JP5930307B2 - Sodium parastyrene sulfonate having excellent fluidity and solubility, and method for producing the same - Google Patents
Sodium parastyrene sulfonate having excellent fluidity and solubility, and method for producing the same Download PDFInfo
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims description 137
- 229910052708 sodium Inorganic materials 0.000 title claims description 137
- 239000011734 sodium Substances 0.000 title claims description 137
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims description 91
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 84
- 238000006243 chemical reaction Methods 0.000 claims description 64
- 239000002245 particle Substances 0.000 claims description 56
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 52
- VPXYRQWRQLIJQC-UHFFFAOYSA-N 2-(2-bromoethyl)benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1CCBr VPXYRQWRQLIJQC-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 62
- 239000012535 impurity Substances 0.000 description 32
- 239000000523 sample Substances 0.000 description 24
- 238000000746 purification Methods 0.000 description 23
- 239000007864 aqueous solution Substances 0.000 description 21
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000004090 dissolution Methods 0.000 description 13
- 239000002002 slurry Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 235000010288 sodium nitrite Nutrition 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003125 aqueous solvent Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- -1 silver halide Chemical class 0.000 description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- CBSIEJGODQIOKA-UHFFFAOYSA-N 2-bromoethyl benzenesulfonate Chemical compound BrCCOS(=O)(=O)C1=CC=CC=C1 CBSIEJGODQIOKA-UHFFFAOYSA-N 0.000 description 3
- BJFRCYIYQLHUDS-UHFFFAOYSA-N 2-hydroxyethyl benzenesulfonate Chemical compound OCCOS(=O)(=O)C1=CC=CC=C1 BJFRCYIYQLHUDS-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- WGQVSSXGZIYYMT-UHFFFAOYSA-M sodium 1-bromo-2-phenylethenesulfonate Chemical compound BrC(=CC1=CC=CC=C1)S(=O)(=O)[O-].[Na+] WGQVSSXGZIYYMT-UHFFFAOYSA-M 0.000 description 3
- XESUCHPMWXMNRV-UHFFFAOYSA-M sodium;2-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=C XESUCHPMWXMNRV-UHFFFAOYSA-M 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 1
- BRIXOPDYGQCZFO-UHFFFAOYSA-N 4-ethylphenylsulfonic acid Chemical compound CCC1=CC=C(S(O)(=O)=O)C=C1 BRIXOPDYGQCZFO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004153 Potassium bromate Substances 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 239000013566 allergen Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229940094037 potassium bromate Drugs 0.000 description 1
- 235000019396 potassium bromate Nutrition 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000006886 vinylation reaction Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Description
本発明は、流動性と溶解性に優れるパラスチレンスルホン酸ナトリウム、並びにその製造方法に関する。即ち、適度な粒径で低水分のパラスチレンスルホン酸ナトリウムであり、流動性および溶解性に優れたパラスチレンスルホン酸ナトリウム、並びにその製造方法に関するものである。 The present invention relates to sodium parastyrene sulfonate having excellent fluidity and solubility, and a method for producing the same. That is, the present invention relates to sodium parastyrene sulfonate having an appropriate particle size and low moisture content, excellent fluidity and solubility, and a method for producing the same.
パラスチレンスルホン酸ナトリウムに代表されるパラスチレンスルホン酸（塩）は、分子内にラジカル重合性ビニル基、π電子を有する疎水性のベンゼン環、及び強電解質であるスルホン酸（塩）基を有する機能性モノマーであり、産業上の様々な分野で重用されている。例えば、エマルジョン重合において、エマルジョンの安定性、及び（エマルジョン）ポリマーの耐水性やカチオン染料染色性を向上させるため、反応性乳化剤として使用されている。また、パラスチレンスルホン酸ナトリウムの重合体や共重合体は、顔料、酸化防止剤、各種ポリマー（粘着付与樹脂、クロロプレンゴム、ポリアクリル酸エステル、ポリエステル、スチレン−ブタジエン共重合体、ポリ塩化ビニル、ポリアクリロニトリル、ポリシリコーン、導電性ポリマーなど）、ナノカーボン材料、熱間鍛造離型剤や研磨材用のシリカ粒子、電池電極材料（カーボン、リン酸鉄リチウム、リン酸マンガンリチウムなど）、写真用ハロゲン化銀などの各種水性分散体を製造するための分散剤として使用されている。さらに、パラスチレンスルホン酸（塩）の重合体は、アイロン剤などの衣料仕上げ用の合成糊、ヘアケア用品、帯電防止剤、レジスト酸発生剤、水処理剤、アレルゲン補足剤、イオン交換樹脂、メッキ液添加剤、半導体やハードディスク製造用の洗浄剤、シェールオイル採掘用流体の添加剤として利用されている。 Parastyrene sulfonic acid (salt) represented by sodium parastyrene sulfonate has a radical polymerizable vinyl group, a hydrophobic benzene ring having π electrons, and a sulfonic acid (salt) group that is a strong electrolyte in the molecule. It is a functional monomer and is used extensively in various industrial fields. For example, in emulsion polymerization, it is used as a reactive emulsifier in order to improve the stability of the emulsion and the water resistance and cationic dye dyeability of the (emulsion) polymer. Polymers and copolymers of sodium parastyrene sulfonate include pigments, antioxidants, various polymers (tackifier resins, chloroprene rubber, polyacrylate esters, polyesters, styrene-butadiene copolymers, polyvinyl chloride, Polyacrylonitrile, polysilicone, conductive polymer, etc.), nanocarbon materials, hot forging release agents and silica particles for abrasives, battery electrode materials (carbon, lithium iron phosphate, lithium manganese phosphate, etc.), for photography It is used as a dispersant for producing various aqueous dispersions such as silver halide. In addition, polymers of parastyrene sulfonic acid (salts) are used for synthetic adhesives for clothing finishing such as ironing agents, hair care products, antistatic agents, resist acid generators, water treatment agents, allergen supplements, ion exchange resins, plating. It is used as a liquid additive, a cleaning agent for manufacturing semiconductors and hard disks, and an additive for fluid for mining shale oil.
従来から、パラスチレンスルホン酸ナトリウムは、β−ブロモエチルベンゼンスルホン酸と水酸化ナトリウムとの反応によって製造できることが知られている（例えば、特許文献１及び特許文献２参照）。
特許文献１には、窒素雰囲気下、反応器に重合禁止剤として微量の亜硝酸ナトリウムを含む水酸化ナトリウム水溶液を仕込み、ここへβ−ブロモエチルベンゼンスルホン酸を滴下しながら９０℃で反応させ、パラスチレンスルホン酸ナトリウムの結晶を得た後、冷却、遠心濾過、及び強制流動してパラスチレンスルホン酸ナトリウムの半水和物を製造する方法が記載されている。パラスチレンスルホン酸ナトリウムの粒径については、通常、数μｍ〜数ｍｍであると記載されているのみであり、実測値の記載はない。現在、市場に流通しているものと同程度の粒径、即ち、２０μｍ程度のメジアン径を有するものと推測される。また、粒径、水分、溶解性、及び流動性の関係については一切言及されていない。
Conventionally, it is known that sodium parastyrene sulfonate can be produced by a reaction between β-bromoethylbenzene sulfonic acid and sodium hydroxide (see, for example, Patent Document 1 and Patent Document 2).
In Patent Document 1, a sodium hydroxide aqueous solution containing a small amount of sodium nitrite as a polymerization inhibitor is charged in a reactor under a nitrogen atmosphere, and reacted at 90 ° C. while adding β-bromoethylbenzenesulfonic acid dropwise thereto. A method is described in which sodium styrenesulfonate crystals are obtained, followed by cooling, centrifugal filtration, and forced flow to produce sodium parastyrenesulfonate hemihydrate. About the particle size of sodium parastyrene sulfonate, it is only described that it is normally several micrometers-several mm, and there is no description of an actual measurement value. It is presumed that the particle diameter is about the same as that currently on the market, that is, the median diameter is about 20 μm. Further, there is no mention of the relationship among particle size, moisture, solubility, and fluidity.
特許文献２には、反応器に重合禁止剤として微量の亜硝酸ナトリウムを含む水酸化ナトリウム水溶液、及びβ−ブロモエチルベンゼンスルホン酸をそれぞれ同時にフィードしながら９０℃で反応させ、生成したパラスチレンスルホン酸ナトリウム結晶スラリーを連続的に抜出し、遠心濾過、及び強制流動してパラスチレンスルホン酸ナトリウムの半水和物を製造する方法が記載されている。パラスチレンスルホン酸ナトリウムの形状は鱗片状であり、粒径の実測値は１６０μｍ〜７６０μｍと記載されている。また、特許文献１と同様、粒径、水分、溶解性、及び流動性の関係については一切言及されていない。
しかしながら、従来のメジアン径が２５μｍ未満のパラスチレンスルホン酸ナトリウムは、プラントで大量使用する際、投入ホッパーの詰まりが発生するなど、取扱い性に課題があった。即ち、粉体としての流動性が不足していた。一方、パラスチレンスルホン酸ナトリウムのメジアン径が１５０μｍを超えると、流動性は良好だが、プラント使用の際、水への溶解速度が低下し、ストレーナーが閉塞するなどの問題があった。即ち、パラスチレンスルホン酸ナトリウムの溶解性を損なうことなく、流動性が向上したパラスチレンスルホン酸ナトリウムが求められていた。
In Patent Document 2, a sodium hydroxide aqueous solution containing a trace amount of sodium nitrite as a polymerization inhibitor and β-bromoethylbenzenesulfonic acid are reacted at 90 ° C. while simultaneously feeding each into a reactor, and the resulting parastyrenesulfonic acid is produced. A method is described in which sodium crystal slurry is continuously withdrawn, centrifugally filtered, and forced-flowed to produce sodium parastyrenesulfonate hemihydrate. The shape of sodium parastyrene sulfonate is scaly, and the measured value of the particle size is described as 160 μm to 760 μm. Further, as in Patent Document 1, there is no mention of the relationship among particle size, moisture, solubility, and fluidity.
However, conventional sodium parastyrene sulfonate having a median diameter of less than 25 μm has a problem in handling, such as clogging of a charging hopper when used in a large amount in a plant. That is, the fluidity as a powder was insufficient. On the other hand, when the median diameter of sodium parastyrene sulfonate exceeds 150 μm, the fluidity is good, but when using the plant, there is a problem that the rate of dissolution in water decreases and the strainer is blocked. That is, there has been a demand for sodium parastyrene sulfonate having improved fluidity without impairing the solubility of sodium parastyrene sulfonate.
また近年、上記した半導体、ハードディスク製造用の洗浄剤、導電性ポリマー用の分散剤、写真用ハロゲン化銀乳剤など、特に電子材料用途において、パラスチレンスルホン酸（塩）及びパラスチレンスルホン酸（塩）重合体に含まれる臭化ナトリウム、未反応β−ブロモエチルベンゼンスルホン酸及びパラスチレンスルホン酸ナトリウムの核臭素化物など、余剰の金属や臭素分など、不純物の低減が求められている。臭化ナトリウムなどの不純物は、水性溶媒による洗浄や再結晶によって低減できることが知られている（例えば、特許文献３）。特許文献３には純度が記載されているが、ハロゲン化アルカリ金属の含量は不明瞭であり、その他の不純物に関する記載は一切ない。また、精製前のパラスチレンスルホン酸ナトリウムの粒径が、精製効率、即ち精製後の純度に及ぼす影響については一切言及されていない。 In recent years, parastyrene sulfonic acid (salt) and parastyrene sulfonic acid (salt) have been used particularly in electronic materials such as semiconductors, hard disk manufacturing detergents, conductive polymer dispersants, and photographic silver halide emulsions. ) Reduction of impurities such as excess metal and bromine such as sodium bromide, unreacted β-bromoethylbenzenesulfonic acid and nuclear bromide of sodium parastyrene sulfonate contained in the polymer is required. It is known that impurities such as sodium bromide can be reduced by washing with an aqueous solvent or recrystallization (for example, Patent Document 3). Patent Document 3 describes purity, but the content of alkali metal halide is unclear and there is no description of other impurities. Further, there is no mention of the influence of the particle size of sodium parastyrenesulfonate before purification on the purification efficiency, that is, the purity after purification.
