JP6194566B2 - Method for producing aqueous solution containing alkali metal-containing inorganic salt and method for producing solution containing carboxyalkylamino group-containing compound and water-insoluble solution - Google Patents
Method for producing aqueous solution containing alkali metal-containing inorganic salt and method for producing solution containing carboxyalkylamino group-containing compound and water-insoluble solution Download PDFInfo
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- JP6194566B2 JP6194566B2 JP2012139697A JP2012139697A JP6194566B2 JP 6194566 B2 JP6194566 B2 JP 6194566B2 JP 2012139697 A JP2012139697 A JP 2012139697A JP 2012139697 A JP2012139697 A JP 2012139697A JP 6194566 B2 JP6194566 B2 JP 6194566B2
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- Prior art keywords
- alkali metal
- aqueous solution
- water
- group
- inorganic salt
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- 150000001875 compounds Chemical class 0.000 title claims description 167
- 239000007864 aqueous solution Substances 0.000 title claims description 128
- 229910052783 alkali metal Inorganic materials 0.000 title claims description 127
- 150000001340 alkali metals Chemical class 0.000 title claims description 112
- 229910017053 inorganic salt Inorganic materials 0.000 title claims description 91
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 239000000243 solution Substances 0.000 title claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 81
- 239000003799 water insoluble solvent Substances 0.000 claims description 80
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 79
- 229920005989 resin Polymers 0.000 claims description 79
- 239000011347 resin Substances 0.000 claims description 79
- 229920000412 polyarylene Polymers 0.000 claims description 77
- 238000000034 method Methods 0.000 claims description 60
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 43
- 239000008346 aqueous phase Substances 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 125000005843 halogen group Chemical group 0.000 claims description 31
- -1 alkali metal hydrosulfide Chemical class 0.000 claims description 23
- 239000012071 phase Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 20
- 239000002798 polar solvent Substances 0.000 claims description 19
- 239000012074 organic phase Substances 0.000 claims description 18
- 239000011541 reaction mixture Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 15
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims 2
- 238000005406 washing Methods 0.000 description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 34
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 30
- 238000000605 extraction Methods 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 25
- 238000000926 separation method Methods 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 235000011121 sodium hydroxide Nutrition 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
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- 238000002156 mixing Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
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- 238000011084 recovery Methods 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
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- 238000000465 moulding Methods 0.000 description 5
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
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- 238000010791 quenching Methods 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000003495 polar organic solvent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
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- 238000004807 desolvation Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- BZWGZQNUCNUCES-UHFFFAOYSA-N (2,3-dibromophenyl)-phenylmethanone Chemical compound BrC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Br BZWGZQNUCNUCES-UHFFFAOYSA-N 0.000 description 1
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
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- 229940126062 Compound A Drugs 0.000 description 1
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- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
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- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
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- DADSZOFTIIETSV-UHFFFAOYSA-N n,n-dichloroaniline Chemical compound ClN(Cl)C1=CC=CC=C1 DADSZOFTIIETSV-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
本発明は、アルカリ金属含有無機塩を含むＣＯＤ（Chemical Oxygen Demand：化学的酸素消費量）値の低い水溶液の製造方法およびカルボキシアルキルアミノ基含有化合物の製造方法に関する。より詳しくは、ポリアリーレンスルフィド樹脂の製造工程で精製後の廃水として、これまで廃棄されていたアルカリ金属含有無機塩およびＣＯＤ原因物質であるカルボキシアルキルアミノ基含有化合物を含む水溶液から、アルカリ金属含有無機塩を含む水溶液とカルボキシアルキルアミノ基含有化合物とを分離することによって、アルカリ金属含有無機塩を含むＣＯＤ値の低い水溶液を製造する方法、および、カルボキシアルキルアミノ基含有化合物を製造する方法に関する。 The present invention relates to a method for producing an aqueous solution having a low COD (Chemical Oxygen Demand) value containing an alkali metal-containing inorganic salt and a method for producing a carboxyalkylamino group-containing compound. More specifically, from the aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound that is a COD-causing substance, the alkali metal-containing inorganic is used as waste water after purification in the production process of the polyarylene sulfide resin. The present invention relates to a method for producing an aqueous solution having a low COD value containing an alkali metal-containing inorganic salt and a method for producing a carboxyalkylamino group-containing compound by separating an aqueous solution containing a salt and a carboxyalkylamino group-containing compound.
ポリフェニレンスルフィド樹脂に代表されるポリアリーレンスルフィド樹脂（ＰＡＳ樹脂）は、耐熱性、耐薬品性等に優れ、電気電子部品、自動車部品、給湯機部品、繊維、フィルム用途等に幅広く利用されている。特に、リチウムイオン電池用パッキンやガスケット部材といった用途では、近年、特に高分子量ポリアリーレンスルフィド樹脂が、靭性および成形性に優れることから広く用いられている。 A polyarylene sulfide resin (PAS resin) typified by a polyphenylene sulfide resin is excellent in heat resistance and chemical resistance, and is widely used for electrical and electronic parts, automobile parts, water heater parts, fibers, films and the like. In particular, in applications such as packing for lithium ion batteries and gasket members, in recent years, high molecular weight polyarylene sulfide resins have been widely used because of their excellent toughness and moldability.
ポリアリーレンスルフィド樹脂は、Ｎ−メチル−２−ピロリドン（以下、ＮＭＰと略すことがある）などの有機極性溶媒中で、スルフィド化剤と、ポリハロ芳香族化合物とを重合反応させる方法等により得られるが、目的物質のポリアリーレンスルフィド樹脂と共に、溶媒、塩化ナトリウムなどのアルカリ金属含有無機塩や下記一般式（１） The polyarylene sulfide resin is obtained by a method of polymerizing a sulfidizing agent and a polyhaloaromatic compound in an organic polar solvent such as N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP). Together with the target polyarylene sulfide resin, a solvent, an alkali metal-containing inorganic salt such as sodium chloride, and the following general formula (1)
さらに、脱溶媒処理後に得られる反応生成物は目的物質のポリアリーレンスルフィド樹脂と共に、前記アルカリ金属含有無機塩や前記カルボキシアルキルアミノ基含有化合物などの有機塩といった副生成物を含有するため、水洗と濾過が繰り返され、これら副生成物が除去される。一般には、１００℃未満で行う水洗方法と、１００℃以上の高温高圧下で行う熱水洗とがある。水洗又は熱水洗後に得られるポリアリーレンスルフィドは濾過器、遠心濾過器等で分離され、その後乾燥され、必要に応じて熱処理し架橋反応を行い製品とする。 Furthermore, since the reaction product obtained after the desolvation treatment contains by-products such as the organic metal salt such as the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound together with the target polyarylene sulfide resin, Filtration is repeated to remove these by-products. In general, there are a water washing method performed at less than 100 ° C. and a hot water washing performed at a high temperature and high pressure of 100 ° C. or higher. The polyarylene sulfide obtained after washing with water or hot water is separated with a filter, a centrifugal filter or the like, then dried, and subjected to a heat treatment as necessary to obtain a product.
一方、水洗または熱水洗後に得られる廃水は、これまで産業廃棄物として処理されており有効活用されてこなかった。しかしながら、これら廃水中に含まれるカルボキシアルキルアミノ基含有化合物などの有機塩がＣＯＤ負荷原因となることから、環境負荷低減のために、ＣＯＤ物質を低減することが求められていた。 On the other hand, wastewater obtained after washing with water or hot water has been treated as industrial waste and has not been effectively utilized. However, since organic salts such as carboxyalkylamino group-containing compounds contained in these wastewaters cause COD loading, it has been required to reduce COD substances in order to reduce environmental burden.
しかしながら、該廃水中には塩化ナトリウムなどのアルカリ金属含有無機塩も同時に含まれており、アルカリ金属含有無機塩と前記カルボキシアルキルアミノ基含有化合物との分離が困難であった。 However, the wastewater also contains an alkali metal-containing inorganic salt such as sodium chloride, and it was difficult to separate the alkali metal-containing inorganic salt from the carboxyalkylamino group-containing compound.
廃水中のＣＯＤ物質を低減する処理方法としては、たとえば、廃水に、酸性凝集剤を加えてｐＨ調整し、ＣＯＤ物質を不溶化させ、不溶化させたＣＯＤ物質を分離することを特徴とする廃水処理方法などが知られている（特許文献１参照）。しかしながら、この方法は、精製工程の廃水が導入され、混合機能を有し、且つｐＨ指示調節計を備えておりｐＨ調製と凝集処理が可能な凝集反応槽と、前記凝集反応槽より導入された不溶化したＣＯＤ物質を分離する連続式遠心分離装置を用いて分離する方法であるため、分離したＣＯＤ物質の含水率が高く嵩高くなるため取り扱いが煩雑となり、しかも分離したＣＯＤ物質が産業廃棄物となるため、好ましいものとは言えなかった。 As a treatment method for reducing COD substances in wastewater, for example, an acid flocculant is added to wastewater to adjust pH, so that COD substances are insolubilized, and insolubilized COD substances are separated. Etc. are known (see Patent Document 1). However, in this method, the waste water of the purification process is introduced, the mixing function is provided, and the aggregation reaction tank equipped with the pH indicating controller and capable of pH adjustment and aggregation treatment is introduced from the aggregation reaction tank. Since it is a method of separation using a continuous centrifugal separator that separates insolubilized COD material, the water content of the separated COD material becomes high and bulky, and handling becomes complicated, and the separated COD material is separated from industrial waste. Therefore, it was not preferable.
一方、本発明者らは、下記構造式（１） On the other hand, the present inventors have the following structural formula (1)
そこで本発明が解決しようとする課題は、アルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液から、アルカリ金属含有無機塩を含む水溶液と前記カルボキシアルキルアミノ基含有化合物とを効率よく分離し、アルカリ金属含有無機塩を含む水溶液として、または前記カルボキシアルキルアミノ基含有化合物として、それぞれを得る方法、特に、ポリアリーレンスルフィド樹脂の製造工程で精製後の廃水として得られるアルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液から、アルカリ金属含有無機塩を含む水溶液と前記カルボキシアルキルアミノ基含有化合物とを効率よく分離し、アルカリ金属含有無機塩を含む水溶液として、または前記カルボキシアルキルアミノ基含有化合物として、それぞれを得る方法、を提供することにある。 Therefore, the problem to be solved by the present invention is to efficiently separate an aqueous solution containing an alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound from an aqueous solution containing an alkali metal-containing inorganic salt and a carboxyalkylamino group-containing compound. , As an aqueous solution containing an alkali metal-containing inorganic salt or as the carboxyalkylamino group-containing compound, respectively, in particular, an alkali metal-containing inorganic salt and a carboxy obtained as waste water after purification in the production process of polyarylene sulfide resin An aqueous solution containing an alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound are efficiently separated from an aqueous solution containing an alkylamino group-containing compound, and as an aqueous solution containing an alkali metal-containing inorganic salt, or containing the carboxyalkylamino group Conversion As things, is to provide a method for obtaining respectively, the.
本願発明者らは種々の検討を行った結果、アルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液を酸性処理することでカルボキシアルキルアミノ基含有化合物の末端をカルボン酸に変性した後、非水溶性溶媒を加えることで、アルカリ金属含有無機塩を含む水溶液からカルボキシアルキルアミノ基含有化合物を分離することが可能となることを見出し、本発明を完成するに至った。
すなわち本発明は、アルカリ金属含有無機塩および下記一般式（１）
As a result of various investigations, the inventors of the present application modified the terminal of the carboxyalkylamino group-containing compound into a carboxylic acid by acidic treatment of an aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound, It has been found that by adding a water-insoluble solvent, a carboxyalkylamino group-containing compound can be separated from an aqueous solution containing an alkali metal-containing inorganic salt, and the present invention has been completed.
That is, the present invention relates to an alkali metal-containing inorganic salt and the following general formula (1)
（１）前記アルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液をｐＨ６．０以下に調整する工程１、
（２）前記水溶液に非水溶性溶媒を加えて、前記カルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相と、アルカリ金属含有無機塩を含む水相に分離する工程２、
（３）分離したカルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相を除去して、アルカリ金属含有無機塩を含む水溶液を回収する工程３、
を有することを特徴とするアルカリ金属含有無機塩を含む水溶液の製造方法に関する。
(1) Step 1 of adjusting an aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound to pH 6.0 or less,
(2) Step 2, in which a water-insoluble solvent is added to the aqueous solution to separate the organic phase containing the carboxyalkylamino group-containing compound and the water-insoluble solvent into an aqueous phase containing an alkali metal-containing inorganic salt,
(3) Step 3 of removing the organic phase containing the separated carboxyalkylamino group-containing compound and the water-insoluble solvent to recover an aqueous solution containing an alkali metal-containing inorganic salt;
The present invention relates to a method for producing an aqueous solution containing an alkali metal-containing inorganic salt.
