JP4399972B2 - Process for producing β-alanine-N, N-diacetic acid trialkali metal salt - Google Patents
Process for producing β-alanine-N, N-diacetic acid trialkali metal salt Download PDFInfo
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- JP4399972B2 JP4399972B2 JP2000282529A JP2000282529A JP4399972B2 JP 4399972 B2 JP4399972 B2 JP 4399972B2 JP 2000282529 A JP2000282529 A JP 2000282529A JP 2000282529 A JP2000282529 A JP 2000282529A JP 4399972 B2 JP4399972 B2 JP 4399972B2
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- alkali metal
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- alanine
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- 150000003839 salts Chemical class 0.000 title claims description 30
- 229910052751 metal Inorganic materials 0.000 title claims description 29
- 239000002184 metal Substances 0.000 title claims description 29
- UWRBFYBQPCJRRL-UHFFFAOYSA-N 3-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CC(O)=O)CC(O)=O UWRBFYBQPCJRRL-UHFFFAOYSA-N 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 64
- 229910052783 alkali metal Inorganic materials 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 48
- -1 glycine alkali metal salt Chemical class 0.000 claims description 42
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 35
- 238000004519 manufacturing process Methods 0.000 claims description 26
- 239000004471 Glycine Substances 0.000 claims description 22
- 239000012266 salt solution Substances 0.000 claims description 15
- GAUBNQMYYJLWNF-UHFFFAOYSA-N 3-(Carboxymethylamino)propanoic acid Chemical compound OC(=O)CCNCC(O)=O GAUBNQMYYJLWNF-UHFFFAOYSA-N 0.000 claims description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 13
- 150000001340 alkali metals Chemical class 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- KZUBZCHAWPDYQX-UHFFFAOYSA-N 2-(2-cyanoethylamino)acetic acid Chemical compound OC(=O)CNCCC#N KZUBZCHAWPDYQX-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 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 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 12