本発明は、上記の課題に鑑みてなされたものであり、その目的は、メジアン径が２５．００〜１５０．００μｍ、１０．００μｍ未満の小粒が１０．００％以下である、流動性、溶解性に優れたパラスチレンスルホン酸ナトリウムの粉体（粒子）を提供することにある。 The present invention has been made in view of the above-mentioned problems, and its purpose is that the median diameter is 25.00 to 150.00 μm, and small particles less than 10.00 μm are 10.00% or less, fluidity, dissolution The object is to provide powder (particles) of sodium parastyrenesulfonate having excellent properties.
本発明者らは、上記課題を解決すべく鋭意研究を行った結果、特定の条件で製造されたメジアン径が２５．００〜１５０．００μｍ、１０．００μｍ未満の小粒が１０．００％以下のパラスチレンスルホン酸ナトリウムが、流動性と溶解性のバランスに優れ、さらに、水性溶媒を用いて当該パラスチレンスルホン酸ナトリウムを精製し、高純度化する際に、極めて効率よく精製できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the inventors of the present invention have a median diameter of 25.00-150.00 μm and small particles of less than 10.00 μm produced under specific conditions of 10.00% or less. It has been found that sodium parastyrene sulfonate has an excellent balance between fluidity and solubility, and can be purified very efficiently when purifying and purifying the sodium parastyrene sulfonate using an aqueous solvent. The invention has been completed.
本発明は、レーザー回折・散乱式粒度分析計で測定したメジアン径が２５．００〜１５０．００μｍ、１０．００μｍ未満の小粒が１０．００％以下の粒子であって、水分が１０．００ｗｔ％以下、及び安息角が５５度以下であることを特徴とするパラスチレンスルホン酸ナトリウムに関する。
本発明のパラスチレンスルホン酸ナトリウムとしては、溶解性、流動性、及び精製効率の観点から、さらに、レーザー回折・散乱式粒度分析計で測定したメジアン径が４０．００〜９０．００μｍ、１０．００μｍ未満の小粒が３．００％以下の粒子であって、水分が８．００ｗｔ％以下、及び安息角が５０度以下であることが好ましい。
また、本発明のパラスチレンスルホン酸ナトリウムは、純度の観点から、臭化ナトリウム含量が０．２０ｗｔ％以下であることが好ましい。
次に、本発明は、反応釜へ水酸化ナトリウムとβ−ブロモエチルベンゼンスルホン酸を一定速度で同時フィードし、パラスチレンスルホン酸ナトリウムを製造する方法において、反応釜内の水酸化ナトリウム濃度（フィードした全水酸化ナトリウムの重量／反応釜内の全反応液重量×１００）を１０．００〜２０．００ｗｔ％に保ち、かつ、β−ブロモエチルベンゼンスルホン酸濃度〔（フィードした全β−ブロモエチルベンゼンスルホン酸の重量／反応釜内の全反応液重量）×１００〕を、１〜７時間かけて０．００ｗｔ％から３０．００〜５０．００ｗｔ％に増加させるように制御しながら、６０〜１１０℃で１〜７時間反応晶析させ、固液分離して得られた湿潤ケーキを強制流動することを特徴とする、上記パラスチレンスルホン酸ナトリウムの製造方法に関する。
The present invention is a particle having a median diameter of 25.00 to 150.00 μm measured by a laser diffraction / scattering particle size analyzer of less than 10.00 μm and less than 10.00%, and having a water content of 10.00 wt% The following relates to sodium parastyrene sulfonate characterized by an angle of repose of 55 degrees or less.
The sodium parastyrene sulfonate of the present invention has a median diameter of 40.00 to 90.00 μm as measured by a laser diffraction / scattering particle size analyzer from the viewpoint of solubility, fluidity, and purification efficiency. It is preferable that the small particles of less than 00 μm are particles of 3.00% or less, the water content is 8.00 wt% or less, and the angle of repose is 50 degrees or less.
In addition, the sodium parastyrene sulfonate of the present invention preferably has a sodium bromide content of 0.20 wt% or less from the viewpoint of purity.
Next, according to the present invention, sodium hydroxide and β-bromoethylbenzenesulfonic acid are simultaneously fed to a reaction kettle at a constant rate to produce sodium parastyrenesulfonate sodium salt. The total sodium hydroxide weight / total reaction solution weight in the reaction vessel × 100) was kept at 10.00 to 20.00 wt%, and β-bromoethylbenzenesulfonic acid concentration [(total β-bromoethylbenzenesulfonic acid fed Weight / total reaction liquid weight in reaction kettle) × 100] at 60 to 110 ° C. while controlling to increase from 0.00 wt% to 30.00 to 50.00 wt% over 1 to 7 hours. 1 to 7 hours of reaction crystallization, and the wet cake obtained by solid-liquid separation is forcibly fluidized. The present invention relates to a method for producing um.
本発明により、粒径を制御することによって、良好な溶解性を維持したまま、従来の課題だった流動性が向上したパラスチレンスルホン酸ナトリウムが提供される。さらに、本発明の粒径が制御されたパラスチレンスルホン酸ナトリウムは、再結晶精製などによる高純度化に際して、精製効率が優れる。 According to the present invention, by controlling the particle size, sodium parastyrenesulfonate having improved fluidity, which has been a conventional problem, is provided while maintaining good solubility. Furthermore, the sodium parastyrene sulfonate having a controlled particle size according to the present invention is excellent in purification efficiency when it is highly purified by recrystallization purification or the like.
本発明のパラスチレンスルホン酸ナトリウムの最大の特徴は粒径と水分にある。一般に、パラスチレンスルホン酸ナトリウム（下記の「化１」中のＭがナトリウムの場合）は下記の方法で製造されており、その形状と粒径は、主としてビニル化工程（反応晶析）の条件によって左右されると考えられる。 The greatest feature of the sodium parastyrene sulfonate of the present invention is the particle size and moisture. In general, sodium parastyrene sulfonate (when M in the following “chemical formula 1” is sodium) is produced by the following method, and its shape and particle size are mainly the conditions of the vinylation step (reaction crystallization). It is thought that it depends on.
化学原料として、パラスチレンスルホン酸ナトリウムを工場で大量使用する際、メジアン径が２５．００μｍ未満と小さい場合、水への溶解性は良好だが、流動性が不足し、原料投入ホッパーの目詰まりが起り易くなり、一方、メジアン径が１５０．００μｍを超えると、流動性は良好となるが、水への溶解速度が著しく低下し、ストレーナーの目詰まりが起り易くなることを見出した。 When using a large amount of sodium parastyrene sulfonate as a chemical raw material in a factory, if the median diameter is as small as less than 25.00 μm, the solubility in water is good, but the fluidity is insufficient and the raw material charging hopper is clogged. On the other hand, it has been found that when the median diameter exceeds 150.00 μm, the fluidity is improved, but the dissolution rate in water is remarkably lowered, and the strainer is easily clogged.
また、本発明者らは、パラスチレンスルホン酸ナトリウムのメジアン径が２５．００μｍ未満、又は１０．００μｍ未満の小粒が１０．００％を超える場合、水性溶媒を用いて当該パラスチレンスルホン酸ナトリウムを洗浄、又は再結晶精製する際、濾過性（液切れ性）が低下し、効率良く精製できないことを見出した。 In addition, when the median diameter of sodium parastyrene sulfonate is less than 25.00 μm, or when the small particles of less than 10.00 μm exceed 10.00%, the present inventors have used sodium parastyrene sulfonate with an aqueous solvent. When washing or recrystallizing and purifying, it was found that the filterability (liquid cutting property) was lowered and the purification could not be performed efficiently.
かくて、本発明は、レーザー回折・散乱式粒度分析計で測定したメジアン径が２５．００〜１５０．００μｍ、１０．００μｍ未満の小粒が１０．００％以下の粒子であって、水分が１０．００ｗｔ％以下、及び安息角が５５度以下であることを特徴とするパラスチレンスルホン酸ナトリウムである。流動性と溶解性のバランスの面から、メジアン径が４０．００〜９０．００μｍ、１０．００μｍ未満の小粒が３．００％以下、水分が８．００ｗｔ％以下、及び安息角が５０度以下であるのがさらに好ましい。 Thus, the present invention is a particle whose median diameter measured by a laser diffraction / scattering particle size analyzer is 25.00 to 150.00 μm, small particles less than 10.00 μm are 10.00% or less, and has a water content of 10 It is sodium parastyrene sulfonate characterized by having 0.000 wt% or less and an angle of repose of 55 degrees or less. From the viewpoint of the balance between fluidity and solubility, the median diameter is 40.00 to 90.00 μm, small particles less than 10.00 μm are 3.00% or less, moisture is 8.00 wt% or less, and the angle of repose is 50 degrees or less. More preferably.
上記のように、パラスチレンスルホン酸ナトリウムのメジアン径が２５．００μｍ未満、又は１０．００μｍ未満の小粒が１０．００％を超える場合、水性溶媒を用いて当該パラスチレンスルホン酸ナトリウムを洗浄、又は再結晶精製する際、濾過性（液切れ性）が低下し、効率良く精製できない。一方、１５０．０μｍを超えると、（水分が少なくなる結果）流動性は良好であり、水性溶媒を用いて洗浄、又は再結晶精製する際の濾過性も良好であるが、溶解性が劣る。
ここで、上記メジアン径を２５．００〜１５０．００μｍ、好ましくは４０．００〜９０．００μｍの範囲に調整するには、上記反応晶析条件、即ち原料であるβ−ブロモエチルベンゼンスルホン酸と水酸化ナトリウムのフィード条件と反応温度を調整することにより、晶析速度を制御すればよい。
また、１０．００μｍ未満の小粒を１０．００％以下、好ましくは３．００％以下にするには、上記した方法によって、メジアン径が２５．００μｍ以上となるように制御すれば良く、必然的に１０．００μｍ未満の小粒は減少する。
本発明のパラスチレンスルホン酸ナトリウムは、上記特定範囲のメジアン径を有する粒子であるが、「楕円盤状二次粒子」であることが好ましい。ここで、「楕円盤状二次粒子」とは、図２の電子顕微鏡写真に示したような楕円盤状の粒子であり、多数のパラスチレンスルホン酸ナトリウム半水和物の結晶（一次粒子）が物理的な力で凝集したものである。本発明のパラスチレンスルホン酸ナトリウムにおいて、得られる粒子が「楕円盤状二次粒子」となることは詳らかではないが、反応晶析中の晶析速度や撹拌条件、及び後記する強制流動などの物理的な力が上記一次粒子に作用して凝集することによるものと考えられる。
As described above, when the median diameter of sodium parastyrene sulfonate is less than 25.00 μm, or the small particles less than 10.00 μm exceed 10.00%, the aqueous sodium solvent is used to wash the sodium parastyrene sulfonate, or When recrystallizing and purifying, the filterability (liquid cutting property) is lowered and the purification cannot be performed efficiently. On the other hand, if it exceeds 150.0 μm, the fluidity is good (as a result of the reduction in water content), and the filterability during washing or recrystallization purification using an aqueous solvent is good, but the solubility is poor.
Here, in order to adjust the median diameter to a range of 25.00 to 150.00 μm, preferably 40.00 to 90.00 μm, the reaction crystallization conditions, that is, β-bromoethylbenzenesulfonic acid as a raw material and water are used. The crystallization rate may be controlled by adjusting the feed conditions and reaction temperature of sodium oxide.