また、本発明はアルカリ金属含有無機塩および下記一般式（１） The present invention also relates to an alkali metal-containing inorganic salt and the following general formula (1)
（１）前記アルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液をｐＨ６．０以下に調整する工程１、
（２）前記水溶液に非水溶性溶媒を加えて、前記カルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相と、アルカリ金属含有無機塩を含む水相に分離する工程２、
（４）分離したアルカリ金属含有無機塩を含む水相を除去して、前記カルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相を回収する工程４、を有することを特徴とするカルボキシアルキルアミノ基含有化合物および非水溶性溶媒を含む溶液の製造方法に関する。
(1) Step 1 of adjusting an aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound to pH 6.0 or less,
(2) Step 2, in which a water-insoluble solvent is added to the aqueous solution to separate the organic phase containing the carboxyalkylamino group-containing compound and the water-insoluble solvent into an aqueous phase containing an alkali metal-containing inorganic salt,
(4) removing the aqueous phase containing the separated alkali metal-containing inorganic salt, and recovering the organic phase containing the carboxyalkylamino group-containing compound and a water-insoluble solvent. The present invention relates to a method for producing a solution containing an amino group-containing compound and a water-insoluble solvent.
さらに、本発明は前記記載の製造方法で得られたカルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む溶液に、さらに、アルカリ性水溶液を加えて、前記非水溶性溶媒と、下記一般式（２） Furthermore, in the present invention, an alkaline aqueous solution is further added to the solution containing the carboxyalkylamino group-containing compound and the water-insoluble solvent obtained by the production method described above, and the water-insoluble solvent and the following general formula (2) )
（６）分離した非水溶性溶媒を除去して、該カルボキシアルキルアミノ基含有化合物を含む水溶液を回収する工程６、を有するカルボキシアルキルアミノ基含有化合物を含む水溶液の製造方法に関する。
(6) It is related with the manufacturing method of the aqueous solution containing the carboxyalkylamino group containing compound which has the process 6 which removes the isolate | separated water-insoluble solvent and collect | recovers the aqueous solution containing this carboxyalkylamino group containing compound.
そしてさらに、本発明は前記記載の製造方法で得られたカルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む溶液に、さらに、アルカリ性水溶液を加えて、前記非水溶性溶媒と、下記一般式（２） Furthermore, the present invention further comprises adding an alkaline aqueous solution to the solution containing the carboxyalkylamino group-containing compound obtained by the production method described above and a water-insoluble solvent, and adding the water-insoluble solvent and the following general formula ( 2)
（７）分離した該カルボキシアルキルアミノ基含有化合物を含む水溶液を除去して、非水溶性溶媒を回収する工程７、を有し、工程７で得られた非水溶性溶媒を工程２で使用することを特徴とするアルカリ金属含有無機塩を含む水溶液またはカルボキシアルキルアミノ基含有化合物と非水溶性溶液を含む溶液の製造方法に関する。
(7) removing the aqueous solution containing the separated carboxyalkylamino group-containing compound and recovering the water-insoluble solvent, and using the water-insoluble solvent obtained in step 7 in step 2 The present invention relates to a method for producing an aqueous solution containing an alkali metal-containing inorganic salt or a solution containing a carboxyalkylamino group-containing compound and a water-insoluble solution.
本発明によれば、アルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液から、アルカリ金属含有無機塩を含む水溶液と前記カルボキシアルキルアミノ基含有化合物とを効率よく分離し、アルカリ金属含有無機塩を含む水溶液として、または前記カルボキシアルキルアミノ基含有化合物として、それぞれを得る方法、特に、ポリアリーレンスルフィド樹脂の製造工程で精製後の廃水として得られるアルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液から、アルカリ金属含有無機塩を含む水溶液と前記カルボキシアルキルアミノ基含有化合物とを効率よく分離し、アルカリ金属含有無機塩を含む水溶液として、または前記カルボキシアルキルアミノ基含有化合物として、それぞれを得る方法を提供することができる。 According to the present invention, an aqueous solution containing an alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound are efficiently separated from an aqueous solution containing an alkali metal-containing inorganic salt and a carboxyalkylamino group-containing compound. Methods for obtaining each as an aqueous solution containing a salt or as the carboxyalkylamino group-containing compound, in particular, an alkali metal-containing inorganic salt and a carboxyalkylamino group-containing compound obtained as waste water after purification in the production process of the polyarylene sulfide resin An aqueous solution containing an alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound are efficiently separated from an aqueous solution containing an alkali metal-containing inorganic salt as an aqueous solution, or as the carboxyalkylamino group-containing compound, respectively. That way it is possible to provide a.
（工程１）
本発明は、アルカリ金属含有無機塩および下記一般式（１）
(Process 1)
The present invention relates to an alkali metal-containing inorganic salt and the following general formula (1)
ここで、アルカリ金属含有無機塩および前記カルボキシアルキルアミノ基含有化合物を含む水溶液の調製は、少なくとも、アルカリ金属含有無機塩および前記カルボキシアルキルアミノ基含有化合物を含む水溶液であって、水溶液中にアルカリ金属含有無機塩を０．１〜２６質量％の範囲および前記カルボキシアルキルアミノ基含有化合物を０．０１〜５質量％の範囲で含有するよう行い、かつ、実質的にポリアリーレンスルフィド樹脂を含まないよう行う。アルカリ金属含有無機塩および前記カルボキシアルキルアミノ基含有化合物を含む水溶液の調整方法は、上記組成を調製できればいかなる方法でも問題ないが、アルカリ金属含有無機塩および前記カルボキシアルキルアミノ基含有化合物を含む水にアルカリを加えてｐＨ１０．０〜１３．０に調整し、４０〜９０℃の範囲に加熱して溶解させればよい。また、ポリアリーレンスルフィド樹脂重合の精製工程で得られる、アルカリ金属含有無機塩および前記カルボキシアルキルアミノ基含有化合物を含む水溶液を用いることもできる。ただし、アルカリ金属含有無機塩および前記カルボキシアルキルアミノ基含有化合物を含む水溶液が実質的にポリアリーレンスルフィド樹脂を含有しないとは、基本的には検出限界以下であることを指すものとするが、下記ポリアリーレンスルフィド樹脂の精製工程で調整される場合には、精製処理の方法やその度合いに応じて極微量のポリアリーレンスルフィド樹脂が含有される場合があり、その濃度は、該水溶液中のポリアリーレンスルフィド樹脂濃度１ｐｐｍ以下、多い場合でも５ｐｐｍ以下である。 Here, the preparation of the aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound is at least an aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound, The inorganic salt is contained in the range of 0.1 to 26% by mass and the carboxyalkylamino group-containing compound is contained in the range of 0.01 to 5% by mass and substantially free of polyarylene sulfide resin. Do. The preparation method of the aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound may be any method as long as the above composition can be prepared, but the water containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound may be used. What is necessary is just to adjust to pH 10.0-13.0 by adding an alkali and to melt | dissolve by heating in the range of 40-90 degreeC. Moreover, the aqueous solution containing the alkali metal containing inorganic salt obtained by the refinement | purification process of polyarylene sulfide resin polymerization and the said carboxyalkylamino group containing compound can also be used. However, the aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound substantially does not contain a polyarylene sulfide resin, which basically means that it is below the detection limit, When adjusted in the purification process of the polyarylene sulfide resin, a very small amount of the polyarylene sulfide resin may be contained depending on the method of purification and its degree, and the concentration of the polyarylene sulfide resin in the aqueous solution The sulfide resin concentration is 1 ppm or less, and even when it is large, it is 5 ppm or less.
アルカリ金属含有無機塩および前記カルボキシアルキルアミノ基含有化合物を含む水溶液をポリアリーレンスルフィド樹脂重合の精製工程で得る方法としては、有機極性溶媒中で、ポリハロ芳香族化合物と、（ｉ）アルカリ金属硫化物とを、または、（ｉｉ）アルカリ金属水硫化物及びアルカリ金属水酸化物とを反応させてポリアリーレンスルフィド樹脂とアルカリ金属含有無機塩と前記カルボキシアルキルアミノ基含有化合物と前記有機極性溶媒を含む粗反応混合物を得（重合工程）、その後、粗反応混合物から前記有機極性溶媒を固液分離させてポリアリーレンスルフィド樹脂とアルカリ金属含有無機塩と前記カルボキシアルキルアミノ基含有化合物を含む反応混合物を得（固液分離工程）、その後、該反応混合物を水と接触させてポリアリーレンスルフィド樹脂を濾別する工程（精製工程）を経て、アルカリ金属含有無機塩および前記カルボキシアルキルアミノ基含有化合物を含む水溶液を得る方法を挙げることができる。 As a method of obtaining an aqueous solution containing an alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound in the purification step of polyarylene sulfide resin polymerization, in a polar organic solvent, a polyhaloaromatic compound and (i) an alkali metal sulfide Or (ii) a crude containing a polyarylene sulfide resin, an alkali metal-containing inorganic salt, the carboxyalkylamino group-containing compound, and the organic polar solvent by reacting an alkali metal hydrosulfide and an alkali metal hydroxide. A reaction mixture is obtained (polymerization step), and then the organic polar solvent is solid-liquid separated from the crude reaction mixture to obtain a reaction mixture containing a polyarylene sulfide resin, an alkali metal-containing inorganic salt, and the carboxyalkylamino group-containing compound ( Solid-liquid separation step), and then contacting the reaction mixture with water to Through the step (purification step) filtering off the Lee sulfide resin may be a method of obtaining an aqueous solution containing an alkali metal-containing inorganic salt and said carboxyalkyl amino group-containing compound.
ここで、ポリアリーレンスルフィド樹脂の重合工程で用いられるポリハロ芳香族化合物としては、例えば、芳香族環に直接結合した２個以上のハロゲン原子を有するハロゲン化芳香族化合物であり、具体的には、ｐ−ジクロルベンゼン、ｏ−ジクロルベンゼン、ｍ−ジクロルベンゼン、トリクロルベンゼン、テトラクロルベンゼン、ジブロムベンゼン、ジヨードベンゼン、トリブロムベンゼン、ジブロムナフタレン、トリヨードベンゼン、ジクロルジフェニルベンゼン、ジブロムジフェニルベンゼン、ジクロルベンゾフェノン、ジブロムベンゾフェノン、ジクロルジフェニルエーテル、ジブロムジフェニルエーテル、ジクロルジフェニルスルフィド、ジブロムジフェニルスルフィド、ジクロルビフェニル、ジブロムビフェニル等のジハロ芳香族化合物及びこれらの混合物が挙げられ、これらの化合物をブロック共重合してもよい。これらの中でも好ましいのはジハロゲン化ベンゼン類であり、特に好ましいのはｐ−ジクロルベンゼンを８０モル％以上含むものである。 Here, the polyhaloaromatic compound used in the polymerization process of the polyarylene sulfide resin is, for example, a halogenated aromatic compound having two or more halogen atoms directly bonded to the aromatic ring, and specifically, p-dichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dibromobenzene, diiodobenzene, tribromobenzene, dibromonaphthalene, triiodobenzene, dichlorodiphenylbenzene, Dihaloaromatics such as dibromodiphenylbenzene, dichlorobenzophenone, dibromobenzophenone, dichlorodiphenyl ether, dibromodiphenyl ether, dichlorodiphenyl sulfide, dibromodiphenyl sulfide, dichlorobiphenyl, dibromobiphenyl Compounds and mixtures thereof, these compounds may be block copolymerized. Of these, dihalogenated benzenes are preferred, and those containing p-dichlorobenzene of 80 mol% or more are particularly preferred.
また、枝分かれ構造とすることによってポリアリーレンスルフィド樹脂の粘度増大を図る目的で、１分子中に３個以上のハロゲン置換基を有するポリハロ芳香族化合物を分岐剤として所望に応じて用いてもよい。このようなポリハロ芳香族化合物としては、例えば、１，２，４−トリクロルベンゼン、１，３，５−トリクロルベンゼン、１，４，６−トリクロルナフタレン等が挙げられる。 Further, for the purpose of increasing the viscosity of the polyarylene sulfide resin by using a branched structure, a polyhaloaromatic compound having 3 or more halogen substituents in one molecule may be used as a branching agent as desired. Examples of such polyhaloaromatic compounds include 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,4,6-trichloronaphthalene, and the like.
更に、アミノ基、チオール基、ヒドロキシル基等の活性水素を持つ官能基を有するポリハロ芳香族化合物を挙げることが出来、具体的には、２，６−ジクロルアニリン、２，５−ジクロルアニリン、２，４−ジクロルアニリン、２，３−ジクロルアニリン等のジハロアニリン類；２，３，４−トリクロルアニリン、２，３，５−トリクロルアニリン、２，４，６−トリクロルアニリン、３，４，５−トリクロルアニリン等のトリハロアニリン類；２，２’−ジアミノ−４，４’−ジクロルジフェニルエーテル、２，４’−ジアミノ−２’，４−ジクロルジフェニルエーテル等のジハロアミノジフェニルエーテル類およびこれらの混合物においてアミノ基がチオール基やヒドロキシル基に置き換えられた化合物などが例示される。 Furthermore, polyhaloaromatic compounds having a functional group having active hydrogen such as amino group, thiol group, hydroxyl group can be mentioned. Specifically, 2,6-dichloroaniline, 2,5-dichloroaniline 2,4-dichloroaniline, 2,3-dichloroaniline and other dihaloanilines; 2,3,4-trichloroaniline, 2,3,5-trichloroaniline, 2,4,6-trichloroaniline, 3, Trihaloanilines such as 4,5-trichloroaniline; dihaloaminodiphenyl ethers such as 2,2′-diamino-4,4′-dichlorodiphenyl ether and 2,4′-diamino-2 ′, 4-dichlorodiphenyl ether Examples thereof include compounds in which the amino group is replaced by a thiol group or a hydroxyl group in a mixture thereof.