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- UVLMYKDGSGLQHH-UHFFFAOYSA-L disodium 3-(carboxylatomethylamino)propanoate Chemical compound [Na+].[Na+].[O-]C(=O)CCNCC([O-])=O UVLMYKDGSGLQHH-UHFFFAOYSA-L 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- HCNXOAVRFDDVDB-UHFFFAOYSA-M sodium;2-(2-cyanoethylamino)acetate Chemical compound [Na+].[O-]C(=O)CNCCC#N HCNXOAVRFDDVDB-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IVZOJBMAVRDAOD-UHFFFAOYSA-K trisodium;3-[bis(carboxylatomethyl)amino]propanoate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CCN(CC([O-])=O)CC([O-])=O IVZOJBMAVRDAOD-UHFFFAOYSA-K 0.000 description 3
- NBTKLDOLKQLAMC-UHFFFAOYSA-N 2-(dicarboxyamino)butanoic acid Chemical compound CCC(C(O)=O)N(C(O)=O)C(O)=O NBTKLDOLKQLAMC-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
- 229940000635 beta-alanine Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- AGSPXMVUFBBBMO-UHFFFAOYSA-N beta-aminopropionitrile Chemical compound NCCC#N AGSPXMVUFBBBMO-UHFFFAOYSA-N 0.000 description 1
- AGSPXMVUFBBBMO-UHFFFAOYSA-O beta-ammoniopropionitrile Chemical compound [NH3+]CCC#N AGSPXMVUFBBBMO-UHFFFAOYSA-O 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は生分解性キレート剤として有用であり、詳しくは洗剤組成物、洗剤ビルダー、特にハロゲン化銀写真感光材料分野で使用される酸化剤、例えばハロゲン化銀カラー写真感光材料の漂白処理に使われる漂白処理剤の原料として有用なβ−アラニン−Ｎ,Ｎ−二酢酸三アルカリ金属塩の製造方法に関するものである。
【０００２】
【従来の技術】
β−アラニン−Ｎ,Ｎ−二酢酸三アルカリ金属塩の製造方法は、３−アミノプロピオニトリルに、青酸とホルムアルデヒドをアルカリ金属水酸化物の存在下で反応させる方法（特開平７−２４２６０７号公報）、イミノ二酢酸をアクリロニトリルと弱酸酸性から弱塩基性の水性媒体中で反応させ、引き続きニトリルを酸又は塩に鹸化する方法 （特表平７−５０６５８１号公報）、β−アラニンをアルカリ金属シアン化物及びホルムアルデヒドと水性アルカリ性媒体中で反応させる方法（特開平４−２９０８５４号公報）が知られている。
【０００３】
しかしながら、３−アミノプロピオニトリルやイミノ二酢酸やβ−アラニンを原料とする場合は原料の製造工程が煩雑であり、非効率であった。
【０００４】
【発明が解決しようとする課題】
本発明は従来技術の問題点を解決すべくなされたもので、β−アラニン−Ｎ,Ｎ−二酢酸三アルカリ金属塩の効率の良い製造方法を提供することを課題とする。具体的には工業的に容易に入手可能な原料を用い収率の良いβ−アラニン−Ｎ,Ｎ−二酢酸三アルカリ金属塩の製造方法を提供することを課題とする。
【０００５】
【課題を解決するための手段】
上記課題は以下の製造方法により解決された。
【０００６】
すなわち、本発明は以下の事項からなる。
【０００７】
[1] アクリロニトリルとグリシン又はグリシンアルカリ金属塩を反応させて一般式（１）、
【化４】
【化５】
【化６】
【０００８】
[2] 第１工程におけるグリシン又はグリシンアルカリ金属塩に対するアクリロニトリルのモル比が０．５〜１．５である[1]の製造方法。
[3] 第１工程の反応温度が０℃〜７０℃である[1]または[2]の製造方法。
[4] 第２工程の加水分解反応を、アルカリ金属水酸化物水溶液にＮ−２−シアノエチルグリシンアルカリ金属塩溶液を滴下して行うことを特徴とする[1]〜[3]の製造方法。
[5] 第２工程の反応温度が、３０℃〜８０℃である[1]〜[4]の製造方法。
【０００９】
[6] 第３工程の反応圧力が２０ｋＰａ〜７０ｋＰａであり反応温度が７０℃〜９５℃である[1]〜[5]の製造方法。