Further, in order to make small particles of less than 10.00 μm 10.00% or less, preferably 3.00% or less, it is necessary to control the median diameter to be 25.00 μm or more by the above-described method. In addition, the number of grains less than 10.00 μm decreases.
The sodium parastyrene sulfonate of the present invention is a particle having a median diameter in the above specific range, but is preferably “ellipsoidal secondary particles”. Here, the “ellipsoidal secondary particles” are elliptical particles as shown in the electron micrograph of FIG. 2 and a large number of sodium parastyrenesulfonate hemihydrate crystals (primary particles). Are aggregated by physical force. In the sodium parastyrene sulfonate of the present invention, it is not clear that the resulting particles are "ellipsoidal secondary particles", such as the crystallization speed and stirring conditions during reaction crystallization, forced flow described later This is considered to be due to the physical force acting on the primary particles and aggregating.
パラスチレンスルホン酸ナトリウムは、保存安定性が優れる理由で半水和物が好ましく、１００％純度のパラスチレンスルホン酸ナトリウム半水和物中の水分（結晶水）は、理論上４．１８ｗｔ％である。従って、４．１８ｗｔ％を超える水分は付着水である。パラスチレンスルホン酸ナトリウムのメジアン径が小さいほど、トータル表面積の増大によって付着水が増加する結果、流動性が低下し、一方、メジアン径が大きいほど、トータル表面積の低減によって付着水が減少する結果、流動性が良好になったと考えられる。付着水の増加は、流動性の低下のみならず、パラスチレンスルホン酸ナトリウムの純度（製品有姿重量当たりのパラスチレンスルホン酸ナトリウム含量）低下を意味するので、実用上好ましくない。
この点から、本発明のパラスチレンスルホン酸ナトリウムは、水分が１０．００重量％以下、好ましくは８．０重量％以下、さらに好ましくは４．５〜７．０重量％の半水和物である。水分が１０重量％を超えると、パラスチレンスルホン酸ナトリウムの粒径に関わらず流動性が低下し、また、有姿製品の純度低下を意味するので好ましくない。このように、本発明のパラスチレンスルホン酸ナトリウムを水分が１０％以下の半水和物として得るには、上記反応晶析条件、即ち原料であるβ−ブロモエチルベンゼンスルホン酸と水酸化ナトリウムのフィード条件と反応温度を調整し、晶析速度を制御することによって、メジアン径が２５．００μｍ以上となるようにすればよい。
Sodium parastyrene sulfonate is preferably hemihydrate because of its excellent storage stability, and the water (crystal water) in 100% pure sodium parastyrene sulfonate hemihydrate is theoretically 4.18 wt%. is there. Therefore, moisture exceeding 4.18 wt% is adhering water. As the median diameter of sodium parastyrene sulfonate is smaller, the amount of adhering water increases due to the increase in total surface area, resulting in a decrease in fluidity, while as the median diameter is larger, the amount of adhering water decreases due to the reduction in total surface area. The fluidity is considered to have improved. An increase in the amount of attached water is not practically preferable because it means not only a decrease in fluidity but also a decrease in the purity of sodium parastyrenesulfonate (the content of sodium parastyrenesulfonate per product weight).
From this point, the sodium parastyrene sulfonate of the present invention is a hemihydrate having a water content of 10.00% by weight or less, preferably 8.0% by weight or less, more preferably 4.5 to 7.0% by weight. is there. When the water content exceeds 10% by weight, the fluidity is lowered regardless of the particle size of sodium parastyrene sulfonate, and the purity of the solid product is lowered, which is not preferable. As described above, in order to obtain the sodium parastyrenesulfonate of the present invention as a hemihydrate having a water content of 10% or less, the above-mentioned reaction crystallization conditions, that is, feed of β-bromoethylbenzenesulfonic acid and sodium hydroxide as raw materials are used. By adjusting the conditions and reaction temperature and controlling the crystallization rate, the median diameter may be 25.00 μm or more.
また、本発明のパラスチレンスルホン酸ナトリウムは、後記で定義される安息角が５５度以下、好ましくは５０度以下である。５５度を超えると、流動性が劣るものとなる。安息角が５５度以下であると、流動性に優れ、工場で大量使用する際に、ホッパーでの目詰まりなどのトラブルが解消され好ましい。安息角を小さくするためには、粉体の流動性を高くすればよい。流動性とパラスチレンスルホン酸ナトリウム粉体の構造、組成との関係は必ずしも明らかではないが、粉体中の水分の影響が大きいと考えられる。即ち、粉体の粒径が小さいほど、全表面積の増大によって水分が増大する結果、流動性が低下するものと考えられ、水分は上記した粒径制御により調整することができる。 The sodium parastyrene sulfonate of the present invention has an angle of repose defined by the following description of 55 degrees or less, preferably 50 degrees or less. When it exceeds 55 degrees, fluidity will be inferior. When the angle of repose is 55 degrees or less, it is excellent in fluidity, and troubles such as clogging in a hopper are solved when used in a large amount in a factory. In order to reduce the angle of repose, the fluidity of the powder may be increased. Although the relationship between fluidity and the structure and composition of sodium parastyrene sulfonate powder is not necessarily clear, it is considered that the influence of moisture in the powder is large. That is, it is considered that as the particle size of the powder is smaller, the water content increases due to the increase in the total surface area, resulting in a decrease in fluidity, and the water content can be adjusted by controlling the particle size described above.
なお、本発明のパラスチレンスルホン酸ナトリウムの水への溶解性（後記「溶解速度の測定」を参照）は、好ましくは２００秒以下、さらに好ましくは１６０秒以下である。溶解性が高すぎることによる弊害はないが、２００秒を超えると、化学原料としてパラスチレンスルホン酸ナトリウムを工場で大量使用する際に、生産性が低下したり、ストレーナーの目詰まりなどのトラブルが起り易くなり好ましくない。この溶解性は、上記した粒径制御により調整することができる。 The solubility of sodium parastyrenesulfonate of the present invention in water (see “Measurement of Dissolution Rate” below) is preferably 200 seconds or less, more preferably 160 seconds or less. Although there is no harmful effect due to too high solubility, if it exceeds 200 seconds, when using a large amount of sodium parastyrene sulfonate as a chemical raw material in a factory, problems such as decreased productivity and clogging of the strainer occur. It tends to occur and is not preferable. This solubility can be adjusted by controlling the particle size described above.
次に、本発明のパラスチレンスルホン酸ナトリウムの製造法について説明する。パラスチレンスルホン酸ナトリウムの製造法は、特に限定するものではないが、例えば、反応釜内の水酸化ナトリウム濃度〔（フィードした全水酸化ナトリウムの重量／反応釜内の全反応液重量）×１００〕を１０．００〜２０．００ｗｔ％に保ち、かつ、β−ブロモエチルベンゼンスルホン酸濃度〔（フィードした全β−ブロモエチルベンゼンスルホン酸の重量／反応釜内の全反応液重量）×１００〕を、１〜７時間かけて０．００ｗｔ％から３０．００〜５０．００ｗｔ％まで増加させるようにフィードしながら、６０〜１１０℃で１〜７時間反応晶析させることが重要である。生成したパラスチレンスルホン酸ナトリウムのスラリーを、好ましくは１０〜４０℃まで冷却後、例えば遠心濾過器で固液分離して、パラスチレンスルホン酸ナトリウムの湿潤ケーキを得る。次いで、当該湿潤ケーキを一軸のスクリュー式ブレンダーを用いて、例えば２０〜４０℃で５〜３０分強制流動させることにより、本発明のパラスチレンスルホン酸ナトリウムの半水和物を製造することができる。 Next, the manufacturing method of the sodium parastyrene sulfonate of this invention is demonstrated. The method for producing sodium parastyrene sulfonate is not particularly limited. For example, sodium hydroxide concentration in the reaction kettle [(weight of fed total sodium hydroxide / total weight of reaction solution in the reaction kettle) × 100 ] And the β-bromoethylbenzenesulfonic acid concentration [(weight of fed total β-bromoethylbenzenesulfonic acid / total reaction solution weight in reaction kettle) × 100] It is important to carry out reaction crystallization at 60 to 110 ° C. for 1 to 7 hours while feeding to increase from 0.00 wt% to 30.00 to 50.00 wt% over 1 to 7 hours. The produced slurry of sodium parastyrene sulfonate is preferably cooled to 10 to 40 ° C., and then solid-liquid separated using, for example, a centrifugal filter to obtain a wet cake of sodium parastyrene sulfonate. Next, the sodium cake of sodium parastyrenesulfonate of the present invention can be produced by forcibly flowing the wet cake using a uniaxial screw type blender, for example, at 20 to 40 ° C. for 5 to 30 minutes. .
全反応液中の濃度が２０ｗｔ％を超える水酸化ナトリウム水溶液に、例えば、濃度７０ｗｔ％のβ−ブロモエチルベンゼンスルホン酸をフィードすると（例えば、特許第３６０１２２２号公報）、得られるパラスチレンスルホン酸ナトリウム結晶が小さくなりすぎるため、水分が多く、流動性が劣るパラスチレンスルホン酸ナトリウム半水和物が得られる。また、水性溶媒を用いて洗浄又は再結晶精製する際、固液分離性が低下して精製効率が悪化する。一方、全反応液中の水酸化ナトリウム濃度が２０ｗｔ％以下であっても、β−ブロモエチルベンゼンスルホン酸のフィード速度が速すぎる場合（特許第３８９０６４２号公報）、例えば、フィード開始１時間以内に全反応液中のβ−ブロモエチルベンゼンスルホン酸濃度が４０ｗｔ％を超えると、得られるパラスチレンスルホン酸ナトリウム結晶が大きくなりすぎるため、流動性は良好だが溶解性が悪いパラスチレンスルホン酸ナトリウム半水和物が得られる。 When, for example, β-bromoethylbenzenesulfonic acid having a concentration of 70 wt% is fed to a sodium hydroxide aqueous solution having a concentration of more than 20 wt% in the total reaction solution (for example, Japanese Patent No. 36001222), the resulting sodium parastyrene sulfonate crystals Becomes too small, so that a sodium parastyrenesulfonate hemihydrate having a high water content and poor fluidity can be obtained. In addition, when washing or recrystallization purification is performed using an aqueous solvent, the solid-liquid separability is lowered and the purification efficiency is deteriorated. On the other hand, if the feed rate of β-bromoethylbenzenesulfonic acid is too high (Patent No. 3890642) even if the sodium hydroxide concentration in the total reaction solution is 20 wt% or less, When the concentration of β-bromoethylbenzenesulfonic acid in the reaction solution exceeds 40 wt%, the resulting sodium parastyrenesulfonate crystal becomes too large, so that the sodium parastyrenesulfonate hemihydrate has good fluidity but poor solubility. Is obtained.
本発明で製造されるパラスチレンスルホン酸ナトリウムは、反応晶析条件の改良によって、粒径を制御したものであり、優れた溶解性を維持したまま、流動性が向上しているため、取扱い性が良く、さらに、高純度なパラスチレンスルホン酸ナトリウムを効率よく製造できるため、上記した産業分野において利用価値が高い。 The sodium parastyrene sulfonate produced in the present invention is controlled in particle size by improving the reaction crystallization conditions, and has improved fluidity while maintaining excellent solubility. In addition, since high-purity sodium parastyrenesulfonate can be efficiently produced, the utility value is high in the industrial fields described above.