また、これらの活性水素含有ポリハロ芳香族化合物中の芳香族環を形成する炭素原子に結合した水素原子が他の不活性基、例えばアルキル基などの炭化水素基に置換している活性水素含有ポリハロ芳香族化合物も使用できる。 In addition, active hydrogen-containing polyhalo compounds in which the hydrogen atom bonded to the carbon atom forming the aromatic ring in these active hydrogen-containing polyhaloaromatic compounds is substituted with another inert group, for example, a hydrocarbon group such as an alkyl group. Aromatic compounds can also be used.
これらの各種活性水素含有ポリハロ芳香族化合物の中でも、好ましいのは活性水素含有ジハロ芳香族化合物であり、特に好ましいのはジクロルアニリンである。 Among these various active hydrogen-containing polyhaloaromatic compounds, an active hydrogen-containing dihaloaromatic compound is preferable, and dichloroaniline is particularly preferable.
ニトロ基を有するポリハロ芳香族化合物としては、例えば、２，４−ジニトロクロルベンゼン、２，５−ジクロルニトロベンゼン等のモノまたはジハロニトロベンゼン類；２−ニトロ−４，４’−ジクロルジフェニルエーテル等のジハロニトロジフェニルエーテル類；３，３’−ジニトロ−４，４’−ジクロルジフェニルスルホン等のジハロニトロジフェニルスルホン類；２，５−ジクロル−３−ニトロピリジン、２−クロル−３，５−ジニトロピリジン等のモノまたはジハロニトロピリジン類；あるいは各種ジハロニトロナフタレン類などが挙げられる。 Examples of the polyhaloaromatic compound having a nitro group include mono- or dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene; 2-nitro-4,4′-dichlorodiphenyl ether Dihalonitrodiphenyl ethers; dihalonitrodiphenyl sulfones such as 3,3′-dinitro-4,4′-dichlorodiphenyl sulfone; 2,5-dichloro-3-nitropyridine, 2-chloro-3,5 -Mono or dihalonitropyridines such as dinitropyridine; or various dihalonitronaphthalenes.
また、ポリアリーレンスルフィド樹脂の重合工程で用いられるアルカリ金属硫化物としては、硫化リチウム、硫化ナトリウム、硫化ルビジウム、硫化セシウム及びこれらの混合物が含まれる。かかるアルカリ金属硫化物は、水和物あるいは水性混合物あるいは無水物として使用することができる。また、アルカリ金属硫化物はアルカリ金属水硫化物とアルカリ金属水酸化物との反応によっても導くことができる。尚、通常、アルカリ金属硫化物中に微量存在するアルカリ金属水硫化物、チオ硫酸アルカリ金属と反応させるために、少量のアルカリ金属水酸化物を加えても差し支えない。 The alkali metal sulfide used in the polymerization process of the polyarylene sulfide resin includes lithium sulfide, sodium sulfide, rubidium sulfide, cesium sulfide and a mixture thereof. Such alkali metal sulfides can be used as hydrates, aqueous mixtures or anhydrides. The alkali metal sulfide can also be derived from the reaction between an alkali metal hydrosulfide and an alkali metal hydroxide. Normally, a small amount of alkali metal hydroxide may be added to react with alkali metal hydrosulfide or alkali metal thiosulfate present in a trace amount in the alkali metal sulfide.
また、ポリアリーレンスルフィド樹脂の重合工程で用いられるアルカリ金属水硫化物としては、水硫化リチウム、水硫化ナトリウム、水硫化ルビジウム、水硫化セシウム及びこれらの混合物が含まれる。かかるアルカリ金属水硫化物は、水和物あるいは水性混合物あるいは無水物として使用することができる。 The alkali metal hydrosulfide used in the polymerization process of the polyarylene sulfide resin includes lithium hydrosulfide, sodium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures thereof. Such alkali metal hydrosulfides can be used as hydrates, aqueous mixtures or anhydrides.
また、ポリアリーレンスルフィド樹脂の重合工程で用いられるアルカリ金属水酸化物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウム等が挙げられるが、これらはそれぞれ単独で用いても良いし、２種以上を混合して用いても良い。これらの中でも、入手が容易なことから水酸化リチウムと水酸化ナトリウム及び水酸化カリウムが好ましく、特に水酸化ナトリウムが好ましい。 Examples of the alkali metal hydroxide used in the polymerization process of the polyarylene sulfide resin include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and the like. You may use, and may mix and use 2 or more types. Among these, lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferable because they are easily available, and sodium hydroxide is particularly preferable.
また、ポリアリーレンスルフィド樹脂の重合工程で用いられる有機極性溶媒としては、ホルムアミド、アセトアミド、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、テトラメチル尿素、Ｎ−メチル−２−ピロリドン、２−ピロリドン、Ｎ−メチル−ε−カプロラクタム、ε−カプロラクタム、ヘキサメチルホスホルアミド、Ｎ−ジメチルプロピレン尿素、１，３−ジメチル−２−イミダゾリジノン酸などのアミド、尿素及びラクタム類；スルホラン、ジメチルスルホラン等のスルホラン類；ベンゾニトリル等のニトリル類；メチルフェニルケトン等のケトン類及びこれらの混合物を挙げることができ、これらの中でもＮ−メチル−２−ピロリドン、２−ピロリドン、Ｎ−メチル−ε−カプロラクタム、ε−カプロラクタム、ヘキサメチルホスホルアミド、Ｎ−ジメチルプロピレン尿素、１，３−ジメチル−２−イミダゾリジノン酸の脂肪族系環状構造を有するアミドが好ましい。 Examples of the organic polar solvent used in the polymerization process of the polyarylene sulfide resin include formamide, acetamide, N-methylformamide, N, N-dimethylacetamide, tetramethylurea, N-methyl-2-pyrrolidone, 2-pyrrolidone, Amides such as N-methyl-ε-caprolactam, ε-caprolactam, hexamethylphosphoramide, N-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone acid, urea and lactams; sulfolane, dimethylsulfolane, etc. Sulfolanes; nitriles such as benzonitrile; ketones such as methyl phenyl ketone; and mixtures thereof, among which N-methyl-2-pyrrolidone, 2-pyrrolidone, N-methyl-ε-caprolactam , Ε-caprolactam, hexa Chill phosphoramide, N- dimethyl propylene urea, amide with 1,3-dimethyl-2-aliphatic ring structure imidazolidinone acid.
ポリアリーレンスルフィド樹脂の重合反応は、これらの有機極性溶媒の存在下、スルフィド化剤として上記アルカリ金属硫化物と、ポリハロ芳香族化合物とを反応させる。または、ポリアリーレンスルフィド樹脂の重合反応は、これらの有機極性溶媒の存在下、スルフィド化剤として上記アルカリ金属水硫化物及びアルカリ金属水酸化物と、ポリハロ芳香族化合物とを反応させる。重合条件は一般に、温度２００〜３３０℃の範囲であり、圧力は重合溶媒及び重合モノマーであるポリハロ芳香族化合物を実質的に液相に保持するような範囲であるべきであり、一般には０．１〜２０ＭＰａの範囲、好ましくは０．１〜２ＭＰａの範囲より選択される。ポリハロ芳香族化合物の配合量は、前記スルフィド化剤の硫黄原子１モルに対して、０．２モル〜５．０モルの範囲が挙げられる。 In the polymerization reaction of the polyarylene sulfide resin, the alkali metal sulfide is reacted with the polyhaloaromatic compound as a sulfidizing agent in the presence of these organic polar solvents. Alternatively, in the polymerization reaction of the polyarylene sulfide resin, the alkali metal hydrosulfide and alkali metal hydroxide are reacted with the polyhaloaromatic compound as a sulfidizing agent in the presence of these organic polar solvents. The polymerization conditions are generally in the range of 200 to 330 ° C., and the pressure should be in such a range as to keep the polymerization solvent and the polymerization monomer polyhaloaromatic compound in a substantially liquid phase. It is selected from the range of 1-20 MPa, preferably from the range of 0.1-2 MPa. The compounding quantity of a polyhalo aromatic compound has the range of 0.2 mol-5.0 mol with respect to 1 mol of sulfur atoms of the said sulfidizing agent.
上記した有機極性溶媒の存在下、スルフィド化剤とポリハロ芳香族化合物とを重合させる具体的態様としては、例えば、
１）アルカリ金属カルボン酸塩またはハロゲン化リチウム等の重合助剤を使用する方法、
２）芳香族ポリハロゲン化合物等の架橋剤を使用する方法、
３）少量の水の存在下に重合反応を行い次いで水を追加してさらに重合する方法、
４）アルカリ金属硫化物と芳香族ジハロゲン化合物との反応中に、反応釜の気相部分を冷却して反応釜内の気相の一部を凝縮させ液相に還流させる方法、などが挙げられる。
５）ポリハロ芳香族化合物の存在下、アルカリ金属硫化物、又は、含水アルカリ金属水硫化物及びアルカリ金属水酸化物と、脂肪族環状構造を有するアミド、尿素またはラクタムとを、脱水させながら反応させて固形のアルカリ金属硫化物を含むスラリーを製造する工程、該スラリーを製造した後、更にＮＭＰなどの極性有機溶媒を加え、水を留去して脱水を行う工程、次いで、脱水工程を経て得られたスラリー中で、ポリハロ芳香族化合物と、アルカリ金属水硫化物と、前記脂肪族環状構造を有するアミド、尿素またはラクタムの加水分解物のアルカリ金属塩とを、ＮＭＰなどの極性有機溶媒１モルに対して反応系内に現存する水分量が０．０２モル以下で反応させて重合を行う工程を必須の製造工程として有するポリアリーレンスルフィド樹脂の製造方法が挙げられる。
As a specific embodiment for polymerizing a sulfidizing agent and a polyhaloaromatic compound in the presence of the organic polar solvent described above, for example,
1) A method using a polymerization aid such as an alkali metal carboxylate or lithium halide,
2) A method using a crosslinking agent such as an aromatic polyhalogen compound,
3) A method in which a polymerization reaction is carried out in the presence of a small amount of water and then water is added for further polymerization
4) During the reaction between the alkali metal sulfide and the aromatic dihalogen compound, a method of cooling the gas phase part of the reaction vessel to condense a part of the gas phase in the reaction vessel and refluxing it to the liquid phase, etc. .
5) In the presence of a polyhaloaromatic compound, an alkali metal sulfide, or a hydrous alkali metal hydrosulfide and an alkali metal hydroxide, and an amide, urea or lactam having an aliphatic cyclic structure are reacted while being dehydrated. Obtained through a step of producing a slurry containing a solid alkali metal sulfide, a step of adding a polar organic solvent such as NMP and dehydrating by distilling off water after producing the slurry, followed by a dehydration step. In the resulting slurry, a polyhaloaromatic compound, an alkali metal hydrosulfide, and an alkali metal salt of an amide, urea or lactam hydrolyzate having an aliphatic cyclic structure are mixed with 1 mol of a polar organic solvent such as NMP. In contrast, polyarylene sulfide having a process of performing polymerization by reacting at a water content of 0.02 mol or less in the reaction system as an essential process. Method for manufacturing a resin.
このうち１）〜４）の重合方法でポリアリーレンスルフィド樹脂を製造すると、副生成物の生成がより多くなるため、精製後の廃水中に含まれるＣＯＤ値も高い傾向にある。このため、特に１）〜４）の重合方法でポリアリーレンスルフィド樹脂を製造する場合に、本発明の方法により、廃水中のＣＯＤ原因物質であるカルボキシアルキルアミノ基含有化合物を低減することが好ましい。 Among these, when a polyarylene sulfide resin is produced by the polymerization methods 1) to 4), more by-products are produced, and therefore the COD value contained in the wastewater after purification tends to be high. For this reason, particularly when producing a polyarylene sulfide resin by the polymerization methods 1) to 4), it is preferable to reduce the carboxyalkylamino group-containing compound which is a COD-causing substance in wastewater by the method of the present invention.
なお、ポリアリーレンスルフィド樹脂の製造時に、ポリアリーレンスルフィド樹脂の製造原料として、例えば、有機極性溶媒がＮ−メチル−２−ピロリドン、ポリハロ芳香族化合物がｐ−ジクロロベンゼンである場合には前記カルボキシアルキルアミノ基含有化合物として、下記一般式（３） In the production of the polyarylene sulfide resin, as a raw material for producing the polyarylene sulfide resin, for example, when the organic polar solvent is N-methyl-2-pyrrolidone and the polyhaloaromatic compound is p-dichlorobenzene, the carboxyalkyl As an amino group-containing compound, the following general formula (3)
ポリアリーレンスルフィド樹脂の重合終了後に、ポリアリーレンスルフィド樹脂とアルカリ金属含有無機塩と前記カルボキシアルキルアミノ基含有化合物と前記有機極性溶媒を含む粗反応混合物を得ることができる。次に、得られた粗反応混合物から有機極性溶媒を固液分離させて、ポリアリーレンスルフィド樹脂およびアルカリ金属含有無機塩と前記カルボキシアルキルアミノ基含有化合物を含む反応混合物を得る。該固液分離には大きく分けて、後述するフラッシュ法とクウェンチ法の２種類がある。フラッシュ法は、溶媒を蒸発させて溶媒回収し、同時に固形物を回収する方法であり、一般的に、減圧下に加熱して溶媒を留去することにより行われる。 After the polymerization of the polyarylene sulfide resin, a crude reaction mixture containing the polyarylene sulfide resin, the alkali metal-containing inorganic salt, the carboxyalkylamino group-containing compound, and the organic polar solvent can be obtained. Next, the organic polar solvent is subjected to solid-liquid separation from the obtained crude reaction mixture to obtain a reaction mixture containing a polyarylene sulfide resin, an alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound. The solid-liquid separation is roughly classified into two types, a flash method and a quench method described later. The flash method is a method of recovering a solvent by evaporating the solvent and simultaneously recovering a solid substance, and is generally performed by heating under reduced pressure to distill off the solvent.