[7] 第３工程の反応を、シアン化アルカリ金属塩とホルムアルデヒドをＮ−２−カルボキシエチルグリシン二アルカリ金属塩に添加し、かつシアン化アルカリ金属塩の添加をホルムアルデヒドの添加よりも先に完了させることを特徴とする[1]〜[6]の製造方法。
[8] アルカリ金属がナトリウムである[1]〜[7]の製造方法。
【００１０】
【発明の実施の形態】
以下、本発明の製造方法につき詳細に説明する。
【００１１】
本発明のβ−アラニン−Ｎ,Ｎ−二酢酸三アルカリ金属塩の製造方法は、アクリロニトリルとグリシン又はグリシンアルカリ金属塩を反応させて一般式（１）、
【００１２】
【化７】
【００１３】
【化８】
【００１４】
【化９】
【００１５】
以下、本発明のβ−アラニン−Ｎ,Ｎ−二酢酸三アルカリ金属塩の製造方法を工程毎に説明する。
【００１６】
第 1 工程
本工程においては、アクリロニトリルとグリシン又はグリシンアルカリ金属塩を反応容器に仕込み所定時間、所定温度で攪拌下反応させて、式（１）で示されるＮ−２−シアノエチルグリシンアルカリ金属塩を製造する。
【００１７】
本工程の反応温度は、０℃〜７０℃が好ましい。反応温度が高すぎると生成したＮ−２−シアノエチルグリシンアルカリ金属塩の分解および、Ｎ，Ｎ−二カルボキエチルグリシンの副生量が増加するので好ましくない。一方、反応温度が低すぎると反応速度が遅くなり、Ｎ−２−シアノエチルグリシンアルカリ金属塩の生産性が悪くなる。
【００１８】
本工程におけるグリシンに対するアクリロニトリルのモル比は０．５〜１．５が好ましい。グリシンに対するアクリロニトリルのモル比が小さいと未反応のグリシンが第３工程においてホルムアルデヒド水溶液とシアン化アルカリ金属塩と反応しイミノ二酢酸やニトリロ三酢酸が増加してしまう。一方グリシンに対するアクリロニトリルのモル比が大きいと不純物であるＮ，Ｎ−二カルボキエチルグリシンの副生量が増加するので好ましくない。
【００１９】
本工程の原料に用いられるアクリロニトリル、グリシン及びグリシンアルカリ金属塩は、いかなる方法で得られたものでも用いられる。入手容易な工業用グレードが通常用いられる。
【００２０】
本工程で得られるＮ−２−シアノエチルグリシンアルカリ金属塩は、濃縮、蒸発乾固等の後処理をして濃縮液または固体として取得し次工程に使用してもよいが、効率化の観点から反応で得られるＮ−２−シアノエチルグリシンアルカリ金属塩溶液をそのまま次工程の原料として使用するのが好ましい。
【００２１】
第２工程
本工程においては、第1工程で得られた式（１）で示されるＮ−２−シアノエチルグリシンアルカリ金属塩およびアルカリ金属水酸化物を反応容器に仕込み攪拌下加水分解反応し、一般式（２）で示されるＮ−２−カルボキシエチルグリシン二アルカリ金属塩を製造する。
【００２２】
本工程においては、アルカリ金属水酸化物水溶液にＮ−２−シアノエチルグリシンアルカリ金属塩溶液を滴下して反応させることが好ましい。Ｎ−２−シアノエチルグリシンアルカリ金属塩溶液とアルカリ金属水酸化物水溶液を一括混合、又はＮ−２−シアノエチルグリシンアルカリ金属塩溶液にアルカリ金属水酸化物水溶液を滴下すると反応が暴走する場合があり好ましくない。
【００２３】
本工程においては、反応温度が３０℃〜８０℃であることが好ましい。温度が高すぎると、この工程の原料であるＮ−２−シアノエチルグリシンアルカリ金属塩および生成物であるＮ−２−カルボキシエチルグリシン二アルカリ塩の分解が起こるので好ましくない。一方温度が低すぎると反応速度が遅くなり、生産性が悪くなる。
【００２４】
本工程で使用される原料であるアルカリ金属水酸化物としては、例えば，水酸化ナトリウム、水酸化カリウム等が用いられる。汎用性の観点から水酸化ナトリウムが好ましい。
【００２５】
本工程で得られるＮ−２−カルボキシエチルグリシン二アルカリ金属塩は、濃縮、蒸発乾固等の後処理をして、濃縮液または固体として取得し次工程に使用してもよいが、効率化の観点から反応で得られるＮ−２−カルボキシエチルグリシン二アルカリ金属塩溶液をそのまま次工程の原料として使用するのが好ましい。
【００２６】
第 3 工程
本工程においては、第2工程で得られた式（２）で示されるＮ−２−カルボキシエチルグリシン二アルカリ金属塩、シアン化アルカリ金属塩およびホルムアルデヒドを反応容器に仕込み攪拌下反応させて、一般式（３）で示されるβ−アラニン−Ｎ,Ｎ−二酢酸三アルカリ金属塩を製造する。
【００２７】
本工程におけるシアン化アルカリ金属塩とホルムアルデヒドの反応方法は、Ｎ−２−カルボキシエチルグリシン二アルカリ金属塩にシアン化アルカリ金属塩とホルムアルデヒドを添加し、かつシアン化アルカリ金属塩の添加をホルムアルデヒドの添加よりも先に完了させる反応方法が好ましい。シアン化アルカリ金属塩、ホルムアルデヒドおよびＮ−２−カルボキシエチルグリシン二アルカリ金属塩を一括混合すると、β−アラニン−Ｎ,Ｎ−二酢酸三アルカリ金属塩収率の低下、不純物の増加および反応液の着色が起こるので好ましくない。また、シアン化アルカリ金属塩とホルムアルデヒドをＮ−２−カルボキシエチルグリシン二アルカリ塩に添加して反応させる場合でもシアン化アルカリ金属塩の添加をホルムアルデヒドの添加と同時に終わらせたり、またはホルムアルデヒドの添加の終了する前に終わらせると、生成するβ−アラニン−Ｎ,Ｎ−二酢酸三アルカリ金属塩収率の低下、不純物の増加および反応液の着色が起こる。