なお、本発明は、パラスチレンスルホン酸ナトリウム（以下「ＰＳＳナトリウム」ともいう）中の不純物でとしては、臭化ナトリウムが２．５０ｗｔ％未満であり、（ａ）オルソスチレンスルホン酸ナトリウム、（ｂ）β−ブロモエチルベンゼンスルホン酸ナトリウム、（ｃ）メタスチレンスルホン酸ナトリウム、（ｄ）ブロモスチレンスルホン酸ナトリウム、（ｅ）β−ヒドロキシエチルベンゼンスルホン酸ナトリウムの高速液体クロマトグラフィー（ＨＰＬＣ）で求めたピーク面積比が、各々（ａ）≦０．４０％、（ｂ）≦４．００％、（ｃ）≦８．００％、（ｄ）≦０．１０％、及び（ｅ）≦０．８０％（ただし、パラスチレンスルホン酸ナトリウムと（ａ）〜（ｅ）ピーク面積の総和は１００）であることが好ましい。 In the present invention, as an impurity in sodium parastyrene sulfonate (hereinafter also referred to as “PSS sodium”), sodium bromide is less than 2.50 wt%, (a) sodium orthostyrene sulfonate, (b Peak areas determined by high-performance liquid chromatography (HPLC) of β) sodium β-bromoethylbenzenesulfonate, (c) sodium metastyrenesulfonate, (d) sodium bromostyrenesulfonate, and (e) sodium β-hydroxyethylbenzenesulfonate. The ratios are (a) ≦ 0.40%, (b) ≦ 4.00%, (c) ≦ 8.00%, (d) ≦ 0.10%, and (e) ≦ 0.80%, respectively. However, it is preferable that the sum of the sodium parastyrenesulfonate and the peak areas (a) to (e) is 100).
通常、市販のパラスチレンスルホン酸ナトリウムは、主要不純物である臭化ナトリウム（上記式においてＭ＝ナトリウムの場合）の他に、未反応臭素化中間体、有機異性体が不純物として含まれる。本発明の製造方法や下記に示す精製方法により、これらの不純物を低減することができる。 Usually, commercially available sodium parastyrene sulfonate contains unreacted brominated intermediates and organic isomers as impurities in addition to sodium bromide (in the case of M = sodium in the above formula) which is a main impurity. These impurities can be reduced by the production method of the present invention and the purification method described below.
パラスチレンスルホン酸ナトリウムに含まれる不純物としては、主要不純物である臭化ナトリウムの他に、（ａ）オルソスチレンスルホン酸ナトリウム、（ｂ）β−ブロモエチルベンゼンスルホン酸ナトリウム、（ｃ）メタスチレンスルホン酸ナトリウム、（ｄ）ブロモスチレンスルホン酸ナトリウム、（ｅ）β−ヒドロキシエチルベンゼンスルホン酸ナトリウムが含まれる。 As impurities contained in sodium parastyrene sulfonate, in addition to sodium bromide as a main impurity, (a) sodium orthostyrene sulfonate, (b) sodium β-bromoethylbenzene sulfonate, (c) metastyrene sulfonic acid Sodium, (d) sodium bromostyrene sulfonate, (e) sodium β-hydroxyethylbenzenesulfonate.
本発明者らは、本発明の上記の製造方法、あるいは上記不純物を含むパラスチレンスルホン酸ナトリウムを水性溶媒に一部溶解し、再結晶する方法、純水で洗浄する方法又は反応温度などの製造条件をコントロールすることにより、臭化ナトリウムが２．５０ｗｔ％未満、好ましくは０．２０ｗｔ％以下であり、（ａ）オルソスチレンスルホン酸ナトリウム、（ｂ）β−ブロモエチルベンゼンスルホン酸ナトリウム、（ｃ）メタスチレンスルホン酸ナトリウム、（ｄ）ブロモスチレンスルホン酸ナトリウム、（ｅ）β−ヒドロキシエチルベンゼンスルホン酸ナトリウムの高速液体クロマトグラフィー（ＨＰＬＣ）で求めたピーク面積比が、各々（ａ）≦０．４０％、（ｂ）≦４．００％、（ｃ）≦８．００％、（ｄ）≦０．１０％、及び（ｅ）≦０．８０％（ただし、パラスチレンスルホン酸ナトリウムと（ａ）〜（ｅ）ピーク面積の総和は１００）である高純度パラスチレンスルホン酸ナトリウムを製造することができることを見出した。 The inventors have prepared the production method of the present invention, or a method of partially dissolving sodium parastyrenesulfonate containing the impurities in an aqueous solvent and recrystallizing, a method of washing with pure water, or a reaction temperature. By controlling the conditions, sodium bromide is less than 2.50 wt%, preferably 0.20 wt% or less, (a) sodium orthostyrenesulfonate, (b) sodium β-bromoethylbenzenesulfonate, (c) Peak area ratios determined by high performance liquid chromatography (HPLC) of sodium metastyrene sulfonate, (d) sodium bromostyrene sulfonate, and (e) sodium β-hydroxyethylbenzene sulfonate are (a) ≦ 0.40%, respectively. (B) ≦ 4.00%, (c) ≦ 8.00%, (d) ≦ 0.10%, and (e) It was found that high-purity sodium parastyrene sulfonate that is ≦ 0.80% (however, the sum of sodium parastyrene sulfonate and (a) to (e) peak areas is 100) can be produced.
これらの不純物を除去する方法は、特に限定するものではないが、例えば、本発明の上記の製造方法、あるいはこれに加えて、パラスチレンスルホン酸ナトリウムを純水、又はアセトン、メタノール、イソプロパノールなどの水溶性溶媒と水の混合溶媒に投入し、４０〜７０℃で３０〜１時間加熱、撹拌、一部溶解させた後、３０分〜２時間かけて３０℃以下まで冷却し、パラスチレンスルホン酸ナトリウムを洗浄、又は再結晶することによって、臭化ナトリウム、異性体、及びβ−ハロエチルベンゼンスルホン酸ナトリウムなどの主要不純物を低減できる。この操作を繰返すことにより、鉄以外の不純物を低減できる。この再結晶化の操作は１回以上、生産性やコストを考慮すると、好ましくは１〜３回である。 The method for removing these impurities is not particularly limited. For example, the above-described production method of the present invention, or in addition to this, sodium parastyrenesulfonate is purified water, or acetone, methanol, isopropanol or the like. It was added to a mixed solvent of water-soluble solvent and water, heated at 40 to 70 ° C. for 30 to 1 hour, stirred and partially dissolved, then cooled to 30 ° C. or lower over 30 minutes to 2 hours, and parastyrene sulfonic acid Washing or recrystallizing sodium can reduce major impurities such as sodium bromide, isomers, and sodium β-haloethylbenzenesulfonate. By repeating this operation, impurities other than iron can be reduced. This recrystallization operation is performed once or more, preferably 1 to 3 times in consideration of productivity and cost.
さらに具体的に上記この精製方法を示すと、例えばパラスチレンスルホン酸ナトリウムを、５〜６ｗｔ％濃度でメタノールに加熱溶解（通常、４０〜５０℃で１０〜６０分程度）し、ゆっくり常温〜１０℃付近まで冷却することにより、パラスチレンスルホン酸ナトリウムの結晶を析出させた後、濾過、乾燥することによって、高純度パラスチレンスルホン酸ナトリウムを得ることができる。 More specifically, this purification method is shown by dissolving, for example, sodium parastyrene sulfonate in methanol at a concentration of 5 to 6 wt% (usually about 40 to 50 ° C. for about 10 to 60 minutes), and slowly adding from 10 to 10 minutes. By cooling to around 0 ° C., crystals of sodium parastyrene sulfonate are precipitated, followed by filtration and drying, whereby high-purity sodium parastyrene sulfonate can be obtained.
以下の実施例により、本発明をさらに具体的に説明するが、本発明はこれらの実施例により何らの制限を受けるものではない。
なお、以下の実施例において、パラスチレンスルホン酸ナトリウムは以下の条件で分析した。
The following examples further illustrate the present invention, but the present invention is not limited to these examples.
In the following examples, sodium parastyrene sulfonate was analyzed under the following conditions.
＜試料中のスチレンスルホン酸ナトリウム分（純分）の定量＞
酸化還元滴定法により、活性二重結合を定量し、試料中のスチレンスルホン酸ナトリウム含量（即ち、パラ体の他、オルソ、メタ体も含む）とした。
（１）器具及び装置
１）秤量瓶：直径５０ｍｍ、深さ７０ｍｍ
２）５００ｍｌ、１０００ｍｌメスフラスコ
３）５００ｍｌ共栓付三角フラスコ
３）電子化学天秤
（２）試薬
１）臭素液：臭化カリウム（ＫＢｒ）２２．００ｇ、臭素酸カリウム（ＫＢｒＯ３）３．００ｇを純水に溶解し、全体を１０００ｍｌとした。
２）硫酸水溶液（濃硫酸／純水体積比＝１／１）
３）ヨウ化カリウム水溶液（２００ｇ／Ｌ）
４）０．１ｍｏｌ／Ｌチオ硫酸ナトリウム水溶液
５）でんぷん水溶液：６．００ｇのでんぷんを純水に溶解し、全体を１０００ｍｌとした。
（３）操作
１）試料２０ｇを０．１ｍｇの桁まで秤量瓶に秤取る。
２）５００ｍｌメスフラスコに純水で洗い移し、液量を約４００ｍｌとする。
３）磁気回転子を入れて撹拌し、試料を溶解する。
４）回転子を取り出し、純水で標線を合わせて振り混ぜ、検液とする。
５）純水２００ｍｌを入れた５００ｍｌ共栓付三角フラスコに臭素液２５ｍｌを加える。
６）検液５ｍｌを加えた後、硫酸水溶液１０ｍｌを加えて密栓し、２０分間放置する。
７）ヨウ化カリウム水溶液１０ｍｌを素早く加えて１０分間放置する。
８）チオ硫酸ナトリウム水溶液で滴定し、溶液の黄色が薄くなってから、指示薬として、でんぷん溶液１ｍｌを加え、生じたヨウ素でんぷんの青色が消えるまで滴定する。
９）別に空試験として、純水２００ｍｌを加えて共栓付三角フラスコに臭素液２５ｍｌを加え、ヨウ化カリウム水溶液１０ｍｌ、硫酸水溶液１０ｍｌを素早く加え、８）の操作を行う。
（４）計算
次式によってスチレンスルホン酸ナトリウム含量を算出する。
Ａ＝１００×[０．０１０３１×（ａ−ｂ）×ｆ]／（Ｓ×５／５００）
Ａ：スチレンスルホン酸ナトリウム含量（％）
ａ：空試験に要したチオ硫酸ナトリウム水溶液（ｍｌ）
ｂ：本試験に要したチオ硫酸ナトリウム水溶液（ｍｌ）
ｆ：チオ硫酸ナトリウム水溶液の力価
Ｓ：試料量（ｇ）
<Quantification of sodium styrenesulfonate content (pure content) in sample>
The active double bond was quantified by the oxidation-reduction titration method, and the content of sodium styrenesulfonate in the sample (that is, including the ortho and meta forms in addition to the para form) was determined.
(1) Instrument and device 1) Weighing bottle: diameter 50 mm, depth 70 mm
2) 500 ml, 1000 ml measuring flask 3) Erlenmeyer flask with 500 ml stopper 3) Electrochemical balance (2) Reagent 1) Bromine solution: 22.00 g of potassium bromide (KBr), 3.00 g of potassium bromate (KBrO 3 ) The whole was dissolved in pure water to make 1000 ml.
2) Aqueous sulfuric acid solution (concentrated sulfuric acid / pure water volume ratio = 1/1)
3) Potassium iodide aqueous solution (200 g / L)
4) 0.1 mol / L sodium thiosulfate aqueous solution 5) Starch aqueous solution: 6.00 g of starch was dissolved in pure water to make 1000 ml as a whole.
(3) Operation 1) Weigh 20 g of sample to the order of 0.1 mg in a weighing bottle.
2) Rinse into a 500 ml volumetric flask with pure water to make the liquid volume about 400 ml.
3) Put a magnetic rotor and stir to dissolve the sample.
4) Take out the rotor, align the mark with pure water and shake to make the test solution.