一方、クウェンチ法は、重合反応物を、除冷して粒子状のポリアリーレンスルフィド樹脂を回収する方法であり、一般的に、反応釜内で反応スラリーを冷却後、ポリアリーレンスルフィド樹脂を晶析させた後に固液分離する方法が挙げられる。クウェンチ法における固液分離は、濾過やスクリューデカンター等の遠心分離機を用いて分離した後、得られた濾過残渣に直接水を加えスラリー化したのち、固液分離を繰り返し行う方法や、得られた濾過残渣を非酸化性雰囲気下で加熱して、残存する溶媒を除去する方法などが挙げられる。フラッシュ法は、固形物を比較的簡便に回収することができる点で好ましく、クウェンチ法は、ポリアリーレンスルフィド樹脂の粒度を制御しやすい点や晶析時にポリマー粒子にアルカリ金属含有無機塩やその他の不純物を取り込みにくくなるため、高純度のポリマーが得られる点で好ましい。 On the other hand, the quench method is a method in which the polymerization reaction product is removed by cooling to recover the particulate polyarylene sulfide resin. Generally, after cooling the reaction slurry in a reaction kettle, the polyarylene sulfide resin is crystallized. For example, a solid-liquid separation method may be used. Solid-liquid separation in the Quench method is a method in which after separation using a centrifugal separator such as filtration or screw decanter, water is directly added to the obtained filtration residue to form a slurry, and then solid-liquid separation is repeated. For example, a method of removing the remaining solvent by heating the filtered residue in a non-oxidizing atmosphere can be used. The flash method is preferable because solids can be collected relatively easily, and the quench method is easy to control the particle size of the polyarylene sulfide resin, and the polymer particles contain alkali metal-containing inorganic salts and other salts during crystallization. Since it becomes difficult to take in impurities, it is preferable in that a high-purity polymer is obtained.
続いて、前記反応混合物を、水と接触させてポリアリーレンスルフィド樹脂を濾別することによって、アルカリ金属含有無機塩および前記カルボキシアルキルアミノ基含有化合物を含む水溶液を調製することができる。 Subsequently, an aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound can be prepared by bringing the reaction mixture into contact with water and filtering off the polyarylene sulfide resin.
前記反応混合物を、水と接触させた後、固液分離しポリアリーレンスルフィド樹脂を濾別する方法（以下、「水洗」ということがある）としては、例えば、前記粗反応混合物から有機極性溶媒を固液分離させて得られた反応スラリーに水を加えて撹拌した後にろ過装置を用いてろ過する方法、前記したろ過によって得られた水分を含有するろ過残渣（以下「含水ケーキ」と略記する。）に再度水を加えてスラリーとした後にろ過する方法、または前記含水ケーキがろ過器に保持された状態で再度水を加えろ過する方法等が挙げられる。 Examples of the method of bringing the reaction mixture into contact with water, followed by solid-liquid separation and filtering off the polyarylene sulfide resin (hereinafter sometimes referred to as “washing”) include, for example, removing an organic polar solvent from the crude reaction mixture. A method in which water is added to the reaction slurry obtained by solid-liquid separation and stirred, followed by filtration using a filtration device, and a filtration residue containing moisture obtained by the filtration described above (hereinafter abbreviated as “water-containing cake”). And a method of adding water again to form a slurry, and a method of filtering, or a method of adding water again and filtering in a state where the water-containing cake is held in a filter.
前記水洗の際に反応スラリーに加える水の量は最終的に得られるポリアリーレンスルフィドの理論収量に対して２倍〜１０倍の範囲にあることが好ましく洗浄効率の点から好ましく、上記の量の水を２〜１０回、好ましくは２〜４回に分割して水洗に供することが好ましい。前記水洗は、窒素ないし空気雰囲気下、水温５０℃〜１００℃の範囲、洗浄効率が良好となる点から、なかでも７０℃〜９０℃の範囲で行うことが好ましい。前記水洗は、一回または複数回繰り返し行うことができる。複数回繰り返し水洗浄する場合、前記雰囲気・温度条件は同一でも異なっていても良い。 The amount of water added to the reaction slurry during the water washing is preferably in the range of 2 to 10 times the theoretical yield of the polyarylene sulfide finally obtained, from the viewpoint of washing efficiency, It is preferable to divide the water into 2 to 10 times, preferably 2 to 4 times, and wash it with water. The water washing is preferably performed in a nitrogen or air atmosphere in a water temperature range of 50 ° C. to 100 ° C. and a cleaning efficiency of 70 ° C. to 90 ° C., in particular. The water washing can be repeated once or a plurality of times. When water washing is repeated a plurality of times, the atmosphere and temperature conditions may be the same or different.
濾別されたポリアリーレンスルフィド樹脂には、微量のアルカリ金属含有無機塩やカルボキシアルキルアミノ基含有化合物が残留していることがあるため、さらに１００〜２７５℃の範囲の水と接触させた後に固液分離し（以下、「熱水洗」ということがある）、ポリアリーレンスルフィド樹脂を濾別し、残留していたアルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液を抽出することができ、この水溶液も本発明に用いることができる。 The polyarylene sulfide resin separated by filtration may contain a trace amount of an alkali metal-containing inorganic salt or a carboxyalkylamino group-containing compound. Therefore, the polyarylene sulfide resin may be further solidified after contact with water in the range of 100 to 275 ° C. Liquid separation (hereinafter sometimes referred to as “hot water washing”), the polyarylene sulfide resin is filtered off, and the remaining aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound can be extracted. This aqueous solution can also be used in the present invention.
熱水洗の温度は、例えば、１２０〜２７５℃の範囲であることが、カルボキシアルキルアミノ基含有化合物の抽出効率が良好となる点から好ましい。更に具体的には、反応器内の気相の圧力を０．２〜４．６ＭＰａなる条件下、１４０〜２６０℃の熱水で抽出処理を行うことが好ましい。このような熱水処理によりポリアリーレンスルフィド樹脂中に包含されて残留しているアルカリ金属や前記カルボキシアルキルアミノ基含有化合物をより効率よく水中に抽出することができ、続いてポリアリーレンスルフィド樹脂を濾別することによってアルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液を得ることができる。 The temperature of the hot water washing is preferably in the range of 120 to 275 ° C., for example, from the viewpoint of good extraction efficiency of the carboxyalkylamino group-containing compound. More specifically, it is preferable to perform the extraction treatment with hot water at 140 to 260 ° C. under the condition that the pressure of the gas phase in the reactor is 0.2 to 4.6 MPa. By such hydrothermal treatment, the remaining alkali metal contained in the polyarylene sulfide resin and the carboxyalkylamino group-containing compound can be more efficiently extracted into water, and then the polyarylene sulfide resin is filtered. By separating, an aqueous solution containing an alkali metal-containing inorganic salt and a carboxyalkylamino group-containing compound can be obtained.
このような熱水洗を行う具体的方法は、前記の水洗後に濾別されたポリアリーレンスルフィド樹脂を圧力容器中において所定の圧力条件及び温度条件下に水で攪拌下に洗浄する方法が挙げられる。熱水洗時の水量はポリアリーレンスルフィドの質量に対して１．５倍〜１０倍であることが、前記カルボキシアルキルアミノ基含有化合物の抽出効率が良好となる点から好ましく、この量の熱水を２回以上に分けて熱水洗を行ってもよい。例えば、熱水洗を２回繰り返す場合、１回目の熱水洗と２回目の熱水洗の間にはろ過を行い、１回目の熱水洗で抽出したカルボキシアルキルアミノ基含有化合物を除去することが好ましい。また、熱水洗を一回実施した後に濾過を行い、前記した水洗を実施しても良い。この操作によってもカルボキシアルキルアミノ基含有化合物の除去がより促進される。また１回目の熱水洗工程と２回目の熱水洗工程の条件は前記の条件より任意に選ぶことができるものの、１回目の熱水洗工程の温度は例えば１２０℃〜２００℃の範囲にある温度に設定して、まず高アルカリ性の濾液を濾別して除去した後に、２回目の熱水洗工程の温度を１回目の熱水洗工程の温度より高い温度、例えば１５０℃〜２７５℃の範囲にある温度に設定して実施することが前記熱水洗で用いられる装置の耐薬品性の観点から好ましい。 As a specific method for performing such hot water washing, there is a method of washing the polyarylene sulfide resin filtered off after the water washing with stirring in water under a predetermined pressure condition and temperature condition in a pressure vessel. The amount of water at the time of hot water washing is preferably 1.5 times to 10 times the mass of polyarylene sulfide, from the point that the extraction efficiency of the carboxyalkylamino group-containing compound is good. The hot water washing may be performed in two or more times. For example, when hot water washing is repeated twice, it is preferable to perform filtration between the first hot water washing and the second hot water washing to remove the carboxyalkylamino group-containing compound extracted by the first hot water washing. Moreover, after performing hot water washing once, it may filter and may carry out an above described water washing. This operation also promotes the removal of the carboxyalkylamino group-containing compound. Moreover, although the conditions of the 1st hot water washing process and the 2nd hot water washing process can be selected arbitrarily from said conditions, the temperature of the 1st hot water washing process is the temperature which exists in the range of 120 to 200 degreeC, for example. After setting and removing the first highly alkaline filtrate by filtration, the temperature of the second hot water washing step is set to a temperature higher than the temperature of the first hot water washing step, for example, in the range of 150 ° C. to 275 ° C. It is preferable to implement it from the viewpoint of chemical resistance of the apparatus used in the hot water washing.
さらに、熱水洗の際に酸や塩基を添加してｐＨ調整をすることができ、特にカルボキシアルキルアミノ基含有化合物において式中Ｘがアルカリ金属原子となり水に抽出され易くなることから、熱水洗後のｐＨが１１．０以上１３．０未満の範囲になるように制御することが好ましい。熱水洗時に用いる酸としては、例えば、塩酸、硫酸、炭酸、酢酸等が挙げられ、これらの中でも炭酸や酢酸が好ましい。熱水洗時に用いる塩基としては水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、または炭酸ナトリウム、炭酸アンモニウム、リン酸ナトリウム等が挙げられ、これらの中でも水酸化ナトリウムが好ましい。 Furthermore, the pH can be adjusted by adding an acid or a base during hot water washing. In particular, in a carboxyalkylamino group-containing compound, X in the formula becomes an alkali metal atom and is easily extracted into water. It is preferable to control so that the pH is in the range of 11.0 or more and less than 13.0. Examples of the acid used at the time of hot water washing include hydrochloric acid, sulfuric acid, carbonic acid, acetic acid and the like, and among these, carbonic acid and acetic acid are preferable. Examples of the base used in the hot water washing include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, or sodium carbonate, ammonium carbonate, sodium phosphate, and the like. Among these, sodium hydroxide is preferable.
本発明において水洗は、撹拌機を有する水洗槽や、固液分離するための遠心分離機を用いることも可能であるが、容器内部に撹拌翼を有し、且つ、底部に濾過用フィルターが配設された混合機能を有す容器内で行うことができる。また、１００℃を超える熱水洗でも、撹拌機を有する水洗槽や、固液分離するための遠心分離機を用いることも可能であるが、容器内部に撹拌翼を有し、且つ、底部に濾過用フィルターが配設された密閉型あるいは密閉可能な混合機能を有す容器内で行うことができる。本発明において、水洗ないし熱水洗は連続的に行っても良いし、バッチ式に行ってもいずれでも良い。 In the present invention, washing with water can be carried out using a washing tank having a stirrer or a centrifuge for solid-liquid separation. However, the container has a stirring blade inside and a filter for filtration is arranged at the bottom. It can be carried out in a container having a mixing function. It is also possible to use a water washing tank having a stirrer or a centrifuge for solid-liquid separation even in hot water washing exceeding 100 ° C., but it has a stirring blade inside the container and is filtered at the bottom. It can be carried out in a closed type container provided with a filter for use or in a container having a mixing function capable of being sealed. In the present invention, water washing or hot water washing may be carried out continuously or in a batch manner.
なお、濾別されたポリアリーレンスルフィド樹脂は、その後、そのまま乾燥してポリアリーレンスルフィド樹脂粉末を得ても良いし、更に洗浄処理した後、固液分離し、乾燥を行って粉末状ないし顆粒状のポリアリーレンスルフィド樹脂として調製することができる。 The filtered polyarylene sulfide resin may then be dried as it is to obtain a polyarylene sulfide resin powder. After further washing treatment, it is separated into solid and liquid, and dried to form a powder or granule. The polyarylene sulfide resin can be prepared.