【００２８】
本工程における反応圧力は７０ｋＰａ〜２０ｋＰａであり、反応温度は９５℃〜７０℃である。反応圧力および反応温度が高すぎると、この工程の原料であるＮ−２−カルボキシエチルグリシン二アルカリ塩および生成物であるβ−アラニン−Ｎ,Ｎ−二酢酸三アルカリ金属塩の分解が起こるので、好ましくない。更に、本反応で副生するアンンモニアは、反応圧力が高いと反応液から除去されず反応液中に溶存し、ホルムアルデヒドおよびシアン化アルカリ金属塩と反応し不純物であるイミノ二酢酸やニトリロ三酢酸を生成するので好ましくない。一方、反応圧力、反応温度が低すぎると反応速度が遅くなり、生産性が悪くなる。
【００２９】
本工程の原料に用いられるホルムアルデヒドには、特に制限はないが、通常工業的に入手可能なホルムアルデヒドの水溶液が用いられる。
【００３０】
本工程の原料に用いられるシアン化アルカリ金属塩には、特に制限はないが、通常工業的に入手可能なシアン化ナトリウムやシアン化カリウムが用いられる。
【００３１】
本発明の製造方法により得られるβ−アラニン−Ｎ,Ｎ−二酢酸三アルカリ金属塩溶液は、所望の場合は、反応完了液を濃縮、蒸発乾固等により結晶化させて取得することもできる。
【００３２】
また、β−アラニン−Ｎ,Ｎ−二酢酸を取得する場合は、本発明の製造方法により得られるβ−アラニン−Ｎ,Ｎ−二酢酸三アルカリ金属塩溶液を常法により酸で中和、冷却するとβ−アラニン−Ｎ,Ｎ−二酢酸が晶出するので、常法により、ろ過、乾燥してβ−アラニン−Ｎ,Ｎ−二酢酸の結晶を得ることができる。乾燥等して、
【００３３】
【実施例】
以下、実施例により更に詳しく本発明を説明するが、本発明の技術範囲を制限するものではない。
【００３４】
（参考例１）
第一工程 １Ｌガラス製セパラブルフラスコに５０％グリシンナトリウム溶液３８９gを仕込み、フラスコを氷−水バスで４０℃に冷却しながら２５％アクリル酸ナトリウム水溶液７５２ｇを４０分間で滴下した。その後、４０℃で１時間攪拌した。
第二工程 １Ｌガラス製セパラブルフラスコに１０％水酸化ナトリウム４４０gを仕込み、第一工程で合成したＮ−２−シアノエチルグリシンナトリウム塩溶液３３１gを７０℃で４０分間かけて滴下した。２０kＰaで１時間攪拌し、反応で発生したアンモニアを留去した。
【００３５】
第三工程 第二工程で合成したＮ−２−カルボキシエチルグリシン二ナトリウム塩溶液を８０℃に加熱し３２％シアン化ナトリウムを１８．４ｇ添加した。３４ｋＰaでアンモニアを留去しながら３２％シアン化ナトリウム１６６ｇ及び４０％ホルムアルデヒド水溶液９１ｇを同時に滴下開始した。
【００３６】
シアン化ナトリウムは１１０分で滴下し、ホルムアルデヒド水溶液は１２０分で滴下した。その後、８０℃で３０分攪拌した。β−アラニン−Ｎ,Ｎ−二酢酸三ナトリウム塩のグリシンナトリウムベースの収率は２５％であった。
【００３７】
（実施例１）
第一工程 １Ｌガラス製セパラブルフラスコに５０％グリシンソーダ３８９gと純水１０７ｇを仕込み、フラスコを氷−水バスで４０℃に冷却しながらアクリロニトリル１０６ｇを４０分間で滴下した。その後、４０℃で１時間攪拌した。
第二工程 １Ｌガラス製セパラブルフラスコに１０％水酸化ナトリウム４４０gを仕込み、第一工程で合成したＮ−２−シアノエチルグリシンナトリウム塩溶液３３１gを７０℃で４０分間かけて滴下した。２０kＰaで１時間攪拌し、反応で発生したアンモニアを留去した。
【００３８】
第三工程 第二工程で合成したＮ−２−カルボキシエチルグリシン二ナトリウム塩溶液を８０℃に加熱し３２％シアン化ナトリウムを１８．４ｇ添加した。３４ｋＰaでアンモニアを留去しながら３２％シアン化ナトリウム１６６ｇ及び４０％ホルムアルデヒド水溶液９１ｇを同時に滴下開始した。
【００３９】
シアン化ナトリウムは１１０分で滴下し、ホルムアルデヒド水溶液は１２０分で滴下した。その後、８０℃で３０分攪拌した。反応液のシアン濃度は０．１％であり、残存シアンを無くすために、４０％ホルムアルデヒド水溶液を１ｇ添加し８０℃で３０分間攪拌した。β−アラニン−Ｎ,Ｎ−二酢酸三ナトリウム塩のグリシンナトリウムベースの収率は８５％であった。
【００４０】
（実施例２）
第一工程 ７０Ｌステンレス製反応槽に５０％グリシンソーダ２１．１Kｇを仕込み、反応槽のジャケットに冷却水を流して４０℃に冷却しながらアクリロニトリル５．６２Kｇを３０分間で滴下した。その後、４０℃で１時間攪拌した。