5) Add 25 ml of bromine solution to a 500 ml conical stoppered flask containing 200 ml of pure water.
6) Add 5 ml of the test solution, add 10 ml of sulfuric acid aqueous solution, seal tightly and leave for 20 minutes.
7) Add 10 ml of potassium iodide aqueous solution quickly and leave for 10 minutes.
8) Titrate with an aqueous sodium thiosulfate solution, and after the solution becomes light yellow, add 1 ml of starch solution as an indicator, and titrate until the blue color of the resulting iodine starch disappears.
9) Separately, as a blank test, add 200 ml of pure water, add 25 ml of bromine solution to a conical flask with a stopper, quickly add 10 ml of potassium iodide aqueous solution and 10 ml of sulfuric acid aqueous solution, and perform the operation of 8).
(4) Calculation The sodium styrenesulfonate content is calculated by the following formula.
A = 100 × [0.01031 × (ab) × f] / (S × 5/500)
A: Sodium styrenesulfonate content (%)
a: Sodium thiosulfate aqueous solution (ml) required for the blank test
b: Sodium thiosulfate aqueous solution (ml) required for this test
f: Potency of sodium thiosulfate aqueous solution S: Sample amount (g)
＜水分の測定＞
試料２ｇを０．１ｍｇの桁まで秤量瓶（直径５５ｍｍ×高さ３０ｍｍ）に秤とり、乾燥機（１０５±５℃）で９０分乾燥した。直ちにデシケータに移して室温まで冷却後、その質量を０．１ｍｇの桁まで量り、次式から水分を算出した。
水分（ｗｔ％）＝１００×[（ａ−ｂ）／Ｓ]
ａ＝乾燥前の試料と秤量瓶の重量（ｇ）、ｂ＝乾燥後の試料と秤量瓶の重量（ｇ）、Ｓ＝試料量（ｇ）
<Measurement of moisture>
2 g of the sample was weighed in a weighing bottle (diameter 55 mm × height 30 mm) to the order of 0.1 mg, and dried for 90 minutes with a dryer (105 ± 5 ° C.). Immediately after moving to a desiccator and cooling to room temperature, the mass was measured to the order of 0.1 mg, and moisture was calculated from the following equation.
Moisture (wt%) = 100 × [(ab) / S]
a = weight of the sample and weighing bottle before drying (g), b = weight of the sample and weighing bottle after drying (g), S = sample amount (g)
＜パラスチレンスルホン酸ナトリウム中の臭化ナトリウムの定量＞
（１）試料の調製
試料２０ｇを０．１ｍｇの桁まで秤量瓶（５０ｍｍφ×７０ｍｍ）に秤取り、５００ｍｌメスフラスコに純水で洗い移し、液量を約４００ｍｌとした。磁気撹拌子を入れて攪拌、溶解後、撹拌子を取出し、標線まで純水を加えて振り混ぜた。当該溶液５ｍｌを１００ｍｌメスフラスコに正しく採取し、標線まで純水を加えて試料溶液とした。
上記試料溶液及び混合標準液（関東化学（株）製の標準液を用い、Ｂｒ＝５,０００μｇ／１００ｍｌ、Ｃｌ＝５００μｇ／１００ｍｌ、ＳＯ４＝２,０００μｇ／１００ｍｌとなるように調製）をイオンクロマトグラフに注入し、各ピーク面積から試料中の臭化ナトリウム量を算出した。
（２）測定条件
機種＝東ソー社製、イオンクロマトグラフィーシステム８０２０
カラム＝ＴＳＫ−Ｇｅｌ ＩＣ−Ａｎｉｏｎ−ＰＷ
カラム温度＝４０℃
試料注入量＝１００μｌ
流量＝０．７ｍｌ
溶離液＝フタル酸水素カリウム５ｇとアセトニトリル３００ｍｌに純水を加えてトータル３０００ｍｌに調製した。
（３）計算
次式によって臭化ナトリウム（ＮａＢｒ）の含有量を算出した。
Ａ＝〔〔（５，０００μg×１.２８８×ａ／ｂ）＋（５００μｇ×２．８９９×ｃ／ｄ）〕／（Ｓ×５／５００）〕×１０−４
Ａ：臭化ナトリウム（NaBr）の含有量（%）
ａ：試料面積（Br）
ｂ：標準面積（Br）
ｃ：試料面積（Cl）
ｄ：標準面積（Cl）
Ｓ：試料量（g）
<Quantification of sodium bromide in sodium parastyrene sulfonate>
(1) Preparation of sample 20 g of sample was weighed in a weighing bottle (50 mmφ × 70 mm) to the order of 0.1 mg, washed with pure water into a 500 ml volumetric flask, and the liquid volume was about 400 ml. After stirring and dissolving with a magnetic stirring bar, the stirring bar was taken out, and pure water was added to the marked line and shaken. 5 ml of the solution was correctly collected in a 100 ml volumetric flask, and pure water was added up to the marked line to obtain a sample solution.
Ion the sample solution and mixed standard solution (prepared using Kanto Chemical Co., Ltd. standard solution so that Br = 5,000 μg / 100 ml, Cl = 500 μg / 100 ml, SO 4 = 2,000 μg / 100 ml) The sample was injected into the chromatograph, and the amount of sodium bromide in the sample was calculated from each peak area.
(2) Measurement conditions Model = Tosoh Corporation, ion chromatography system 8020
Column = TSK-Gel IC-Anion-PW
Column temperature = 40 ° C
Sample injection volume = 100 μl
Flow rate = 0.7ml
Eluent: 5 g of potassium hydrogen phthalate and 300 ml of acetonitrile were added pure water to prepare a total of 3000 ml.
(3) Calculation The content of sodium bromide (NaBr) was calculated by the following formula.
A = [[(5,000 μg × 1.288 × a / b) + (500 μg × 2.899 × c / d)] / (S × 5/500)] × 10 −4
A: Content of sodium bromide (NaBr) (%)
a: Sample area (Br)
b: Standard area (Br)
c: Sample area (Cl)
d: Standard area (Cl)
S: Sample amount (g)
＜ＨＰＬＣによるパラスチレンスルホン酸ナトリウム中の不純物の分析＞
パラスチレンスルホン酸ナトリウム（結晶水及び付着水を含む有姿の試料）試料を下記溶離液Ａで溶解して濃度０．５ｍｇ／ｍｌの溶液を調製し、ＨＰＬＣ分析を実施した。測定条件は以下の通りである。
機種＝東ソー社製ＬＣ−８０２０
（デガッサー：ＳＤ−８０２２、ポンプ：ＣＣＰＭ−II、カラムオーブン：ＣＯ−８０２０、紫外可視検出器：ＵＶ−８０２０）
カラム＝ＴＳＫｇｅｌ ＯＤＳ-８０ＴｓＱＡ（４．６ｍｍ×２５ｃｍ）
溶離液＝
Ａ液）水／アセトニトリル体積比＝９５／５＋０．１ｗｔ％トリフルオロ酢酸
Ｂ液）水／アセトニトリル体積比＝８０／２０＋０．１ｗｔ％トリフルオロ酢酸
グラジエント条件＝５５分までＡ液１００％、５５分〜９５分までＢ液１００％
流量＝０．８ｍｌ／ｍｉｎ、ＵＶ検出条件＝２３０ｎｍ、カラム温度＝常温、注入量＝２０μｌ
各不純物（ａ）〜（ｅ）の含有率は、パラスチレンスルホン酸ナトリウムと本条件で検出される（ａ）〜（ｅ）のＨＰＬＣピーク面積の総和を１００とした面積比である。
なお、ＨＰＬＣで検出される各ピークは、予め下記の方法で同定した。
ＨＰＬＣで検出される各成分を分取し、カチオン交換樹脂で処理してパラスチレンスルホン酸塩をスルホン酸型へ変換した後、スルホン酸基をジアゾメタンでメチルエステル化し、ガスクロマトグラフ質量分析（日立製作所製Ｍ−８０Ｂ）、フーリエ変換赤外分析（パーキンエルマー社製、Ｓｙｓｔｅｍ２０００）、有機元素分析（ヤナコ製、ＣＨＮコーダーＭＴ−３）、及び核磁気共鳴分析（バリアン社製、ＶＸＲ−３００）を実施し、構造を決定した。
<Analysis of impurities in sodium parastyrene sulfonate by HPLC>
A sodium parastyrenesulfonate (solid sample containing crystal water and adhering water) sample was dissolved in the following eluent A to prepare a solution having a concentration of 0.5 mg / ml, and HPLC analysis was performed. The measurement conditions are as follows.
Model = LC-8020 manufactured by Tosoh Corporation
(Degasser: SD-8022, pump: CCPM-II, column oven: CO-8020, UV-visible detector: UV-8020)
Column = TSKgel ODS-80TsQA (4.6 mm × 25 cm)
Eluent =
Liquid A) Water / acetonitrile volume ratio = 95/5 + 0.1 wt% trifluoroacetic acid Liquid B) Water / acetonitrile volume ratio = 80/20 + 0.1 wt% trifluoroacetic acid Gradient condition = Up to 55 minutes Liquid A 100%, 55 minutes- Liquid B 100% up to 95 minutes
Flow rate = 0.8 ml / min, UV detection condition = 230 nm, column temperature = room temperature, injection amount = 20 μl
The content rate of each impurity (a)-(e) is an area ratio which set the sum total of the HPLC peak area of sodium parastyrenesulfonate and (a)-(e) detected on these conditions to 100.
Each peak detected by HPLC was previously identified by the following method.
After separating each component detected by HPLC and treating with cation exchange resin to convert parastyrene sulfonate to sulfonic acid type, methyl ester of sulfonic acid group with diazomethane, gas chromatograph mass spectrometry (Hitachi, Ltd.) M-80B), Fourier transform infrared analysis (Perkin Elmer, System 2000), organic element analysis (Yanaco, CHN coder MT-3), and nuclear magnetic resonance analysis (Varian, VXR-300) And the structure was determined.
＜形状観察＞
電界放出形走査型電子顕微鏡（日立製作所製Ｓ−４５００）を用い、加速電圧１５ｋＶで観察した。
＜粒径分布の測定＞
試料０．５５ｇとイソプロパノール１５．０ｇを３０ｍｌガラス製サンプル瓶に採取し、超音波洗浄機で４分間処理してスラリーを調製後、レーザー回折・散乱式粒度分析計マイクロトラックＨＲＡ（日機装株式会社製）を用い、下記の条件で粒度分布測定を行なった。
Ｐａｒｔｉｃｌｅ Ｔｒａｎｓｐａｒｅｎｃｙ ＝Ｔｒａｎｓｐ
Ｓｐｈｅｒｉｃａｌ Ｐａｒｔｉｃｌｅｓ ＝Ｎｏ
Ｐａｒｔｉｃｌｅ Ｒｅｆｒａｃｔｉｖｅ Ｉｎｄｅｘ＝１．５５
Ｆｌｕｉｄ Ｒｅｆｒａｃｔｉｖｅ Ｉｎｄｅｘ ＝１．３８
<Shape observation>
Using a field emission scanning electron microscope (S-4500, manufactured by Hitachi, Ltd.), observation was performed at an acceleration voltage of 15 kV.
<Measurement of particle size distribution>
0.55 g of sample and 15.0 g of isopropanol were collected in a 30 ml glass sample bottle, treated with an ultrasonic cleaner for 4 minutes to prepare a slurry, and then laser diffraction / scattering particle size analyzer Microtrac HRA (manufactured by Nikkiso Co., Ltd.) The particle size distribution was measured under the following conditions.