上記の１）〜４）の重合方法を経由して調整されたアルカリ金属含有無機塩および前記カルボキシアルキルアミノ基含有化合物を含む水溶液は、前記カルボキシアルキルアミノ基含有化合物を多く含む傾向にあり、その量は水洗工程での洗浄の程度にもよるが、工業的な観点から一般的に２０００〔ｍｇ／Ｌ〕以上、より水洗浄を行ったものでも１５００〔ｍｇ／Ｌ〕以上の割合である。また、上記の５）の重合方法を経由して調整されたアルカリ金属含有無機塩および前記カルボキシアルキルアミノ基含有化合物を含む水溶液では、一般的に１５００〔ｍｇ／Ｌ〕以上、より水洗浄を行ったものでも１１００〔ｍｇ／Ｌ〕以上の割合である。 The aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound prepared via the polymerization methods 1) to 4) described above tends to contain a large amount of the carboxyalkylamino group-containing compound. Although the amount depends on the degree of washing in the water washing step, it is generally 2000 [mg / L] or more from an industrial viewpoint, and even after water washing, the amount is 1500 [mg / L] or more. Moreover, in the aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound prepared through the polymerization method of 5) above, the aqueous washing is generally performed at 1500 [mg / L] or more. Even the ratio is 1100 [mg / L] or more.
（工程１）
このようにして調製されたアルカリ金属含有無機塩および前記カルボキシアルキルアミノ基含有化合物を含む水溶液は、次に、酸を添加してｐＨ６．０以下に調整する。これにより前記一般式（１）は、主に、式中のＸが水素原子であるカルボキシアルキルアミノ基含有化合物（以下、カルボキシアルキルアミノ基含有化合物（ａ１）という）となる。続く工程２において分離効率がさらに向上するため、該ｐＨ範囲は２．５〜５．５の範囲、さらには３．５〜４．５の範囲とすることが好ましい。この際に用いる酸としては、塩酸、硫酸、炭酸、酢酸などが挙げられ、これらの中でも塩酸が好ましい。また、酸の添加は０〜６０℃の範囲、より好ましくは１０〜４０℃の範囲で、圧力０〜１．０Ｐａの範囲で行うことができる。
(Process 1)
The aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound thus prepared is then adjusted to pH 6.0 or less by adding an acid. Thereby, the general formula (1) mainly becomes a carboxyalkylamino group-containing compound (hereinafter referred to as carboxyalkylamino group-containing compound (a1)) in which X in the formula is a hydrogen atom. In order to further improve the separation efficiency in the subsequent step 2, the pH range is preferably in the range of 2.5 to 5.5, more preferably in the range of 3.5 to 4.5. Examples of the acid used in this case include hydrochloric acid, sulfuric acid, carbonic acid, and acetic acid. Among these, hydrochloric acid is preferable. The acid can be added in the range of 0 to 60 ° C., more preferably in the range of 10 to 40 ° C. and the pressure in the range of 0 to 1.0 Pa.
（工程２）
本発明は、前記水溶液に非水溶性溶媒を加えて、前記カルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相と、アルカリ金属含有無機塩を含む水相に分離する工程２を有する。
(Process 2)
This invention has the process 2 which adds a water-insoluble solvent to the said aqueous solution, and isolate | separates into the organic phase containing the said carboxyalkylamino group containing compound and a water-insoluble solvent, and the water phase containing an alkali metal containing inorganic salt.
工程２は、工程１で得られた、酸性にｐＨ調整されたアルカリ金属含有無機塩および前記カルボキシアルキルアミノ基含有化合物（ａ１）を含む水溶液に非水溶性溶媒を加えて、前記カルボキシアルキルアミノ基含有化合物（ａ１）と非水溶性溶媒を含む有機相と、アルカリ金属含有無機塩を含む水相とに分離する。 Step 2 is a step of adding a water-insoluble solvent to the aqueous solution containing the alkali metal-containing inorganic salt pH adjusted to acid and the carboxyalkylamino group-containing compound (a1) obtained in Step 1, and then adding the carboxyalkylamino group. It isolate | separates into the organic phase containing a containing compound (a1) and a water-insoluble solvent, and the aqueous phase containing an alkali metal containing inorganic salt.
非水溶性溶媒としては、水と混合した後、相分離する有機溶媒であれば特に限定されるものではないが、ｎ−ヘキサン、ｎ−ヘプタンなどの長鎖脂肪族炭化水素や、シクロヘキサン、メチルシクロヘキサンなどの脂環式炭化水素や、ベンゼン、トルエンおよびキシレン等の芳香族炭化水素や、クロロホルム、クロロベンゼンおよびジクロロベンゼン等のハロゲン化炭化水素などを挙げることができる。 The water-insoluble solvent is not particularly limited as long as it is an organic solvent that is mixed with water and then phase-separated, but long-chain aliphatic hydrocarbons such as n-hexane and n-heptane, cyclohexane, methyl Examples thereof include alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as chloroform, chlorobenzene and dichlorobenzene.
工程２における非水溶性溶媒の添加量は、前記水溶液及び非水溶性溶媒の混合後、相分離する量であれば特に限定されるものではない。具体的には、非水溶性溶媒中のカルボキシアルキルアミノ基含有化合物（ａ１）の種類や濃度、溶媒自身の種類等によって異なるものの、前記水溶液１００質量部に対して、例えば、１〜２００質量部の範囲、好ましくは５〜５０質量部の範囲である。 The amount of the water-insoluble solvent added in step 2 is not particularly limited as long as it is an amount that undergoes phase separation after mixing the aqueous solution and the water-insoluble solvent. Specifically, although depending on the type and concentration of the carboxyalkylamino group-containing compound (a1) in the water-insoluble solvent, the type of the solvent itself, etc., for example, 1 to 200 parts by mass with respect to 100 parts by mass of the aqueous solution The range is preferably 5 to 50 parts by mass.
工程２における前記水溶液及び非水溶性溶媒の混合は、例えば、水および非水溶性溶媒が凝固せず、かつ、水または非水溶性溶媒が蒸散しない温度範囲であり、好ましくは、０〜９０℃の温度範囲より好ましくは１０〜６０℃の温度範囲を挙げることができる。
工程２における前記水溶液及び非水溶性溶媒の混合は、攪拌装置、スタティックミキサー等の混合装置を用いて行ってよい。
The mixing of the aqueous solution and the water-insoluble solvent in the step 2 is, for example, a temperature range in which the water and the water-insoluble solvent do not coagulate and the water or the water-insoluble solvent does not evaporate, preferably 0 to 90 ° C. More preferably, a temperature range of 10 to 60 ° C. can be mentioned.
Mixing of the aqueous solution and the water-insoluble solvent in step 2 may be performed using a mixing device such as a stirring device or a static mixer.
（工程３、４）
本発明は、工程２で相分離させたアルカリ金属含有無機塩を含む水溶液と、前記カルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相とを、それぞれ別々に回収する工程として、「分離したカルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相を除去して、アルカリ金属含有無機塩を含む水溶液を回収する工程３」、または、「分離したアルカリ金属含有無機塩を含む水相を除去して、前記カルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相を回収する工程４」を有する。
(Steps 3 and 4)
The present invention includes the steps of separately recovering the aqueous solution containing the alkali metal-containing inorganic salt phase-separated in step 2 and the organic phase containing the carboxyalkylamino group-containing compound and the water-insoluble solvent, respectively. Removing the organic phase containing the carboxyalkylamino group-containing compound and the water-insoluble solvent and recovering the aqueous solution containing the alkali metal-containing inorganic salt, or “the aqueous phase containing the separated alkali metal-containing inorganic salt” To recover an organic phase containing the carboxyalkylamino group-containing compound and a water-insoluble solvent.
相分離させた前記カルボキシアルキルアミノ基含有化合物（ａ２）と非水溶性溶媒を含む有機相とアルカリ金属含有無機塩を含む水相とは、公知の手段によりそれぞれを効率よく分離、回収する。このような方法としては、静置した後、デカンテーション等の分離、回収手段を採用することも可能であるが、特に回収効率を上げるため、工業的には、接触を充分行うための混合（ミキサー）部と、これを分離してそれぞれの対向流を均一に保つ分離（セトラー）部とを備えた、いわゆるミキサー・セトラー式分離抽出装置などを用いて、工程２、工程３および工程４を同時または連続して行うことが好ましい。 The phase-separated carboxyalkylamino group-containing compound (a2), the organic phase containing a water-insoluble solvent, and the aqueous phase containing an alkali metal-containing inorganic salt are efficiently separated and recovered by known means. As such a method, it is possible to adopt separation and recovery means such as decantation after standing, but in order to increase the recovery efficiency, industrially, mixing for sufficient contact ( Step 2, Step 3 and Step 4 are carried out using a so-called mixer / settler type separation / extraction apparatus equipped with a (mixer) unit and a separation (settler) unit that separates this and keeps the respective counterflows uniform. It is preferable to carry out simultaneously or continuously.
また、工程３および工程４の操作は、加圧状態、常圧状態、減圧状態いずれの状態でも行うことができ、装置の簡便さから、常圧状態で行うことが好ましい。また、窒素、希ガスなどの非酸化性雰囲気下で行うこともできるが、装置の簡便さから大気中で行うことが好ましい。 The operations of Step 3 and Step 4 can be performed in any of a pressurized state, a normal pressure state, and a reduced pressure state, and are preferably performed in a normal pressure state from the simplicity of the apparatus. Moreover, although it can also carry out in non-oxidizing atmospheres, such as nitrogen and a noble gas, it is preferable to carry out in air | atmosphere from the simplicity of an apparatus.
なお、前記ＣＯＤ値を低減させるために、相分離された水相に非水溶性溶媒を加え、再び前記工程２および工程３を繰り返してもよい。同様に、前記カルボキシアルキルアミノ基含有化合物の回収率を向上させるために、相分離された水相と非水溶性溶媒を加え、再び前記工程２および工程４を繰り返してもよい。 In order to reduce the COD value, a water-insoluble solvent may be added to the phase-separated aqueous phase, and Steps 2 and 3 may be repeated again. Similarly, in order to improve the recovery rate of the carboxyalkylamino group-containing compound, the phase-separated aqueous phase and water-insoluble solvent may be added, and Step 2 and Step 4 may be repeated again.
工程３を経て得られたアルカリ金属含有無機塩を含む水溶液のＣＯＤ値は、工程１に供された前記アルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液のＣＯＤ値に対し、２０％以上、好ましくは４０％以上、さらに好ましくは７０％以上にまで削減することができる。さらに前記工程２および工程３を繰り返し行うことによってカルボキシアルキルアミノ基含有化合物を検出限界以下にまで削減することができる。 The COD value of the aqueous solution containing the alkali metal-containing inorganic salt obtained through the step 3 is 20% with respect to the COD value of the aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound subjected to the step 1. Thus, it can be reduced to 40% or more, more preferably 70% or more. Furthermore, the carboxyalkylamino group-containing compound can be reduced to below the detection limit by repeating Step 2 and Step 3.
また、工程４を経て得られたカルボキシアルキルアミノ基含有化合物はアルカリ金属含有無機塩を含む水溶液と分離されて、カルボキシアルキルアミノ基含有化合物および非水溶性溶媒を含む溶液として回収され、カルボキシアルキルアミノ基含有化合物の回収率（抽出率）は、工程１に供された前記アルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液中に含まれるカルボキシアルキルアミノ基含有化合物に対して、質量基準で４０％以上、好ましくは５０％以上、より好ましくは７５％以上、さらに好ましくは９０％以上の範囲である。さらに前記工程２および工程４を繰り返し行うことによって、９９％以上とすることも可能である。 The carboxyalkylamino group-containing compound obtained through Step 4 is separated from the aqueous solution containing the alkali metal-containing inorganic salt and recovered as a solution containing the carboxyalkylamino group-containing compound and the water-insoluble solvent. The recovery rate (extraction rate) of the group-containing compound is based on the mass of the carboxyalkylamino group-containing compound contained in the aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound subjected to Step 1. In the range of 40% or more, preferably 50% or more, more preferably 75% or more, and further preferably 90% or more. Furthermore, it is also possible to make it 99% or more by repeating the said process 2 and the process 4.
（工程５）
さらに、本発明は、工程４で回収されたカルボキシアルキルアミノ基含有化合物（ａ１）と非水溶性溶媒を含む溶液に、さらに、アルカリ性水溶液を加えて、前記非水溶性溶媒を分離する工程５、を行うこともできる。
工程４は、該組成物中のカルボキシアルキルアミノ基含有化合物（ａ１）にアルカリ性水溶液を加えることによって、主に、前記一般式（１）中のＸがアルカリ金属原子であるカルボキシアルキルアミノ基含有化合物（以下、カルボキシアルキルアミノ基含有化合物（ａ２）という）となり、水相側に分離する。
(Process 5)
Furthermore, the present invention further comprises a step 5 of separating the water-insoluble solvent by adding an alkaline aqueous solution to the solution containing the carboxyalkylamino group-containing compound (a1) recovered in step 4 and the water-insoluble solvent. Can also be done.
In step 4, by adding an alkaline aqueous solution to the carboxyalkylamino group-containing compound (a1) in the composition, mainly the carboxyalkylamino group-containing compound in which X in the general formula (1) is an alkali metal atom (Hereinafter referred to as a carboxyalkylamino group-containing compound (a2)), which is separated on the aqueous phase side.
工程５で用いるアルカリ性水溶液は、工程１のポリアリーレンスルフィド樹脂の重合工程で用いるものと同様のアルカリ金属水酸化物またはアルカリ金属硫化物を用いて調製することができる。アルカリ性水溶液中の該アルカリ金属水酸化物またはアルカリ金属硫化物の濃度は、カルボキシアルキルアミノ基含有化合物（ａ１）に対して同モル以上となるよう調整すれば特に問題ないが、具体的には０．２〜４９質量％、好ましくは１．０〜１０．０質量％の範囲である。 The alkaline aqueous solution used in Step 5 can be prepared using the same alkali metal hydroxide or alkali metal sulfide as used in the polymerization step of the polyarylene sulfide resin in Step 1. There is no particular problem if the concentration of the alkali metal hydroxide or alkali metal sulfide in the alkaline aqueous solution is adjusted to be equal to or higher than that of the carboxyalkylamino group-containing compound (a1). The range is from 2 to 49% by mass, preferably from 1.0 to 10.0% by mass.