第二工程 ７０Ｌステンレス製反応槽に１０％水酸化ナトリウム４０．２Kｇを仕込み、第一工程で合成したＮ−２−シアノエチルグリシンナトリウム塩溶液２５．０Kｇを７０℃で３０分間かけてフィードした。４０kＰaで２時間攪拌し、反応で発生したアンモニアを留去した。
【００４１】
第三工程 第二 工程で合成したＮ−２−カルボキシエチルグリシン二ナトリウム塩溶液を８０℃に加熱し３４％シアン化ナトリウムを１．４２Kｇ添加した。４５ｋＰaでアンモニアを留去しながら３４％シアン化ナトリウム１２．７Kｇ及び４０％ホルムアルデヒド水溶液６．４６Kｇを同時に滴下開始した。
【００４２】
シアン化ナトリウムは１１０分で滴下し、ホルムアルデヒド水溶液は１２０分で滴下した。その後、９０℃で３０分攪拌した。反応液のシアン濃度は０．１％であり、残存シアンを無くすために、４０％ホルムアルデヒド水溶液を１．１５Kｇ添加し８０℃で６０分間攪拌した。β−アラニン−Ｎ,Ｎ−二酢酸三ナトリウム塩のグリシンナトリウムベースの収率は８６％であった。
【００４３】
【発明の効果】
本発明により、β−アラニン−Ｎ,Ｎ−二酢酸アルカリ金属塩を効率よく製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention is useful as a biodegradable chelating agent. In particular, it is used for bleaching treatment of detergent compositions, detergent builders, particularly oxidizing agents used in the field of silver halide photographic materials, such as silver halide color photographic materials. The present invention relates to a method for producing a β-alanine-N, N-diacetic acid trialkali metal salt useful as a raw material for a bleaching agent.
[0002]
[Prior art]
A method for producing β-alanine-N, N-diacetic acid trialkali metal salt is a method in which 3-aminopropionitrile is reacted with hydrocyanic acid and formaldehyde in the presence of an alkali metal hydroxide (Japanese Patent Laid-Open No. 7-242607). Publication), a method in which iminodiacetic acid is reacted with acrylonitrile in a weak acid acidic to weak basic aqueous medium, followed by saponification of nitrile into an acid or salt (Japanese Patent Publication No. 7-506581), β-alanine as an alkali metal A method of reacting cyanide and formaldehyde with an aqueous alkaline medium (JP-A-4-290854) is known.
[0003]
However, when 3-aminopropionitrile, iminodiacetic acid, or β-alanine is used as a raw material, the raw material manufacturing process is complicated and inefficient.
[0004]
[Problems to be solved by the invention]
The present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide an efficient method for producing β-alanine-N, N-diacetic acid trialkali metal salt. Specifically, it is an object of the present invention to provide a method for producing a β-alanine-N, N-diacetic acid trialkali metal salt having a good yield using industrially easily available raw materials.