Particle Transparency = Transp
Physical Particles = No
Particle Refractive Index = 1.55
Fluid Refractive Index = 1.38
＜安息角の測定＞
（１）器具及び装置
１）安息角測定装置、２）分度器、および３）電子上皿天秤は、図６のとおりの構成とした。
（２）操作
１）試料８０ｇを、装置のロートを通してシャーレ上に自然落下させる。
２）シャーレ上にできた円錐の頂角（a）を分度器で整数の桁まで読みとる。
３）この操作を3回繰り返し、円錐の頂角（a）の平均値を求める。
（３）計算
次式によって安息角を算出する。安息角が小さいほど流動性が優れる。
Ａ＝（１８０−ａ）／２
ここに、Ａ：安息角（度）、ａ：円錐の頂角（度）
<Measurement of repose angle>
(1) Instrument and apparatus 1) A repose angle measuring apparatus, 2) A protractor, and 3) An electronic pan balance were configured as shown in FIG.
(2) Operation 1) The sample 80g is naturally dropped on the petri dish through the funnel of the apparatus.
2) Read the apex angle (a) of the cone on the petri dish to an integer number with a protractor.
3) Repeat this operation three times to obtain the average value of the apex angle (a) of the cone.
(3) Calculation The angle of repose is calculated by the following formula. The smaller the angle of repose, the better the fluidity.
A = (180−a) / 2
Where A: angle of repose (degrees), a: apex angle of the cone (degrees)
＜溶解速度〔水への溶解性〕の測定＞
２５℃の恒温室で、２０ｍｌガラス製サンプルビン（外径２７ｍｍ×深さ５５ｍｍ）にパラスチレンスルホン酸ナトリウム粉体（不純物や水分を含む有姿）を１．００ｇ精秤した後、純水９．００ｇを素早く加えた。その後、当該サンプル瓶の上下を１秒間に１サイクルの周期で逆転させ、パラスチレンスルホン酸ナトリウムが溶解するまでの時間を目視判定した。
<Measurement of dissolution rate [solubility in water]>
In a thermostatic chamber at 25 ° C., after accurately weighing 1.00 g of sodium parastyrenesulfonate powder (impregnated with impurities and moisture) in a 20 ml glass sample bottle (outer diameter 27 mm × depth 55 mm), pure water 9 .00 g was added quickly. Thereafter, the upper and lower sides of the sample bottle were reversed at a cycle of 1 cycle per second, and the time until the sodium parastyrene sulfonate was dissolved was visually determined.
実施例１
ジャケットを備えた攪拌機付のステンレス製反応器に、１１．７ｗｔ％水酸化ナトリウム水溶液７５０ＫＧと亜硝酸ナトリウム２．５ＫＧを仕込み、９０℃まで加熱し、同温度にて７３ｗｔ％β-ブロモエチルベンゼンスルホン酸水溶液２,０００ＫＧと４８ｗｔ％水酸化ナトリウム９５０ＫＧとを一定速度で４時間かけ別々に導入し（反応釜内の水酸化ナトリウム濃度は、反応開始時の１１．６６ｗｔ％から反応開始４時間後（反応終了時）の１４．６９ｗｔ％まで徐々に増加、β-ブロモエチルベンゼンスルホン酸濃度は、反応開始時の０．００ｗｔ％から反応開始４時間後（反応終了時）の３９．４３ｗｔ％まで徐々に増加）、パラスチレンスルホン酸ナトリウムを反応晶析させ、そのスラリーを２時間かけて４０℃まで冷却した。その後遠心分離によって固液分離した。分離は極めて容易であり、３０分の振りきりで、スチレンスルホン酸ナトリウム含量が８８．５ｗｔ％の高純度の湿潤ケーク９４０ＫＧを得た。この湿潤ケークに対し一軸のスクリューブレンダーを用いて、４０℃、２０ｒｐｍの回転速度で６０分間強制流動させた。得られたパラスチレンスルホン酸ナトリウムはメジアン径６３．１μｍ、１０．００μｍ未満の小粒１．５０％、水分７．１ｗｔ％、安息角４７度、及び水への溶解時間は１６０秒であった。比較例２に対して、僅かに流動性は劣るものの、溶解性は遥かに優れることから、流動性と溶解性のバランスが優れることが明らかである。
なお、臭化ナトリウムや有機不純物などの不純物の数値は、表１に示すとおりであった。
また、実施例１で得られたパラスチレンスルホン酸ナトリウムのマイクロトラック粒径分布を図１に、電子顕微鏡像を図２に、ＨＰＬＣクロマトグラフィーを図５に示した。
Example 1
A stainless steel reactor equipped with a stirrer equipped with a jacket was charged with 750 KG of an aqueous solution of 11.7 wt% sodium hydroxide and 2.5 KG of sodium nitrite, heated to 90 ° C., and 73 wt% β-bromoethylbenzenesulfonic acid at the same temperature. An aqueous solution of 2,000 KG and 48 wt% sodium hydroxide 950 KG were separately introduced at a constant rate over 4 hours (the sodium hydroxide concentration in the reaction kettle was changed from 11.66 wt% at the start of the reaction to 4 hours after the start of the reaction (reaction Gradually increased to 14.69 wt% at the end of the reaction, and the β-bromoethylbenzenesulfonic acid concentration gradually increased from 0.00 wt% at the start of the reaction to 39.43 wt% 4 hours after the start of the reaction (at the end of the reaction). ), Sodium parastyrene sulfonate was reacted and crystallized, and the slurry was cooled to 40 ° C. over 2 hours. Thereafter, solid-liquid separation was performed by centrifugation. Separation was extremely easy, and after 30 minutes of shaking, a high-purity wet cake 940KG having a sodium styrenesulfonate content of 88.5 wt% was obtained. The wet cake was forced to flow for 60 minutes at 40 ° C. and a rotation speed of 20 rpm using a uniaxial screw blender. The obtained sodium parastyrene sulfonate had a median diameter of 63.1 μm, a small particle of less than 10.00 μm 1.50%, a moisture content of 7.1 wt%, an angle of repose of 47 degrees, and a dissolution time in water of 160 seconds. Although the fluidity is slightly inferior to Comparative Example 2, it is clear that the solubility is far superior, so that the balance between fluidity and solubility is excellent.
The numerical values of impurities such as sodium bromide and organic impurities are as shown in Table 1.
In addition, the microtrack particle size distribution of sodium parastyrenesulfonate obtained in Example 1 is shown in FIG. 1, the electron microscope image is shown in FIG. 2, and the HPLC chromatography is shown in FIG.
実施例２
実施例1において、β-ブロモエチルベンゼンスルホン酸水溶液と水酸化ナトリウム水溶液を一定速度４時間でフィードした代わりに、一定速度２．５時間でフィードした他は全て実施例１と同じ条件でパラスチレンスルホン酸ナトリウムを反応晶析させ（反応釜内の水酸化ナトリウム濃度は、反応開始時１１．６６ｗｔ％から反応開始２．５時間後（反応終了時）１４．６９ｗｔ％まで徐々に増加、β-ブロモエチルベンゼンスルホン酸濃度は、反応開始時の０．００ｗｔ％から反応開始２．５時間後（反応終了時）の３９．４３ｗｔ％まで徐々に増加）、そのスラリーを２時間かけて４０℃まで冷却した。その後、遠心分離によって固液分離した。分離は極めて容易であり、３０分の振りきりで、スチレンスルホン酸ナトリウム含量が８８．９ｗｔ％の高純度の湿潤ケーク９３０ＫＧを得た。この湿潤ケークに対し一軸のスクリューブレンダーを用いて、４０℃、２０ｒｐｍの回転速度で６０分間強制流動させた。得られたパラスチレンスルホン酸ナトリウムはメジアン径１１０μｍ、１０．００μｍ未満の小粒０．００％、水分６．１ｗｔ％、及び安息角は４３度であった。水への溶解時間は２００秒であり、比較例２と比較して、流動性と溶解性のバランスが優れることが明らかである。なお、臭化ナトリウムや有機不純物などの不純物の数値は、表１に示すとおりであった。
Example 2
In Example 1, instead of feeding the β-bromoethylbenzenesulfonic acid aqueous solution and the sodium hydroxide aqueous solution at a constant rate of 4 hours, all were fed at a constant rate of 2.5 hours under the same conditions as in Example 1, except that parastyrene sulfone was used. Sodium hydroxide was crystallized from the reaction (the sodium hydroxide concentration in the reaction vessel gradually increased from 11.66 wt% at the start of the reaction to 14.69 wt% at 2.5 hours after the start of the reaction (at the end of the reaction). The concentration of ethylbenzenesulfonic acid gradually increased from 0.00 wt% at the start of the reaction to 39.43 wt% after 2.5 hours of reaction start (at the end of the reaction)), and then the slurry was cooled to 40 ° C. over 2 hours. . Thereafter, solid-liquid separation was performed by centrifugation. Separation was very easy, and after 30 minutes of shaking, a high-purity wet cake 930KG having a sodium styrenesulfonate content of 88.9 wt% was obtained. The wet cake was forced to flow for 60 minutes at 40 ° C. and a rotation speed of 20 rpm using a uniaxial screw blender. The obtained sodium parastyrene sulfonate had a median diameter of 110 μm, 0.00% small particles less than 10.00 μm, a moisture content of 6.1 wt%, and an angle of repose of 43 degrees. The dissolution time in water is 200 seconds, and it is clear that the balance between fluidity and solubility is excellent as compared with Comparative Example 2. The numerical values of impurities such as sodium bromide and organic impurities are as shown in Table 1.
実施例３
実施例1において、β-ブロモエチルベンゼンスルホン酸水溶液と水酸化ナトリウム水溶液を一定速度４時間でフィードした代わりに、一定速度５時間でフィードした他は全て実施例１と同じ条件でパラスチレンスルホン酸ナトリウムを反応晶析させ（反応釜内の水酸化ナトリウム濃度は、反応開始時１１．６６ｗｔ％から反応開始５時間後（反応終了時）１４．６９ｗｔ％まで徐々に増加、β-ブロモエチルベンゼンスルホン酸濃度は、反応開始時の０．００ｗｔ％から反応開始５時間後（反応終了時）の３９．４３ｗｔ％まで徐々に増加）、そのスラリーを２時間かけて４０℃まで冷却した。その後、遠心分離によって固液分離した。分離は極めて容易であり、３０分の振りきりで、スチレンスルホン酸ナトリウム含量が８８．９ｗｔ％の高純度の湿潤ケーク９５０ＫＧを得た。この湿潤ケークに対し一軸のスクリューブレンダーを用いて、４０℃、２０ｒｐｍの回転速度で６０分間強制流動させた。得られたパラスチレンスルホン酸ナトリウムはメジアン径３７μｍ、１０．００μｍ未満の小粒３．１％、水分８．６ｗｔ％、及び安息角５１度であった。水への溶解時間は１４０秒だった。比較例１及び３と比較して、僅かに溶解性が劣るものの、流動性は遥かに優れることから、流動性と溶解性のバランスが優れることが明らかである。
なお、臭化ナトリウムや有機不純物などの不純物の数値は、表１に示すとおりであった
Example 3
In Example 1, instead of feeding the β-bromoethylbenzenesulfonic acid aqueous solution and the sodium hydroxide aqueous solution at a constant rate of 4 hours, all of them were fed at a constant rate of 5 hours under the same conditions as in Example 1, sodium parastyrenesulfonate. (The sodium hydroxide concentration in the reaction kettle gradually increased from 11.66 wt% at the start of the reaction to 14.69 wt% after 5 hours from the start of the reaction (at the end of the reaction), and the β-bromoethylbenzenesulfonic acid concentration. Was gradually increased from 0.00 wt% at the start of the reaction to 39.43 wt% 5 hours after the start of the reaction (at the end of the reaction), and the slurry was cooled to 40 ° C. over 2 hours. Thereafter, solid-liquid separation was performed by centrifugation. Separation was very easy, and after 30 minutes of shaking, a high-purity wet cake 950KG having a sodium styrenesulfonate content of 88.9 wt% was obtained. The wet cake was forced to flow for 60 minutes at 40 ° C. and a rotation speed of 20 rpm using a uniaxial screw blender. The obtained sodium parastyrene sulfonate had a median diameter of 37 μm, a small particle of less than 10.00 μm 3.1%, a water content of 8.6 wt%, and an angle of repose of 51 degrees. The dissolution time in water was 140 seconds. Although the solubility is slightly inferior to Comparative Examples 1 and 3, the fluidity is far superior, so that it is clear that the balance between fluidity and solubility is excellent.