（工程６、７）
さらに本発明は、工程５で相分離させたカルボキシアルキルアミノ基含有化合物（ａ２）を含む水溶液と非水溶性溶媒から、「非水溶性溶媒を除去して、カルボキシアルキルアミノ基含有化合物を含む水溶液を回収する工程６」、または「分離した該カルボキシアルキルアミノ基含有化合物を含む水溶液を除去して、非水溶性溶媒を回収する工程７」を有する。
(Steps 6 and 7)
Furthermore, the present invention relates to an aqueous solution containing a carboxyalkylamino group-containing compound by removing the water-insoluble solvent from the aqueous solution containing the carboxyalkylamino group-containing compound (a2) phase-separated in step 5 and the nonaqueous solvent. Step 6 ”or“ step 7 of removing the aqueous solution containing the separated carboxyalkylamino group-containing compound and recovering the water-insoluble solvent ”.
工程５において、カルボキシアルキルアミノ基含有化合物（ａ２）を含む水溶液と非水溶性溶媒とを分離した後、カルボキシアルキルアミノ基含有化合物（ａ２）を含む水溶液または非水溶性溶媒を回収する方法は、公知の手段により行うことができる。このような方法としては、静置した後、デカンテーション等の分離回収手段を採用することも可能であるが、特に回収効率を上げるため、工業的にはミキサー・セトラー式分離抽出装置などを用いて行うことが好ましい。
また、工程７で回収された非水溶性溶媒は、工程２において再利用することができる。
In Step 5, after separating the aqueous solution containing the carboxyalkylamino group-containing compound (a2) and the water-insoluble solvent, the method of recovering the aqueous solution or water-insoluble solvent containing the carboxyalkylamino group-containing compound (a2) is as follows: This can be done by known means. As such a method, it is possible to adopt a separation and recovery means such as decantation after standing, but in order to increase the recovery efficiency in particular, a mixer / settler type separation / extraction device is used industrially. It is preferable to carry out.
Further, the water-insoluble solvent recovered in step 7 can be reused in step 2.
本発明は、工程４で得られたカルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む溶液を、有機極性溶媒中に加え、ポリハロ芳香族化合物と、（ｉ）アルカリ金属硫化物とを、または、（ｉｉ）アルカリ金属水硫化物及びアルカリ金属水酸化物とを反応させるポリアリーレンスルフィド樹脂の製造方法の形態も包含する。また、本発明は、工程６で得られたカルボキシアルキルアミノ基含有化合物を含む水溶液を、有機極性溶媒中に加え、ポリハロ芳香族化合物と、（ｉ）アルカリ金属硫化物とを、または、（ｉｉ）アルカリ金属水硫化物及びアルカリ金属水酸化物とを反応させることを特徴とするポリアリーレンスルフィド樹脂の製造方法の形態をも包含する。ポリアリーレンスルフィド樹脂の原料中に前記カルボキシアルキルアミノ基含有化合物を加えることで、エポキシ接着性に優れたポリアリーレンスルフィド樹脂を製造することができる。 In the present invention, a solution containing the carboxyalkylamino group-containing compound obtained in Step 4 and a water-insoluble solvent is added to an organic polar solvent, and a polyhaloaromatic compound and (i) an alkali metal sulfide are added. And (ii) a form of a method for producing a polyarylene sulfide resin in which an alkali metal hydrosulfide and an alkali metal hydroxide are reacted. In the present invention, the aqueous solution containing the carboxyalkylamino group-containing compound obtained in Step 6 is added to an organic polar solvent to add a polyhaloaromatic compound and (i) an alkali metal sulfide, or (ii) ) A method for producing a polyarylene sulfide resin characterized by reacting an alkali metal hydrosulfide and an alkali metal hydroxide is also included. By adding the carboxyalkylamino group-containing compound to the raw material of the polyarylene sulfide resin, a polyarylene sulfide resin excellent in epoxy adhesiveness can be produced.
さらに、工程４または工程６で得られたカルボキシアルキルアミノ基含有化合物は、熱酸化架橋剤として作用し、ポリアリーレンスルフィド樹脂１質量部に対し０．００２〜０．０１質量部の範囲となる割合で添加し、熱酸化架橋処理を行うことで、溶融成形時の増粘を抑えて樹脂の溶融安定性を向上させるとともに、成形固化時の結晶化速度の速い架橋型ポリアリーレンスルフィド樹脂を製造することができる。 Further, the carboxyalkylamino group-containing compound obtained in Step 4 or Step 6 acts as a thermal oxidation cross-linking agent, and is a ratio in the range of 0.002 to 0.01 parts by mass with respect to 1 part by mass of the polyarylene sulfide resin. In addition to improving the melt stability of the resin by suppressing the thickening at the time of melt molding, a cross-linked polyarylene sulfide resin having a high crystallization speed at the time of molding and solidification is produced. be able to.
なお、従来、カルボキシアルキルアミノ基含有化合物は、産業廃棄物として処理されていたものの、上記工程４または工程６を経て、アルカリ金属含有無機塩と分離することにより、原料としてポリアリーレンスルフィド重合工程で、または、ポリアリーレンスルフィド樹脂の熱酸化架橋時に添加剤として再利用できる。このため、ポリアリーレンスルフィド樹脂の製造工程で排出されていた産業廃棄物の低減が可能である。 In the past, although the carboxyalkylamino group-containing compound has been treated as an industrial waste, it is separated from the alkali metal-containing inorganic salt through the step 4 or step 6 above, so that the raw material is a polyarylene sulfide polymerization step. Alternatively, it can be reused as an additive at the time of thermal oxidative crosslinking of the polyarylene sulfide resin. For this reason, the industrial waste discharged | emitted in the manufacturing process of polyarylene sulfide resin can be reduced.
上記のようにカルボキシアルキルアミノ基含有化合物を原料として重合されたポリアリーレンスルフィド樹脂や、添加剤として添加し熱酸化架橋処理されて得られた架橋型ポリアリーレンスルフィド樹脂は、本発明の効果を損ねない範囲で、離型剤、着色剤、耐熱安定剤、紫外線安定剤、発泡剤、防錆剤、難燃剤、滑剤、カップリング剤、充填材などの添加剤を含有せしめることができる。更に、同様に下記のごとき合成樹脂及びエラストマーを混合して使用することもできる。これら合成樹脂としては、ポリエステル、ポリアミド、ポリイミド、ポリエーテルイミド、ポリカーボネート、ポリフェニレンエーテル、ポリスルフォン、ポリエーテルスルフォン、ポリエーテルエーテルケトン、ポリエーテルケトン、ポリアリーレン、ポリエチレン、ポリプロピレン、ポリ四弗化エチレン、ポリ二弗化エチレン、ポリスチレン、ＡＢＳ樹脂、エポキシ樹脂、シリコーン樹脂、フェノール樹脂、ウレタン樹脂、液晶ポリマー等が挙げられ、エラストマーとしては、ポリオレフィン系ゴム、弗素ゴム、シリコーンゴム等が挙げられる。 As described above, the polyarylene sulfide resin polymerized using a carboxyalkylamino group-containing compound as a raw material, and the crosslinked polyarylene sulfide resin obtained by thermal oxidative crosslinking treatment as an additive, impair the effects of the present invention. As long as there are no additives, additives such as a mold release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust inhibitor, a flame retardant, a lubricant, a coupling agent, and a filler can be contained. Furthermore, the following synthetic resins and elastomers can also be mixed and used. These synthetic resins include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, polyarylene, polyethylene, polypropylene, polytetrafluoroethylene, Examples thereof include poly (difluoroethylene), polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, and liquid crystal polymer. Examples of the elastomer include polyolefin rubber, fluorine rubber, and silicone rubber.
このようにして得られたポリアリーレンスルフィド樹脂は、射出成形、押出成形、圧縮成形、ブロー成形のごとき各種溶融加工法により、耐熱性、成形加工性、寸法安定性等に優れた成形物にすることができ、例えば、コネクタ・プリント基板・封止成形品などの電気・電子部品、ランプリフレクター・各種電装部品などの自動車部品、各種建築物や航空機・自動車などの内装用材料、あるいはＯＡ機器部品・カメラ部品・時計部品などの精密部品等の射出成形・圧縮成形品、あるいは繊維・フィルム・シート・パイプなどの押出成形・引抜成形品等として幅広く利用可能である。 The polyarylene sulfide resin thus obtained is made into a molded product excellent in heat resistance, molding processability, dimensional stability, etc. by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding. For example, electrical and electronic parts such as connectors, printed boards, and sealing molded products, automotive parts such as lamp reflectors and various electrical components, interior materials such as various buildings and aircraft and automobiles, and OA equipment parts -It can be widely used as injection molding / compression molding products such as precision parts such as camera parts and watch parts, or extrusion molding / pulling molding products such as fibers, films, sheets, and pipes.
以下に実施例を挙げて本発明を具体的に説明する。これら例は例示的なものであって限定的なものではない。 The present invention will be specifically described below with reference to examples. These examples are illustrative and not limiting.
〔参考例〕 ポリアリーレンスルフォド樹脂製造
圧力計、温度計、コンデンサーを連結した撹拌翼および底弁付き１５０リットルオートクレーブに、４５％水硫化ソーダ（４７．５５質量％ＮａＳＨ）１４．１４８部、４８％苛性ソーダ（４８．７重量％ＮａＯＨ）９．３１７部と、Ｎ−メチル−２−ピロリドン３８．０部を仕込んだ。窒素気流下攪拌しながら２０９℃まで昇温して、水１２．１５０部を留出させた（残存する水分量はＮａＳＨ１モル当り１．１３モル）。その後、オートクレーブを密閉して１８０℃まで冷却し、パラジクロロベンゼン１７．１２９部及びＮ−メチル−２−ピロリドン１６．０部を仕込んだ。液温１５０℃で窒素ガスを用いてゲージ圧で０．１ＭＰａに加圧して昇温を開始した。液温２６０℃で３時間攪拌しつつ反応を進め、オートクレーブ上部を散水することにより冷却した。次に降温させると共にオートクレーブ上部の冷却を止めた。オートクレーブ上部を冷却中、液温が下がらないように一定に保持した。反応中の最高圧力は、０．８６ＭＰａであった。反応後、冷却し、温度１７０℃の時点でシュウ酸・２水和物０．２８４部をＮ−メチル−２−ピロリドン０．６６３部に含む溶液を加圧注入した。３０分間撹拌後、冷却し、１００℃で底弁を開き、反応スラリーを平板ろ過機に移送し１２０℃で加圧ろ過したのち、Ｎ−メチル−２−ピロリドン１６．０部を加え、加圧ろ過した。ろ過後、撹拌翼付き真空乾燥機を用いて、減圧下１５０℃で２時間撹拌してＮ−メチル−２−ピロリドンを留去した。次に７０℃温水９０部を加え撹拌したのち、濾過し、さらに７０℃温水２５部を加え濾過し、濾液を集めて「水溶液（Ａ）」を調製した。水溶液（Ａ）のｐＨは９．３、ＣＰ−ＭＡＢＡ濃度は１７２２〔ｐｐｍ〕、ＣＯＤは２１０３〔ｍｇ／Ｌ〕、ポリアリーレンスルフォド樹脂濃度は０〔質量％〕であった。
[Reference Example] Production of polyarylene sulfide resin In a 150 liter autoclave with a pressure gauge, a thermometer, a condenser connected with a stirring blade and a bottom valve, 14.148 parts of 45% sodium hydrosulfide (47.55 mass% NaSH), Charged 9.317 parts of 48% caustic soda (48.7 wt% NaOH) and 38.0 parts of N-methyl-2-pyrrolidone. While stirring under a nitrogen stream, the temperature was raised to 209 ° C. to distill 12.150 parts of water (the amount of water remaining was 1.13 mol per 1 mol of NaSH). Thereafter, the autoclave was sealed and cooled to 180 ° C., and 17.129 parts of paradichlorobenzene and 16.0 parts of N-methyl-2-pyrrolidone were charged. The temperature was raised by pressurizing to 0.1 MPa with a gauge pressure using nitrogen gas at a liquid temperature of 150 ° C. The reaction was allowed to proceed with stirring at a liquid temperature of 260 ° C. for 3 hours, and the upper part of the autoclave was sprinkled to cool it. Next, the temperature was lowered and cooling of the upper part of the autoclave was stopped. The upper part of the autoclave was kept constant during cooling to prevent the liquid temperature from dropping. The maximum pressure during the reaction was 0.86 MPa. After the reaction, the mixture was cooled, and at a temperature of 170 ° C., a solution containing 0.284 parts of oxalic acid dihydrate in 0.663 parts of N-methyl-2-pyrrolidone was injected under pressure. After stirring for 30 minutes, it is cooled, the bottom valve is opened at 100 ° C., the reaction slurry is transferred to a flat plate filter and filtered under pressure at 120 ° C., 16.0 parts of N-methyl-2-pyrrolidone is added, and the pressure is increased. Filtered. After filtration, the mixture was stirred for 2 hours at 150 ° C. under reduced pressure using a vacuum dryer with a stirring blade to distill off N-methyl-2-pyrrolidone. Next, 90 parts of 70 ° C. warm water was added and stirred, followed by filtration. Further, 25 parts of 70 ° C. warm water was added and filtered, and the filtrate was collected to prepare “aqueous solution (A)”. The pH of the aqueous solution (A) was 9.3, the CP-MABA concentration was 1722 [ppm], the COD was 2103 [mg / L], and the polyarylene sulfide resin concentration was 0 [mass%].
