例１と同様にＰＰＳを製造した。(Comparative Example 1) PPS was produced in the same manner as in Example 1 using the hydrous crystalline sodium sulfide of Reference Example 2 (before storage).
コンテナバック入り含水結晶硫化ナトリウムを窒素ガス
シール下にホッパースケールへ気流搬送し、４２３．３
ｋｇ （２，５０ｋｍｏ ｌ）を計り出して使用した。Water-containing crystalline sodium sulfide in a container bag is air-flow conveyed to a hopper scale under a nitrogen gas seal, and 423.3
kg (2,50 kmol) was measured out and used.
留出水は１６５ｋｇとし、残水量を実施例１と同様にし
た。The amount of distilled water was 165 kg, and the amount of remaining water was the same as in Example 1.
これ以外は実施例１と同様にしてＰＰＳを得た。以上の
操作を１０回繰返し各々得られたポリマーの溶融粘度を
測定したところ、その平均値は１６００ボイズであった
が、各ロフトごとのポリマーの溶融粘度は１３００〜１
９００ボイズの間で変動した。PPS was obtained in the same manner as in Example 1 except for this. When the above operation was repeated 10 times and the melt viscosity of each obtained polymer was measured, the average value was 1600 voids, but the melt viscosity of the polymer for each loft was 1300 to 1.
It fluctuated between 900 voices.
（比較例２）
参考例２で得られた劣化した含水結晶硫化ナトリウム（
保存後のもの）を用いた以外は比較例１と同様の実験を
３回行なった。(Comparative Example 2) Degraded hydrated crystalline sodium sulfide obtained in Reference Example 2 (
The same experiment as in Comparative Example 1 was conducted three times, except that the sample (after storage) was used.
得られたポリマーの溶融粘度は、それぞれ７００．９０
０および１３００ボイズであり、各ロットごとに相当変
動があり、しかもその平均値は約９７０ボイスと低いも
のであった。The melt viscosity of the obtained polymers was 700.90, respectively.
0 and 1300 voices, which varied considerably from lot to lot, and the average value was as low as about 970 voices.
このように、固体状態の硫化ナトリウムを用いた場合と
比較して、硫化ナトリウ′ム水溶液を使用すると溶融粘
度のバラツキが少ないＰＰＳを得ることができるが、そ
の理由は水溶液であるために計量精度が向上したこと、
酸化防止効果が向上したことなどによるものと推定でき
る。In this way, compared to the case of using solid state sodium sulfide, when using an aqueous sodium sulfide solution, it is possible to obtain PPS with less variation in melt viscosity. improved,
It is presumed that this is due to improved antioxidant effect.
（発明の効果）
本発明によれば、ＰＰＳ製造に当たって、原料の硫化ナ
トリウムを高濃度の水溶液として調製し、これを水溶液
のままで使用することにより、硫化ナトリウムの濃度測
定、貯蔵、移送、計量。(Effects of the Invention) According to the present invention, when producing PPS, sodium sulfide as a raw material is prepared as a highly concentrated aqueous solution, and this is used as an aqueous solution to measure, store, transfer, and weigh the concentration of sodium sulfide. .
空気酸化防止等の取扱が容易となり、そして、高重合度
で、安定した高品質のＰＰＳを得ることができる。Handling such as prevention of air oxidation becomes easy, and stable high-quality PPS with a high degree of polymerization can be obtained.
第１図は、硫化ナトリウムと水との相図である０図中、
斜線１部は、固相または固−液共存相である。第２図は
、水酸化ナトリウムの状態図である。第２図中の符合の
意味は次のとおりである。
１：氷＋溶液 ２：氷＋ＮａＯＨ・７ＨＪ３
： ＮａＯＨ・ＩＨｘＯ＋溶液 ４ ： ＮａＯＨ
・５Ｈ＊０＋溶液５ ： Ｎａ０）１ ・７ＨＪ ＋
ＮａＯＨ・５Ｈｉ０６ ： ＮａＯＨ・４ＨｓＯ＋溶液
７ ： ＮａＯＨ・５ＬＯ＋ ＮａＯＨ・４Ｈ，Ｑ８
： ＮａＯＨ・３．５Ｈ，０＋溶液９ ： Ｎａ０）ｌ
・４Ｈ＊０＋ ＮａＯＨ・３．５Ｈａ０１０ ： Ｎ
ａＯＨ・３．５ＨａＯ＋ ＮａＯＨ・２Ｈ−０１１：
ＮａＯＨ・２ＨｘＯ＋溶液
１２ ： Ｎａ０Ｈ−ＨｓＯ＋溶液
１３ ： ＮａＯＨ・２）１．ｏ＋ Ｎａ０Ｈ−ＬＯｌ
４ ： ＮａＯＨ＋溶液
１５ ： Ｎａ０Ｈ−）１．０ ＋ＮａＯＨ第２図Figure 1 is a phase diagram of sodium sulfide and water.