The values of impurities such as sodium bromide and organic impurities were as shown in Table 1.
実施例４（精製）
ジャケットを備えた攪拌機付のステンレス製反応器に、実施例１で得たパラスチレンスルホン酸ナトリウム１,０００ｇ、亜硝酸ナトリウム１．０ｇ、苛性ソーダ２０．０ｇ、純水９５０．０ｇを仕込み、窒素雰囲気下、４０℃で１時間撹拌した。その後、３時間かけて室温まで冷却後、遠心分離機で固液分離して、高純度パラスチレンスルホン酸ナトリウムの湿潤ケーキ８９８．０ｇを得た。
得られた精製後の高純度パラスチレンスルホン酸ナトリウムはメジアン径４８μｍ、水分８．６ｗｔ％、安息角５０度、及び１０．００μｍ未満の小粒は２．５％であった。水への溶解時間は１３０秒だった。比較例１及び３と比較して、僅かに溶解性が劣るものの、流動性は遥かに優れることから、流動性と溶解性のバランスが優れることが明らかである。
また、上記パラスチレンスルホン酸ナトリウムの純度は８９．１％、水分８．６ｗｔ％、臭化ナトリウム分は０．２０ｗｔ％、異性体等の有機不純物は、（ａ）０．０６％、（ｂ）０．０３％、（ｃ）１．３４％、（ｄ）０．１０％、（ｅ）０．００％だった。
なお、精製前のパラスチレンスルホン酸ナトリウムの純度は８８．５％、水分は７．１ｗｔ％、臭化ナトリウム分は２．１０ｗｔ％、異性体等の有機不純物は、（ａ）０．１６％、（ｂ）０．４３％、（ｃ）２．６４％、（ｄ）０．１２％、（ｅ）０．４８％（ただし、パラスチレンスルホン酸ナトリウムと（ａ）〜（ｅ）ピーク面積の総和は１００））であり、比較例３と比べて、精製度が高いことが明らかである。遠心濾過性が良く、固液分離がスムーズに進行したためと考えられる。
Example 4 (Purification)
A stainless steel reactor equipped with a stirrer equipped with a jacket was charged with 1,000 g of sodium parastyrene sulfonate obtained in Example 1, 1.0 g of sodium nitrite, 20.0 g of sodium hydroxide and 950.0 g of pure water, and a nitrogen atmosphere. The mixture was stirred at 40 ° C. for 1 hour. Then, after cooling to room temperature over 3 hours, solid-liquid separation was performed with a centrifuge to obtain 898.0 g of a wet cake of high-purity sodium parastyrenesulfonate.
The obtained high-purity sodium parastyrenesulfonate after purification had a median diameter of 48 μm, a water content of 8.6 wt%, an angle of repose of 50 degrees, and a small particle of less than 10.00 μm was 2.5%. The dissolution time in water was 130 seconds. Although the solubility is slightly inferior to Comparative Examples 1 and 3, the fluidity is far superior, so that it is clear that the balance between fluidity and solubility is excellent.
Further, the purity of the sodium parastyrene sulfonate is 89.1%, the water content is 8.6 wt%, the sodium bromide content is 0.20 wt%, and the organic impurities such as isomers are (a) 0.06%, (b ) 0.03%, (c) 1.34%, (d) 0.10%, (e) 0.00%.
The purity of sodium parastyrene sulfonate before purification is 88.5%, moisture is 7.1 wt%, sodium bromide content is 2.10 wt%, and organic impurities such as isomers are (a) 0.16% (B) 0.43%, (c) 2.64%, (d) 0.12%, (e) 0.48% (however, sodium parastyrenesulfonate and (a) to (e) peak areas) Is 100)), and it is clear that the degree of purification is higher than that of Comparative Example 3. This is probably because the centrifugal filterability was good and the solid-liquid separation proceeded smoothly.
比較例１（粒径が小さいパラスチレンスルホン酸ナトリウム）
市販のパラスチレンスルホン酸ナトリウムを分析した結果、メジアン径１９．８μｍ、１０．００μｍ未満の小粒１３．６０％（図３にマイクロトラック粒径分布、図４に電子顕微鏡像を示した）、水分１０．４０ｗｔ％、及び安息角５９度、水への溶解時間は１３０秒だった。また、臭化ナトリウムや有機不純物などの不純物の数値は、表１に示すとおりであった。実施例３及び４と比較して、溶解性は同等以上だが、流動性が劣り、水分も多い（パラスチレンスルホン酸ナトリウム含量が低い）ことが明らかである。
次いで、ジャケットを備えた攪拌機付のステンレス製反応器に、上記の市販パラスチレンスルホン酸ナトリウム１,０００ｇ、亜硝酸ナトリウム１．０ｇ、苛性ソーダ２０．０ｇ、純水９５０．０ｇを仕込み、窒素雰囲気下、４０℃で１時間撹拌した。その後、３時間かけて室温まで冷却後、遠心分離機で固液分離して、高純度パラスチレンスルホン酸ナトリウムの湿潤ケーキ８９７．０ｇを得た。
得られた精製後のパラスチレンスルホン酸ナトリウムは、メジアン径２２．３μｍ、水分１０．８ｗｔ％、安息角５８度、及び１０．００μｍ未満の小粒は３．１％であった。水への溶解時間は１２８秒だった（結果は表１にまとめた）。
また、上記パラスチレンスルホン酸ナトリウムの純度は８５．５％、水分１０．８ｗｔ％、臭化ナトリウム分は１．１０ｗｔ％、異性体等の有機不純物は、（ａ）０．２２％、（ｂ）２．８０％、（ｃ）６．９３％、（ｄ）０．０５％、（ｅ）０．２０％だった。
なお、精製前のパラスチレンスルホン酸ナトリウムの純度は８３．４％、水分１０．４ｗｔ％、臭化ナトリウム分は２．１０ｗｔ％、異性体等の有機不純物は、（ａ）０．３５％、（ｂ）３．４６％、（ｃ）７．７４％、（ｄ）０．０６％、（ｅ）０．７０％（ただし、パラスチレンスルホン酸ナトリウムと（ａ）〜（ｅ）ピーク面積の総和は１００）であり、実施例４と比べて、精製度が低いことが明らかである。遠心濾過性が悪く、固液分離がスムーズに進行しなかったためと考えられる。
Comparative Example 1 (sodium parastyrene sulfonate having a small particle size)
As a result of analyzing commercially available sodium parastyrene sulfonate, 13.60% of median diameters of 19.8 μm and less than 10.00 μm (FIG. 3 shows a microtrack particle size distribution and FIG. 4 shows an electron microscope image), moisture content 10.40 wt%, repose angle 59 degrees, dissolution time in water was 130 seconds. Further, the numerical values of impurities such as sodium bromide and organic impurities are as shown in Table 1. Compared to Examples 3 and 4, it is clear that the solubility is equal to or higher, but the fluidity is inferior and the water content is high (the sodium parastyrenesulfonate content is low).
Next, a commercially available stainless steel reactor equipped with a stirrer equipped with a jacket was charged with 1,000 g of the above-mentioned commercially available sodium parastyrenesulfonate, 1.0 g of sodium nitrite, 20.0 g of sodium hydroxide and 950.0 g of pure water, under a nitrogen atmosphere. And stirred at 40 ° C. for 1 hour. Then, after cooling to room temperature over 3 hours, solid-liquid separation was performed with a centrifugal separator to obtain 897.0 g of a wet cake of high-purity sodium parastyrenesulfonate.
The obtained sodium parastyrene sulfonate after purification had a median diameter of 22.3 μm, a water content of 10.8 wt%, an angle of repose of 58 degrees, and small particles of less than 10.00 μm of 3.1%. The dissolution time in water was 128 seconds (results are summarized in Table 1).
Further, the purity of the sodium parastyrene sulfonate is 85.5%, the water content is 10.8 wt%, the sodium bromide content is 1.10 wt%, the organic impurities such as isomers are (a) 0.22%, (b ) 2.80%, (c) 6.93%, (d) 0.05%, (e) 0.20%.
In addition, the purity of sodium parastyrene sulfonate before purification is 83.4%, moisture is 10.4 wt%, sodium bromide content is 2.10 wt%, and organic impurities such as isomers are (a) 0.35%, (B) 3.46%, (c) 7.74%, (d) 0.06%, (e) 0.70% (however, sodium parastyrenesulfonate and (a) to (e) of the peak area) The sum is 100), and it is clear that the degree of purification is lower than that in Example 4. This is probably because the centrifugal filterability was poor and solid-liquid separation did not proceed smoothly.
比較例２（粒径が大きいパラスチレンスルホン酸ナトリウム）
ジャケットを備えた攪拌機付のステンレス製反応器に、反応温度６０℃で、１時間当たり７０ｗｔ％β-ブロモエチルベンゼンスルホン酸水溶液１７９ＫＧと２５ｗｔ％水酸化ナトリウム２０３ＫＧ（０．２ｗｔ％の亜硝酸ナトリウムを含有）とを別々に連続して導入し、パラスチレンスルホン酸ナトリウムを反応晶析させた（反応釜内の水酸化ナトリウム濃度は、反応開始から反応開始１時間後まで１３．２９ｗｔ％だが、β-ブロモエチルベンゼンスルホン酸濃度も、反応開始時から反応開始１時間後まで３２．８０ｗｔ％と高い）。晶析スラリーを５分毎に間欠的に連続して１時間当たり３８２ＫＧ抜出した。スラリーを２時間かけて４０℃まで冷却し、遠心分離によって固液分離した。３０分の振りきりで、スチレンスルホン酸ナトリウム含量が８５．１ｗｔ％の湿潤ケークを得た。この湿潤ケークに対し一軸のスクリューブレンダーを用いて、４０℃、２０ｒｐｍの回転速度で６０分間強制流動させた。得られたパラスチレンスルホン酸ナトリウムはメジアン径１６０μｍ、１０μｍ未満の小粒０．００％、水分５．９ｗｔ％、及び安息角４５度であった。しかし、水への溶解時間は２７０秒であり、実施例１及び２と比較して、溶解性が劣ることが明らかである。なお、臭化ナトリウムや有機不純物などの不純物の数値は、表１に示すとおりであった。
Comparative Example 2 (sodium parastyrene sulfonate having a large particle size)
In a stainless steel reactor equipped with a stirrer equipped with a jacket, the reaction temperature is 60 ° C., and 70 wt% β-bromoethylbenzenesulfonic acid aqueous solution 179KG and 25 wt% sodium hydroxide 203KG per hour (containing 0.2 wt% sodium nitrite) And sodium parastyrene sulfonate were crystallized by reaction (the sodium hydroxide concentration in the reaction kettle was 13.29 wt% from the start of the reaction to 1 hour after the start of the reaction. The bromoethylbenzenesulfonic acid concentration is also high at 32.80 wt% from the start of the reaction to 1 hour after the start of the reaction). The crystallization slurry was withdrawn 382 KG per hour continuously every 5 minutes. The slurry was cooled to 40 ° C. over 2 hours and solid-liquid separated by centrifugation. After 30 minutes of shaking, a wet cake having a sodium styrenesulfonate content of 85.1 wt% was obtained. The wet cake was forced to flow for 60 minutes at 40 ° C. and a rotation speed of 20 rpm using a uniaxial screw blender. The obtained sodium parastyrene sulfonate had a median diameter of 160 μm, 0.00% small granules less than 10 μm, a moisture content of 5.9 wt%, and an angle of repose of 45 degrees. However, the dissolution time in water is 270 seconds, which is clearly inferior in solubility as compared with Examples 1 and 2. The numerical values of impurities such as sodium bromide and organic impurities are as shown in Table 1.