[0005]
[Means for Solving the Problems]
The above problems have been solved by the following manufacturing method.
[0006]
That is, this invention consists of the following matters.
[0007]
[1] By reacting acrylonitrile with glycine or a glycine alkali metal salt,
[Formula 4]
[Chemical formula 5]
[Chemical 6]
[0008]
[2] The process according to [1], wherein the molar ratio of acrylonitrile to glycine or glycine alkali metal salt in the first step is 0.5 to 1.5.
[3] The production method of [1] or [2], wherein the reaction temperature in the first step is 0 ° C to 70 ° C.
[4] The method according to [1] to [3], wherein the hydrolysis reaction in the second step is performed by dropping an N-2-cyanoethylglycine alkali metal salt solution into an alkali metal hydroxide aqueous solution.
[5] The production method of [1] to [4], wherein the reaction temperature in the second step is 30 ° C to 80 ° C.
[0009]
[6] The production method of [1] to [5], wherein the reaction pressure in the third step is 20 kPa to 70 kPa, and the reaction temperature is 70 ° C to 95 ° C.
[7] The third step reaction is completed by adding alkali metal cyanide and formaldehyde to N-2-carboxyethylglycine dialkali metal salt and adding alkali metal cyanide prior to the addition of formaldehyde A production method of [1] to [6], wherein
[8] The production method of [1] to [7], wherein the alkali metal is sodium.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the production method of the present invention will be described in detail.
[0011]
The method for producing a β-alanine-N, N-diacetic acid trialkali metal salt of the present invention comprises reacting acrylonitrile with glycine or a glycine alkali metal salt to give a general formula (1),
[0012]
[Chemical 7]
[0013]
[Chemical 8]
[0014]
[Chemical 9]
[0015]
Hereinafter, the manufacturing method of (beta) -alanine-N, N-diacetic acid trialkali metal salt of this invention is demonstrated for every process.
[0016]
In the first step <br/> present process, acrylonitrile and glycine or charged predetermined time glycine alkali metal salt to the reaction vessel, by stirring the reaction at a predetermined temperature, N-2-cyanoethyl glycine of the formula (1) An alkali metal salt is produced.
[0017]
The reaction temperature in this step is preferably 0 ° C to 70 ° C. If the reaction temperature is too high, decomposition of the produced N-2-cyanoethylglycine alkali metal salt and by-product amount of N, N-dicarboxyethylglycine increase, which is not preferable. On the other hand, when the reaction temperature is too low, the reaction rate becomes slow and the productivity of the N-2-cyanoethylglycine alkali metal salt becomes poor.
[0018]
The molar ratio of acrylonitrile to glycine in this step is preferably 0.5 to 1.5. If the molar ratio of acrylonitrile to glycine is small, unreacted glycine reacts with an aqueous formaldehyde solution and an alkali metal cyanide salt in the third step, and iminodiacetic acid and nitrilotriacetic acid increase. On the other hand, if the molar ratio of acrylonitrile to glycine is large, the amount of by-produced N, N-dicarboxyethylglycine which is an impurity increases, which is not preferable.
[0019]
The acrylonitrile, glycine and glycine alkali metal salt used for the raw material in this step may be those obtained by any method. Industrial grades that are readily available are usually used.
[0020]
The N-2-cyanoethylglycine alkali metal salt obtained in this step may be obtained as a concentrated solution or solid by post-concentration, evaporation to dryness, etc. and used in the next step. The N-2-cyanoethylglycine alkali metal salt solution obtained by the reaction is preferably used as it is as a raw material for the next step.
[0021]
Second step In this step, the N-2-cyanoethylglycine alkali metal salt and alkali metal hydroxide represented by the formula (1) obtained in the first step are charged into a reaction vessel and hydrolyzed with stirring. By reacting, an N-2-carboxyethylglycine dialkali metal salt represented by the general formula (2) is produced.