〔実施例１〕
水溶液（Ａ）５００ｍｌに撹拌しながら１ｍｏｌ／Ｌ塩酸を加えｐＨを４．０に調整した（水溶液（Ｂ）と記す）。その後、加温装置付き分液ロートにｐＨ調整した水溶液（Ｂ）４００ｍｌを入れ、さらに非水溶性溶媒としてｐ−キシレン４０ｍｌを入れ、５分間振とう後、静置した。非水溶性溶媒相（有機相）と水相とに相分離した後、分離した非水溶性溶媒相（ａ）と水相（ａ）とを、デカンテーションし、それぞれ別々に回収した。その後、非水溶性溶媒相（ａ）のＣＰ−ＭＡＢＡ濃度を測定し、水溶液（Ａ）から非水溶性溶媒相（ａ）へ抽出したＣＰ−ＭＡＢＡの抽出率（以下、「ＣＰ−ＭＡＢＡ抽出率ａ」という）を算出し、さらに、水相（ａ）のＣＯＤ値を測定した。その結果を表１に示した。
[Example 1]
1 mol / L hydrochloric acid was added to 500 ml of the aqueous solution (A) with stirring to adjust the pH to 4.0 (denoted as aqueous solution (B)). Thereafter, 400 ml of the aqueous solution (B) whose pH was adjusted was placed in a separatory funnel equipped with a heating device, and 40 ml of p-xylene was further added as a water-insoluble solvent, and the mixture was allowed to stand after shaking for 5 minutes. After phase separation into a water-insoluble solvent phase (organic phase) and an aqueous phase, the separated water-insoluble solvent phase (a) and water phase (a) were decanted and recovered separately. Thereafter, the CP-MABA concentration in the water-insoluble solvent phase (a) was measured, and the extraction rate of CP-MABA extracted from the aqueous solution (A) into the water-insoluble solvent phase (a) (hereinafter referred to as “CP-MABA extraction rate”). a ”) and the COD value of the aqueous phase (a) was measured. The results are shown in Table 1.
次に、非水溶性溶媒相（ａ）２５ｍｌと３％苛性ソーダ２．５ｍｌを分液ロートに入れ、５分間振とう後、静置した。非水溶性溶媒相（ｂ）と水相（ｂ）に相分離したら、デカンテーションを行い、それぞれ別々に回収した。水相（ｂ）のＣＰ−ＭＡＢＡの濃度を測定し、非水溶性溶媒相（ａ）から水相（ｂ）へ抽出したＣＰ−ＭＡＢＡの抽出率（以下、「ＣＰ−ＭＡＢＡ抽出率ｂ」という）と、水溶液（Ａ）から水相（ｂ）へ抽出したＣＰ−ＭＡＢＡの抽出率（以下、「ＣＰ−ＭＡＢＡ抽出率ｃ」という）を算出した。これらの結果を表１に示した。 Next, 25 ml of water-insoluble solvent phase (a) and 2.5 ml of 3% caustic soda were placed in a separatory funnel, shaken for 5 minutes, and allowed to stand. After phase separation into a water-insoluble solvent phase (b) and an aqueous phase (b), decantation was performed and each was recovered separately. The concentration of CP-MABA in the aqueous phase (b) was measured, and the extraction rate of CP-MABA extracted from the water-insoluble solvent phase (a) to the aqueous phase (b) (hereinafter referred to as “CP-MABA extraction rate b”) ) And the extraction rate of CP-MABA extracted from the aqueous solution (A) into the aqueous phase (b) (hereinafter referred to as “CP-MABA extraction rate c”). These results are shown in Table 1.
〔実施例２〕
水溶液（Ａ）５００ｍｌに撹拌しながら１ｍｏｌ／Ｌ塩酸を加えｐＨを３．５に調整したこと以外は実施例１と同様に行い、ＣＰ−ＭＡＢＡ抽出率、水相のＣＯＤを測定した。その結果を表１に示した。
[Example 2]
The same procedure as in Example 1 was conducted except that 1 mol / L hydrochloric acid was added to 500 ml of the aqueous solution (A) while stirring to adjust the pH to 3.5, and the CP-MABA extraction rate and the COD of the aqueous phase were measured. The results are shown in Table 1.
〔実施例３〕
水溶液（Ａ）５００ｍｌに撹拌しながら１ｍｏｌ／Ｌ塩酸を加えｐＨを４．５に調整したこと以外は実施例１と同様に行い、ＣＰ−ＭＡＢＡ抽出率、水相のＣＯＤを測定した。その結果を表１に示した。
Example 3
The same procedure was followed as in Example 1 except that 1 mol / L hydrochloric acid was added to 500 ml of the aqueous solution (A) and the pH was adjusted to 4.5, and the CP-MABA extraction rate and the COD of the aqueous phase were measured. The results are shown in Table 1.
〔実施例４〕
非水溶性溶媒としてｐ−キシレンの代わりにｏ−キシレンを用いたこと以外は実施例１と同様に行い、ＣＰ−ＭＡＢＡ抽出率、水相のＣＯＤを測定した。その結果を表１に示した。
〔実施例５〕
３％苛性ソーダ２．５ｍｌの代わりに２４％苛性ソーダ２．５ｍｌを用いたこと以外は実施例１と同様に行い、ＣＰ−ＭＡＢＡ抽出率、水相のＣＯＤを測定した。その結果を表１に示した。
〔実施例６〕
非水溶性溶媒としてｐ−キシレンの代わりにｎ−オクタンを用いたこと以外は実施例１と同様に行い、ＣＰ−ＭＡＢＡ抽出率、水相のＣＯＤを測定した。その結果を表１に示した。
〔実施例７〕
非水溶性溶媒としてｐ−キシレンの代わりにトルエンを用いたこと以外は実施例１と同様に行い、ＣＰ−ＭＡＢＡ抽出率、水相のＣＯＤを測定した。その結果を表１に示した。
Example 4
Except that o-xylene was used in place of p-xylene as the water-insoluble solvent, the same procedure as in Example 1 was performed, and the CP-MABA extraction rate and the COD of the aqueous phase were measured. The results are shown in Table 1.
Example 5
The same procedure as in Example 1 was conducted except that 2.5 ml of 24% caustic soda was used instead of 2.5 ml of 3% caustic soda, and the CP-MABA extraction rate and the COD of the aqueous phase were measured. The results are shown in Table 1.
Example 6
Except that n-octane was used in place of p-xylene as the water-insoluble solvent, the same procedure as in Example 1 was carried out, and the CP-MABA extraction rate and the COD of the aqueous phase were measured. The results are shown in Table 1.
Example 7
Except having used toluene instead of p-xylene as a water-insoluble solvent, it carried out similarly to Example 1, and measured CP-MABA extraction rate and COD of the aqueous phase. The results are shown in Table 1.
〔比較例１〕
水溶液（Ａ）のｐＨ調整を行わなかったこと以外は実施例１と同様に行い、ＣＰ−ＭＡＢＡ抽出率、水相のＣＯＤを測定した。その結果を表２に示した。
[Comparative Example 1]
Except not adjusting pH of aqueous solution (A), it carried out like Example 1 and measured CP-MABA extraction rate and COD of the water phase. The results are shown in Table 2.
〔比較例２〕
水溶液（Ａ）５００ｍｌに撹拌しながら１ｍｏｌ／Ｌ塩酸を加えｐＨを６．５に調整したこと以外は実施例１と同様に行い、ＣＰ−ＭＡＢＡ抽出率、水相のＣＯＤを測定した。その結果を表２に示した。
[Comparative Example 2]
The same procedure as in Example 1 was conducted except that 1 mol / L hydrochloric acid was added to 500 ml of the aqueous solution (A) while stirring to adjust the pH to 6.5, and the CP-MABA extraction rate and the COD of the aqueous phase were measured. The results are shown in Table 2.
水溶液（Ａ）から非水溶性溶媒相（有機相）へ抽出したＣＰ−ＭＡＢＡの抽出率および水相のＣＯＤは以下のとおり行った。 The extraction rate of CP-MABA extracted from the aqueous solution (A) into the water-insoluble solvent phase (organic phase) and the COD of the aqueous phase were as follows.
［ＣＰ−ＭＡＢＡ抽出率］
ＣＰ−ＭＡＢＡ抽出率はＨＰＬＣで液中のＣＰ−ＭＡＢＡ濃度を測定し、算出した。
サンプル調製：非水溶性溶媒中にＣＰ-ＭＡＢＡが含まれる場合は、非水溶性溶媒をエバポレータで留去したたのち、残渣にＨＰＬＣの移動相を加え溶解して測定サンプルを調製した。水相中にＣＰ−ＭＡＢＡが含まれる場合は、そのまま移動相を加えて調製した。
測定サンプルのＨＰＬＣ測定を行い、下記の方法で作製した標準サンプルと同じ保持時間のピーク面積と検量線とから液中の濃度を求め、下記式よりＣＰ−ＭＡＢＡ抽出率ａ、ＣＰ−ＭＡＢＡ抽出率ｂ、ＣＰ−ＭＡＢＡ抽出率ｃを算出した。
[CP-MABA extraction rate]
The CP-MABA extraction rate was calculated by measuring the CP-MABA concentration in the liquid by HPLC.
Sample preparation: When CP-MABA was contained in the water-insoluble solvent, the water-insoluble solvent was distilled off with an evaporator, and then the HPLC mobile phase was added to the residue and dissolved to prepare a measurement sample. When CP-MABA was contained in the aqueous phase, it was prepared by adding the mobile phase as it was.
Perform HPLC measurement of the measurement sample, obtain the concentration in the liquid from the peak area and calibration curve of the same retention time as the standard sample prepared by the following method, CP-MABA extraction rate a, CP-MABA extraction rate from the following formula b, CP-MABA extraction rate c was calculated.
（標準物質：ＣＰ−ＭＡＢＡの合成）
４８％ＮａＯＨ水溶液８３．４ｇ（１．０モル）とＮ−メチル−２−ピロリドン２９７．４ｇ（３．０モル）を、撹拌機付き耐圧容器に仕込み、２３０℃で３時間撹拌した。この撹拌が終了した後、温度２３０℃のままバルブを開き、放圧し、Ｎ−メチル−２−ピロリドンの蒸気圧程度である２３０℃において０．１ＭＰａまで圧力を低下させ、水を留去した。その後、再び密閉し２００℃程度まで温度を低下させた。
(Synthesis of standard substance: CP-MABA)
83.4 g (1.0 mol) of 48% NaOH aqueous solution and 297.4 g (3.0 mol) of N-methyl-2-pyrrolidone were charged into a pressure vessel equipped with a stirrer and stirred at 230 ° C. for 3 hours. After the stirring was completed, the valve was opened at a temperature of 230 ° C., the pressure was released, and the pressure was reduced to 0.1 MPa at 230 ° C., which is about the vapor pressure of N-methyl-2-pyrrolidone, and water was distilled off. Then, it sealed again and the temperature was reduced to about 200 degreeC.
ｐ−ジクロロベンゼン１４７．０ｇ（１．０モル）を６０℃以上の温度条件下で加熱溶解して反応混合物中に投入し、２５０℃まで昇温後４時間撹拌した。この撹拌が終了した後、室温まで冷却した。ｐ−ジクロロベンゼンの反応率は３１モル％であった。冷却後、内容物を取り出し、水を加えて撹拌後、未反応のｐ−ジクロロベンゼンが不溶物となって残ったものをろ過によって取り除いた。 147.0 g (1.0 mol) of p-dichlorobenzene was heated and dissolved under a temperature condition of 60 ° C. or higher, charged into the reaction mixture, heated to 250 ° C., and stirred for 4 hours. After completion of this stirring, the mixture was cooled to room temperature. The reaction rate of p-dichlorobenzene was 31 mol%. After cooling, the contents were taken out, water was added, and the mixture was stirred. Unreacted p-dichlorobenzene remained as an insoluble matter and was removed by filtration.
次いで、ろ液である水溶液に塩酸を加えて該水溶液のｐＨを４に調整した。このとき水溶液中に褐色オイル状のＣＰ−ＭＡＢＡ（水素型）が生じた。そこにクロロホルムを加えて褐色オイル状物質を抽出した。このときの水相には、Ｎ−メチル−２−ピロリドン及びその開環物である４−メチルアミノ酪酸（以下「ＭＡＢＡ」と略記する。）が含まれるため水相は廃棄した。クロロホルム相は水洗を２回繰り返した。 Next, hydrochloric acid was added to the aqueous solution as the filtrate to adjust the pH of the aqueous solution to 4. At this time, brown oily CP-MABA (hydrogen type) was formed in the aqueous solution. Chloroform was added thereto to extract a brown oily substance. Since the aqueous phase at this time contained N-methyl-2-pyrrolidone and its ring-opened product, 4-methylaminobutyric acid (hereinafter abbreviated as “MABA”), the aqueous phase was discarded. The chloroform phase was washed twice with water.