比較例３
ジャケットを備えた攪拌機付のステンレス製反応器に、３５ｗｔ％水酸化ナトリウム１０５４ＫＧと亜硝酸ナトリウム１．２ＫＧを仕込み、９０℃まで加熱し、窒素雰囲気中、撹拌下、７０ｗｔ％β-ブロモエチルベンゼンスルホン酸水溶液１,０１２ＫＧを一定速度３時間かけて導入し、パラスチレンスルホン酸ナトリウムを反応晶析させ（反応開始時の反応釜内の水酸化ナトリウム濃度は３４．９６ｗｔ％と高く、反応開始３時間後（反応終了時）は１７．８５ｗｔ％まで徐々に低下、β-ブロモエチルベンゼンスルホン酸濃度は、反応開始時の０．００ｗｔ％から反応開始３時間後（反応終了時）の３４．２９ｗｔ％まで徐々に増加）、そのスラリーを２時間かけて４０℃まで冷却した。その後、遠心分離によって固液分離した。４０分の振りきりで、スチレンスルホン酸ナトリウム含量が８４．２ｗｔ％の湿潤ケーク９８０ＫＧを得た。この湿潤ケークに対し一軸のスクリューブレンダーを用いて、４０℃、２０ｒｐｍの回転速度で６０分間強制流動させた。得られたパラスチレンスルホン酸ナトリウムはメジアン径２２．０μｍ、１０．００μｍ未満の小粒１２．５０ｗｔ％、水分１０．２ｗｔ％、及び安息角５９度であった。水への溶解時間は１２７秒だったが、実施例４と比較して、流動性が劣り、水分も多い（パラスチレンスルホン酸ナトリウム含量が低い）ことが明らかである。
次いで、ジャケットを備えた攪拌機付のステンレス製反応器に、上記パラスチレンスルホン酸ナトリウム１,０００ｇ、亜硝酸ナトリウム１．０ｇ、苛性ソーダ２０．０ｇ、純水９５０．０ｇを仕込み、窒素雰囲気下、４０℃で１時間撹拌した。その後、３時間かけて室温まで冷却後、遠心分離機で固液分離して、高純度パラスチレンスルホン酸ナトリウムの湿潤ケーキ８９１．０ｇを得た。
上記精製後のパラスチレンスルホン酸ナトリウムの純度は８５．５％、水分１０．５ｗｔ％、臭化ナトリウム分は１．２１ｗｔ％、異性体等の有機不純物は、（ａ）０．１５％、（ｂ）２．５６％、（ｃ）６．２０％、（ｄ）０．０３％、（ｅ）０．２０％だった。
なお、精製前のパラスチレンスルホン酸ナトリウムの純度は８４．２％、水分は１０．２ｗｔ％、臭化ナトリウム分は２．２０ｗｔ％、異性体等の有機不純物は、（ａ）０．４１％、（ｂ）３．２１％、（ｃ）７．１２％、（ｄ）０．０５％、（ｅ）０．７０％（ただし、パラスチレンスルホン酸ナトリウムと（ａ）〜（ｅ）ピーク面積の総和は１００）であり、実施例４と比べて、精製度が低いことが明らかである。遠心濾過性が悪く、固液分離がスムーズに進行しなかったためと考えられる。
Comparative Example 3
A stainless steel reactor equipped with a stirrer equipped with a jacket was charged with 35 wt% sodium hydroxide 1054KG and sodium nitrite 1.2KG, heated to 90 ° C, and stirred in a nitrogen atmosphere with 70wt% β-bromoethylbenzenesulfonic acid. Aqueous solution 1,012KG was introduced over a constant rate of 3 hours, and sodium parastyrene sulfonate was reacted and crystallized (the sodium hydroxide concentration in the reaction kettle at the start of the reaction was as high as 34.96 wt%, 3 hours after the start of the reaction) (At the end of the reaction) gradually decreases to 17.85 wt%, and the concentration of β-bromoethylbenzenesulfonic acid gradually increases from 0.00 wt% at the start of the reaction to 34.29 wt% after 3 hours (at the end of the reaction). The slurry was cooled to 40 ° C. over 2 hours. Thereafter, solid-liquid separation was performed by centrifugation. After 40 minutes of shaking, a wet cake 980KG having a sodium styrenesulfonate content of 84.2 wt% was obtained. The wet cake was forced to flow for 60 minutes at 40 ° C. and a rotation speed of 20 rpm using a uniaxial screw blender. The obtained sodium parastyrene sulfonate had a median diameter of 22.0 μm, a small particle of less than 10.00 μm of 12.50 wt%, a water content of 10.2 wt%, and an angle of repose of 59 degrees. Although the dissolution time in water was 127 seconds, it is apparent that the fluidity is inferior and the water content is high (the sodium parastyrenesulfonate content is low) as compared with Example 4.
Next, a stainless steel reactor equipped with a stirrer equipped with a jacket was charged with 1,000 g of the above sodium parastyrene sulfonate, 1.0 g of sodium nitrite, 20.0 g of sodium hydroxide and 950.0 g of pure water. Stir for 1 hour at ° C. Then, after cooling to room temperature over 3 hours, solid-liquid separation was performed with a centrifugal separator to obtain 891.0 g of a high purity sodium parastyrene sulfonate wet cake.
The purity of sodium parastyrene sulfonate after the above purification is 85.5%, the moisture is 10.5 wt%, the sodium bromide content is 1.21 wt%, the organic impurities such as isomers are (a) 0.15%, ( b) 2.56%, (c) 6.20%, (d) 0.03%, (e) 0.20%.
In addition, the purity of sodium parastyrene sulfonate before purification is 84.2%, moisture is 10.2 wt%, sodium bromide content is 2.20 wt%, and organic impurities such as isomers are (a) 0.41% (B) 3.21%, (c) 7.12%, (d) 0.05%, (e) 0.70% (however, sodium parastyrenesulfonate and (a) to (e) peak areas) Is 100), and it is clear that the degree of purification is lower than that of Example 4. This is probably because the centrifugal filterability was poor and solid-liquid separation did not proceed smoothly.
本発明の流動性と溶解性に優れるパラスチレンスルホン酸ナトリウムは、エマルジョン重合用の反応性乳化剤、及び顔料、酸化防止剤、各種ポリマー（粘着付与樹脂、クロロプレンゴム、ポリアクリル酸エステル、ポリエステル、スチレン／ブタジエン共重合体、ポリ塩化ビニル、シリコーンポリマー、導電性ポリマーなど）、ナノカーボン材料、熱間鍛造離型剤（シリカ粒子などのスラリー）、電池電極材料（カーボン、リン酸鉄リチウム、リン酸マンガンリチウムなど）、化学機械研磨（所謂ＣＭＰ）スラリー、写真用ハロゲン化銀などの水性分散体に必要な分散剤の製造など、幅広い産業分野で利用価値が高い。
The sodium parastyrene sulfonate excellent in fluidity and solubility of the present invention is a reactive emulsifier for emulsion polymerization, a pigment, an antioxidant, and various polymers (tackifying resin, chloroprene rubber, polyacrylic ester, polyester, styrene. / Butadiene copolymer, polyvinyl chloride, silicone polymer, conductive polymer, etc.), nanocarbon materials, hot forging release agents (slurry such as silica particles), battery electrode materials (carbon, lithium iron phosphate, phosphoric acid) It has a high utility value in a wide range of industrial fields, such as the production of dispersants required for aqueous dispersions such as manganese lithium, chemical mechanical polishing (so-called CMP) slurries, and photographic silver halides.
Claims (4)
In a process for producing sodium parastyrene sulfonate by simultaneously feeding sodium hydroxide and β-bromoethylbenzene sulfonic acid to a reaction kettle at a constant rate, the sodium hydroxide concentration in the reaction kettle [(weight of total fed sodium hydroxide / Total reaction liquid weight in reaction kettle) × 100] is maintained at 10.00 to 20.00 wt%, and β-bromoethylbenzenesulfonic acid concentration [(weight of fed total β-bromoethylbenzenesulfonic acid / reaction kettle The total reaction solution weight) × 100] is controlled to increase from 0.00 wt% to 30.00 to 50.00 wt% over 1 to 7 hours, while reacting at 60 to 110 ° C. for 1 to 7 hours. The wet cake obtained by crystallization and solid-liquid separation is forcibly fluidized, and has excellent fluidity and solubility according to any one of claims 1 to 3. A method for producing sodium parastyrene sulfonate.
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| CN201380053883.6A CN104736516B (en) | 2012-10-15 | 2013-09-02 | It sodium p styrene sulfonate and its manufacturing method, poly (sodium 4-styrenesulfonate) and is pasted using its dispersing agent and the synthesis of dress material arrangement |
| MYPI2015700943A MY186412A (en) | 2012-10-15 | 2013-09-02 | High-purity sodium p-styrenesulfonate with excellent hue, method for producing the same, poly(sodium p-styrenesulfonate) with excellent hue using the same, and dispersant and synthetic starch for clothing finishing using the poly(sodium p-styrenesulfonate) |
| PCT/JP2013/073503 WO2014061357A1 (en) | 2012-10-15 | 2013-09-02 | High purity sodium p-styrene sulfonate with excellent hue, method for producing same, sodium polystyrenesulfonate with excellent hue using same, and dispersant and finishing synthetic paste for clothes using sodium polystyrenesulfonate |
| US14/432,049 US9505713B2 (en) | 2012-10-15 | 2013-09-02 | High-purity sodium p-styrenesulfonate with excellent hue, method for producing the same, poly(sodium p-styrenesulfonate) with excellent hue using the same, and dispersant and synthetic starch for clothing finishing using the poly(sodium p-styrenesulfonate) |
| TW102136196A TWI579261B (en) | 2012-10-15 | 2013-10-07 | Hue excellent high purity p-styrene sulfonate, and its manufacturing method, using its excellent hue Sodium polystyrene sulfonate, and a dispersant using sodium polystyrene sulfonate, and a synthetic paste for finishing the cloth |
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| JPS5223038A (en) * | 1975-07-03 | 1977-02-21 | Toyo Soda Mfg Co Ltd | Process for preparation of styrenesulfonic acid alkali metal salts |
| JPS5531059A (en) * | 1978-10-18 | 1980-03-05 | Toyo Soda Mfg Co Ltd | Preparation of alkali metal p-styrenesulfonate |
| JPH03168239A (en) * | 1989-11-28 | 1991-07-22 | Mita Ind Co Ltd | Resin particle having polar group on surface of particle and production thereof |
| JP3890642B2 (en) * | 1996-12-20 | 2007-03-07 | 東ソー株式会社 | Continuous production method of alkali metal styrene sulfonate |
| JP5954798B2 (en) * | 2011-11-16 | 2016-07-20 | 東ソー有機化学株式会社 | High-purity parastyrene sulfonic acid (salt), polystyrene sulfonic acid (salt) using the same, and dispersant, conductive polymer dopant, nanocarbon material aqueous dispersion, conductive polymer using polystyrene sulfonic acid (salt) Aqueous dispersion and method for producing polystyrene sulfonic acid (salt) |
| JP5946094B2 (en) * | 2012-10-16 | 2016-07-05 | 東ソー有機化学株式会社 | High-purity sodium parastyrene sulfonate with excellent hue, polystyrene sodium sulfonate with excellent hue using the same, dispersant using the sodium polystyrene sulfonate, and synthetic paste for clothing finishing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10011563B2 (en) | 2014-02-05 | 2018-07-03 | Tosoh Corporation | Lithium styrene sulfonate |
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