[0022]
In this step, it is preferable to cause the N-2-cyanoethylglycine alkali metal salt solution to drop and react with the alkali metal hydroxide aqueous solution. N-2-cyanoethylglycine alkali metal salt solution and alkali metal hydroxide aqueous solution are mixed at once, or the reaction may run out of control when the alkali metal hydroxide aqueous solution is dropped into N-2-cyanoethylglycine alkali metal salt solution. Absent.
[0023]
In this step, the reaction temperature is preferably 30 ° C to 80 ° C. If the temperature is too high, decomposition of the N-2-cyanoethylglycine alkali metal salt, which is the raw material of this step, and the N-2-carboxyethylglycine dialkali salt, which is the product, is not preferable. On the other hand, when the temperature is too low, the reaction rate becomes slow, and the productivity becomes worse.
[0024]
Examples of the alkali metal hydroxide that is a raw material used in this step include sodium hydroxide and potassium hydroxide. Sodium hydroxide is preferable from the viewpoint of versatility.
[0025]
The N-2-carboxyethylglycine dialkali metal salt obtained in this step may be post-treated by concentration, evaporation to dryness, etc. to obtain it as a concentrate or solid and use it in the next step. From the viewpoint of the above, it is preferable to use the N-2-carboxyethylglycine dialkali metal salt solution obtained by the reaction as it is as a raw material for the next step.
[0026]
In the third step <br/> this step, charged N-2- carboxyethyl glycine di-alkali metal salt of the formula (2) obtained in the second step, a cyanide alkali metal salt and formaldehyde in a reaction vessel The reaction is carried out with stirring to produce a β-alanine-N, N-diacetic acid trialkali metal salt represented by the general formula (3).
[0027]
The reaction method of alkali metal cyanide salt and formaldehyde in this step is to add alkali metal cyanide salt and formaldehyde to N-2-carboxyethylglycine dialkali metal salt, and add alkali metal cyanide salt to formaldehyde. A reaction method that is completed earlier than this is preferred. When alkali metal cyanide, formaldehyde, and N-2-carboxyethylglycine dialkali metal salt were mixed together, β-alanine-N, N-diacetic acid trialkali metal salt yield decreased, impurities increased, and reaction solution Since coloring occurs, it is not preferable. In addition, even when alkali metal cyanide and formaldehyde are added to N-2-carboxyethylglycine dialkali salt for reaction, the addition of alkali metal cyanide salt is terminated simultaneously with the addition of formaldehyde, or the addition of formaldehyde If the process is terminated before completion, the yield of β-alanine-N, N-diacetic acid trialkali metal salt produced, increase in impurities, and coloring of the reaction solution occur.
[0028]
The reaction pressure in this step is 70 kPa to 20 kPa, and the reaction temperature is 95 ° C to 70 ° C. If the reaction pressure and temperature are too high, decomposition of N-2-carboxyethylglycine dialkali salt, which is the raw material of this step, and β-alanine-N, N-diacetic acid trialkali metal salt, which is the product, occurs. It is not preferable. Furthermore, the ammonia produced as a by-product in this reaction is not removed from the reaction solution when the reaction pressure is high, but dissolves in the reaction solution, reacts with formaldehyde and alkali metal cyanide, and impurities such as iminodiacetic acid and nitrilotriacetic acid. Since it produces | generates, it is not preferable. On the other hand, when the reaction pressure and the reaction temperature are too low, the reaction rate becomes slow and the productivity becomes worse.
[0029]
Although there is no restriction | limiting in particular in the formaldehyde used for the raw material of this process, Usually the aqueous solution of formaldehyde which can be obtained industrially is used.
[0030]
Although there is no restriction | limiting in particular in the alkali metal cyanide salt used for the raw material of this process, Usually, industrially available sodium cyanide and potassium cyanide are used.
[0031]
If desired, the β-alanine-N, N-diacetic acid trialkali metal salt solution obtained by the production method of the present invention can be obtained by concentrating the reaction completion liquid and crystallizing it by evaporation to dryness. .
[0032]
Moreover, when obtaining β-alanine-N, N-diacetic acid, the β-alanine-N, N-diacetic acid trialkali metal salt solution obtained by the production method of the present invention is neutralized with an acid by a conventional method. When cooled, β-alanine-N, N-diacetic acid crystallizes, and thus, crystals of β-alanine-N, N-diacetic acid can be obtained by filtration and drying by a conventional method. Dry etc.