The first part with diagonal lines is a solid phase or a solid-liquid coexistence phase. FIG. 2 is a phase diagram of sodium hydroxide. The meanings of the symbols in FIG. 2 are as follows. 1: Ice + solution 2: Ice + NaOH・7HJ3
: NaOH・IHxO+solution 4 : NaOH
・5H*0+Solution 5: Na0)1 ・7HJ +
NaOH・5Hi06: NaOH・4HsO+ Solution 7: NaOH・5LO+ NaOH・4H,Q8
: NaOH・3.5H,0+ solution 9 : Na0)l
・4H*0+ NaOH・3.5Ha010: N
aOH・3.5HaO+ NaOH・2H-011:
NaOH・2HxO+ solution 12: NaOH−HsO+ solution 13: NaOH・2)1. o+ NaOH−LOl
4: NaOH + solution 15: NaOH-) 1.0 + NaOH Figure 2
Claims (3)
族化合物とを反応させてポリフェニレンスルフィドを製
造する方法において、硫化ナトリウムを４６〜６０重量
％の水溶液として使用することを特徴とするポリフェニ
レンスルフィドの製造方法。(1) A method for producing polyphenylene sulfide by reacting sodium sulfide and a dihaloaromatic compound in an organic amide solvent, characterized in that sodium sulfide is used as an aqueous solution of 46 to 60% by weight. Method.
である請求項１記載のポリフェニレンスルフィドの製造
方法。(2) Concentration of sodium sulfide aqueous solution is 54 to 56% by weight
The method for producing polyphenylene sulfide according to claim 1.
ことがある不溶物を固液分離し、清澄液として使用する
請求項１記載のポリフェニレンスルフィドの製造方法。(3) The method for producing polyphenylene sulfide according to claim 1, wherein the sodium sulfide aqueous solution is subjected to solid-liquid separation to remove insoluble matter that may be present in the aqueous solution, and is used as a clear liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63231468A JP2720050B2 (en) | 1988-09-17 | 1988-09-17 | Method for producing polyphenylene sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63231468A JP2720050B2 (en) | 1988-09-17 | 1988-09-17 | Method for producing polyphenylene sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0280432A true JPH0280432A (en) | 1990-03-20 |
| JP2720050B2 JP2720050B2 (en) | 1998-02-25 |
Family
ID=16923973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63231468A Expired - Lifetime JP2720050B2 (en) | 1988-09-17 | 1988-09-17 | Method for producing polyphenylene sulfide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2720050B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9809681B2 (en) | 2015-02-19 | 2017-11-07 | Ticona Llc | Method for forming a low viscosity polyarylene sulfide |
| US9815942B2 (en) | 2015-03-25 | 2017-11-14 | Ticona Llc | Technique for forming a high melt viscosity polyarylene sulfide |
| US9988494B2 (en) | 2015-02-19 | 2018-06-05 | Ticona Llc | Method for forming a high molecular weight polyarylene sulfide |
| US10106654B2 (en) | 2015-02-19 | 2018-10-23 | Ticona Llc | Method of polyarylene sulfide precipitation |
| US11319441B2 (en) | 2019-12-20 | 2022-05-03 | Ticona Llc | Method for forming a polyarylene sulfide |
| US11407861B2 (en) | 2019-06-28 | 2022-08-09 | Ticona Llc | Method for forming a polyarylene sulfide |
-
1988
- 1988-09-17 JP JP63231468A patent/JP2720050B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9809681B2 (en) | 2015-02-19 | 2017-11-07 | Ticona Llc | Method for forming a low viscosity polyarylene sulfide |
| US9988494B2 (en) | 2015-02-19 | 2018-06-05 | Ticona Llc | Method for forming a high molecular weight polyarylene sulfide |
| US10106654B2 (en) | 2015-02-19 | 2018-10-23 | Ticona Llc | Method of polyarylene sulfide precipitation |
| US10882959B2 (en) | 2015-02-19 | 2021-01-05 | Ticona Llc | Method of polyarylene sulfide precipitation |
| US9815942B2 (en) | 2015-03-25 | 2017-11-14 | Ticona Llc | Technique for forming a high melt viscosity polyarylene sulfide |
| US11407861B2 (en) | 2019-06-28 | 2022-08-09 | Ticona Llc | Method for forming a polyarylene sulfide |
| US11319441B2 (en) | 2019-12-20 | 2022-05-03 | Ticona Llc | Method for forming a polyarylene sulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2720050B2 (en) | 1998-02-25 |
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