クロロホルム相に水を加えてスラリー化した状態で４８％ＮａＯＨ水溶液を加え、該スラリーのｐＨを１３に調整した。このときＣＰ−ＭＡＢＡはナトリウム塩となって水相に移り、クロロホルム相には副生成物であるｐ−クロロ−Ｎ−メチルアニリン及びＮ−メチルアニリンが溶解しているためクロロホルム相は廃棄した。水相はクロロホルム洗浄を２回繰り返した。 In a state where water was added to the chloroform phase to form a slurry, a 48% NaOH aqueous solution was added to adjust the pH of the slurry to 13. At this time, CP-MABA was converted to a sodium salt and moved to the aqueous phase, and the chloroform phase was discarded because p-chloro-N-methylaniline and N-methylaniline as by-products were dissolved in the chloroform phase. The aqueous phase was washed twice with chloroform.
水溶液に希塩酸を加えて該水溶液のｐＨを１以下に調整した。このときＣＰ−ＭＡＢＡは塩酸塩となって水溶液中にとどまるので、水溶液にクロロホルムを加えて、副生成物であるｐ−クロロフェノールを抽出した。ｐ−クロロフェノールが溶解したクロロホルム相は廃棄した。 Dilute hydrochloric acid was added to the aqueous solution to adjust the pH of the aqueous solution to 1 or less. At this time, CP-MABA became hydrochloride and remained in the aqueous solution, so chloroform was added to the aqueous solution to extract p-chlorophenol as a by-product. The chloroform phase in which p-chlorophenol was dissolved was discarded.
残った水溶液に４８％ＮａＯＨ水溶液を加え、該水溶液のｐＨを４に調整した。これにより、ＣＰ−ＭＡＢＡの塩酸塩が中和され、褐色オイル状のＣＰ−ＭＡＢＡ（水素型）が水溶液から析出した。ＣＰ−ＭＡＢＡ（水素型）をクロロホルムで抽出し、クロロホルムを減圧除去することによってＣＰ−ＭＡＢＡ（水素型）を得た。 A 48% aqueous NaOH solution was added to the remaining aqueous solution to adjust the pH of the aqueous solution to 4. As a result, the hydrochloride of CP-MABA was neutralized, and brown oily CP-MABA (hydrogen type) was precipitated from the aqueous solution. CP-MABA (hydrogen type) was extracted with chloroform, and chloroform was removed under reduced pressure to obtain CP-MABA (hydrogen type).
［ＣＯＤの測定］
ＪＩＳ Ｋ０１２０に準拠しＫＭｎＯ４によるＣＯＤを測定した。
[Measurement of COD]
COD by KMnO 4 was measured according to JIS K0120.
［ポリアリーレンスルフィド樹脂濃度の測定］
水溶液（Ａ）中におけるポリアリーレンスルフィド樹脂濃度は以下のとおり測定した。
該水溶液（Ａ）１００質量部にクロロホルム２０質量部を加え、分析ロートで混合抽出し、分液してクロロホルム層と水層に分離した。移動相にクロロホルムを用いた液体クロマトグラフ装置でクロロホルム層を測定し、得られたピークから前記カルボキシアルキルアミノ基含有化合物のピークを除いたエリア面積（Ａ）を求めた。但し、事前に所定濃度の前記カルボキシアルキルアミノ基含有化合物のクロロホルム溶液を測定し、保持時間を測定しておくことで、前記カルボキシアルキルアミノ基含有化合物のピークを判別した。また、別途ポリアリーレンスルフィド樹脂濃度０．３２ｗｔ％のクロロホルム溶液のエリア面積（Ｂ）を求め、下記式より、該水溶液（Ａ）中のポリアリーレンスルフィド樹脂濃度を算出した。
[Measurement of polyarylene sulfide resin concentration]
The polyarylene sulfide resin concentration in the aqueous solution (A) was measured as follows.
To 100 parts by mass of the aqueous solution (A), 20 parts by mass of chloroform was added, mixed and extracted with an analytical funnel, and separated to separate a chloroform layer and an aqueous layer. The chloroform layer was measured with a liquid chromatograph apparatus using chloroform as the mobile phase, and the area area (A) obtained by removing the peak of the carboxyalkylamino group-containing compound from the obtained peak was determined. However, the peak of the carboxyalkylamino group-containing compound was determined by measuring in advance a chloroform solution of the carboxyalkylamino group-containing compound at a predetermined concentration and measuring the retention time. Separately, the area area (B) of a chloroform solution having a polyarylene sulfide resin concentration of 0.32 wt% was obtained, and the polyarylene sulfide resin concentration in the aqueous solution (A) was calculated from the following formula.
Claims (8)
（１）前記アルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液をｐＨ６．０以下に調整する工程１、
（２）前記水溶液に非水溶性溶媒を加えて、前記カルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相と、アルカリ金属含有無機塩を含む水相に分離する工程２、
（３）分離したカルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相を除去して、アルカリ金属含有無機塩を含む水溶液を回収する工程３、
を有することを特徴とするアルカリ金属含有無機塩を含む水溶液の製造方法。 Alkali metal-containing inorganic salt and the following general formula (1)
(1) Step 1 of adjusting an aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound to pH 6.0 or less,
(2) Step 2, in which a water-insoluble solvent is added to the aqueous solution to separate the organic phase containing the carboxyalkylamino group-containing compound and the water-insoluble solvent into an aqueous phase containing an alkali metal-containing inorganic salt,
(3) Step 3 of removing the organic phase containing the separated carboxyalkylamino group-containing compound and the water-insoluble solvent to recover an aqueous solution containing an alkali metal-containing inorganic salt;
A method for producing an aqueous solution containing an alkali metal-containing inorganic salt.
有機極性溶媒中で、ポリハロ芳香族化合物と、（ｉ）アルカリ金属硫化物とを、または、（ｉｉ）アルカリ金属水硫化物及びアルカリ金属水酸化物とを反応させてポリアリーレンスルフィド樹脂とアルカリ金属含有無機塩と前記カルボキシアルキルアミノ基含有化合物と前記有機極性溶媒を含む粗反応混合物を得た後、粗反応混合物から前記有機極性溶媒を固液分離させてポリアリーレンスルフィド樹脂とアルカリ金属含有無機塩と前記カルボキシアルキルアミノ基含有化合物を含む反応混合物を得、その後、該反応混合物を水と接触させてポリアリーレンスルフィド樹脂を濾別する精製工程を経て得られたものである請求項１記載の製造方法。 Alkali metal-containing inorganic salt and the following general formula (1)
In an organic polar solvent, a polyhaloaromatic compound and (i) an alkali metal sulfide or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide are reacted to form a polyarylene sulfide resin and an alkali metal. After obtaining a crude reaction mixture containing a containing inorganic salt, the carboxyalkylamino group-containing compound and the organic polar solvent, the organic polar solvent is solid-liquid separated from the crude reaction mixture to obtain a polyarylene sulfide resin and an alkali metal-containing inorganic salt. And a carboxyalkylamino group-containing compound is obtained, followed by a purification step in which the reaction mixture is brought into contact with water and the polyarylene sulfide resin is filtered off. Method.
（１）前記アルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液をｐＨ６．０以下に調整する工程１、
（２）前記水溶液に非水溶性溶媒を加えて、前記カルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相と、アルカリ金属含有無機塩を含む水相に分離する工程２、
（４）分離したアルカリ金属含有無機塩を含む水相を除去して、前記カルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相を回収する工程４、を有すること、
前記アルカリ金属含有無機塩および下記一般式（１）
有機極性溶媒中で、ポリハロ芳香族化合物と、（ｉ）アルカリ金属硫化物とを、または、（ｉｉ）アルカリ金属水硫化物及びアルカリ金属水酸化物とを反応させてポリアリーレンスルフィド樹脂とアルカリ金属含有無機塩と前記カルボキシアルキルアミノ基含有化合物と前記有機極性溶媒を含む粗反応混合物を得た後、粗反応混合物から前記有機極性溶媒を固液分離させてポリアリーレンスルフィド樹脂とアルカリ金属含有無機塩と前記カルボキシアルキルアミノ基含有化合物を含む反応混合物を得、その後、該反応混合物を水と接触させてポリアリーレンスルフィド樹脂を濾別する精製工程を経て得られたものであること、を特徴とするカルボキシアルキルアミノ基含有化合物及び非水溶性溶媒を含む溶液の製造方法。 Alkali metal-containing inorganic salt and the following general formula (1)
(1) Step 1 of adjusting an aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound to pH 6.0 or less,
(2) Step 2, in which a water-insoluble solvent is added to the aqueous solution to separate the organic phase containing the carboxyalkylamino group-containing compound and the water-insoluble solvent into an aqueous phase containing an alkali metal-containing inorganic salt,
(4) removing the aqueous phase containing the separated alkali metal-containing inorganic salt and recovering the organic phase containing the carboxyalkylamino group-containing compound and a water-insoluble solvent;
The alkali metal-containing inorganic salt and the following general formula (1)
In an organic polar solvent, a polyhaloaromatic compound and (i) an alkali metal sulfide or (ii) an alkali metal hydrosulfide and an alkali metal hydroxide are reacted to form a polyarylene sulfide resin and an alkali metal. After obtaining a crude reaction mixture containing a containing inorganic salt, the carboxyalkylamino group-containing compound and the organic polar solvent, the organic polar solvent is solid-liquid separated from the crude reaction mixture to obtain a polyarylene sulfide resin and an alkali metal-containing inorganic salt. And a reaction mixture containing the carboxyalkylamino group-containing compound, and then obtained through a purification step of contacting the reaction mixture with water and filtering off the polyarylene sulfide resin. A method for producing a solution comprising a carboxyalkylamino group-containing compound and a water-insoluble solvent.
（６）分離した非水溶性溶媒を除去して、該カルボキシアルキルアミノ基含有化合物を含む水溶液を回収する工程６、を有するカルボキシアルキルアミノ基含有化合物を含む水溶液の製造方法。 (5) An alkaline aqueous solution is further added to the solution containing the carboxyalkylamino group-containing compound and the water-insoluble solvent obtained by the production method according to claim 4, and the water-insoluble solvent and the following general formula (2) )
(6) A method for producing an aqueous solution containing a carboxyalkylamino group-containing compound, comprising removing the separated water-insoluble solvent and recovering an aqueous solution containing the carboxyalkylamino group-containing compound.
（１’）前記アルカリ金属含有無機塩およびカルボキシアルキルアミノ基含有化合物を含む水溶液をｐＨ６．０以下に調整する工程１’、
（２’）前記水溶液に非水溶性溶媒を加えて、前記カルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相と、アルカリ金属含有無機塩を含む水相に分離する工程２’、
（３’）分離したカルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む有機相を除去して、アルカリ金属含有無機塩を含む水溶液を回収する工程３’、
を有するアルカリ金属含有無機塩を含む水溶液の製造方法であって、
前記工程２’で使用する非水溶性溶媒は、
（５）請求項４記載の製造方法で得られたカルボキシアルキルアミノ基含有化合物と非水溶性溶媒を含む溶液に、さらに、アルカリ性水溶液を加えて、前記非水溶性溶媒と、下記一般式（２）
（７）分離した該カルボキシアルキルアミノ基含有化合物を含む水溶液を除去して、非水溶性溶媒を回収する工程７を経て得られた非水溶性溶媒を使用することを特徴とするアルカリ金属含有無機塩を含む水溶液の製造方法。 Alkali metal-containing inorganic salt and the following general formula (1)
(1 ′) Step 1 ′ of adjusting an aqueous solution containing the alkali metal-containing inorganic salt and the carboxyalkylamino group-containing compound to pH 6.0 or less,
(2 ′) Step 2 ′ of adding a water-insoluble solvent to the aqueous solution to separate the organic phase containing the carboxyalkylamino group-containing compound and the water-insoluble solvent and the water phase containing the alkali metal-containing inorganic salt,
(3 ′) Step 3 ′ for recovering an aqueous solution containing an alkali metal-containing inorganic salt by removing the organic phase containing the separated carboxyalkylamino group-containing compound and the water-insoluble solvent.
A method for producing an aqueous solution containing an alkali metal-containing inorganic salt having
The water-insoluble solvent used in the step 2 ′ is
(5) An alkaline aqueous solution is further added to the solution containing the carboxyalkylamino group-containing compound and the water-insoluble solvent obtained by the production method according to claim 4, and the water-insoluble solvent and the following general formula (2) )
(7) An alkali metal-containing inorganic, characterized by using the water-insoluble solvent obtained through the step 7 of removing the separated aqueous solution containing the carboxyalkylamino group-containing compound and recovering the water-insoluble solvent. A method for producing an aqueous solution containing a salt.
（７）分離した該カルボキシアルキルアミノ基含有化合物を含む水溶液を除去して、非水溶性溶媒を回収する工程７を有し、工程７で得られた非水溶性溶媒を工程２で使用することを特徴とする請求項４記載の製造方法。 (5) An alkaline aqueous solution is further added to the solution containing the carboxyalkylamino group-containing compound and the water-insoluble solvent obtained by the production method according to claim 4, and the water-insoluble solvent and the following general formula (2) )
(7) removing the aqueous solution containing the separated carboxyalkylamino group-containing compound and recovering the water-insoluble solvent, and using the water-insoluble solvent obtained in step 7 in step 2 The manufacturing method of Claim 4 characterized by these.
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