[0033]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, it does not restrict | limit the technical scope of this invention.
[0034]
(Reference Example 1)
First Step A 1 L glass separable flask was charged with 389 g of a 50% sodium glycine solution, and 752 g of a 25% aqueous sodium acrylate solution was added dropwise over 40 minutes while the flask was cooled to 40 ° C. with an ice-water bath. Then, it stirred at 40 degreeC for 1 hour.
Second Step 440 g of 10% sodium hydroxide was charged into a 1 L glass separable flask, and 331 g of N-2-cyanoethylglycine sodium salt solution synthesized in the first step was added dropwise at 70 ° C. over 40 minutes. The mixture was stirred at 20 kPa for 1 hour, and ammonia generated by the reaction was distilled off.
[0035]
Third Step The N-2-carboxyethylglycine disodium salt solution synthesized in the second step was heated to 80 ° C., and 18.4 g of 32% sodium cyanide was added. While ammonia was distilled off at 34 kPa, 166 g of 32% sodium cyanide and 91 g of 40% formaldehyde aqueous solution were simultaneously added dropwise.
[0036]
Sodium cyanide was added dropwise in 110 minutes, and the aqueous formaldehyde solution was added dropwise in 120 minutes. Then, it stirred at 80 degreeC for 30 minutes. The yield of β-alanine-N, N-diacetic acid trisodium salt based on sodium glycine was 25%.
[0037]
Example 1
First Step: A 1 L glass separable flask was charged with 389 g of 50% glycine soda and 107 g of pure water, and 106 g of acrylonitrile was added dropwise over 40 minutes while cooling the flask to 40 ° C. with an ice-water bath. Then, it stirred at 40 degreeC for 1 hour.
Second Step 440 g of 10% sodium hydroxide was charged into a 1 L glass separable flask, and 331 g of N-2-cyanoethylglycine sodium salt solution synthesized in the first step was added dropwise at 70 ° C. over 40 minutes. The mixture was stirred at 20 kPa for 1 hour, and ammonia generated by the reaction was distilled off.
[0038]
Third Step The N-2-carboxyethylglycine disodium salt solution synthesized in the second step was heated to 80 ° C., and 18.4 g of 32% sodium cyanide was added. While ammonia was distilled off at 34 kPa, 166 g of 32% sodium cyanide and 91 g of 40% formaldehyde aqueous solution were simultaneously added dropwise.
[0039]
Sodium cyanide was added dropwise in 110 minutes, and the aqueous formaldehyde solution was added dropwise in 120 minutes. Then, it stirred at 80 degreeC for 30 minutes. The cyan concentration of the reaction solution was 0.1%, and 1 g of 40% formaldehyde aqueous solution was added and stirred at 80 ° C. for 30 minutes in order to eliminate residual cyan. The yield of β-alanine-N, N-diacetic acid trisodium salt based on sodium glycine was 85%.
[0040]
(Example 2)
First Step: 21.1 kg of 50% glycine soda was charged in a 70 L stainless steel reaction vessel, and 5.62 kg of acrylonitrile was added dropwise over 30 minutes while cooling water to the jacket of the reaction vessel and cooling to 40 ° C. Then, it stirred at 40 degreeC for 1 hour.
Second Step 40.2 kg of 10% sodium hydroxide was charged into a 70 L stainless steel reaction vessel, and 25.0 kg of the N-2-cyanoethylglycine sodium salt solution synthesized in the first step was fed at 70 ° C. over 30 minutes. The mixture was stirred at 40 kPa for 2 hours, and ammonia generated by the reaction was distilled off.
[0041]
Third Step The N-2-carboxyethylglycine disodium salt solution synthesized in the second step was heated to 80 ° C., and 1.42 kg of 34% sodium cyanide was added. While distilling off ammonia at 45 kPa, 12.7 kg of 34% sodium cyanide and 6.46 kg of 40% aqueous formaldehyde were simultaneously added dropwise.
[0042]
Sodium cyanide was added dropwise in 110 minutes, and the aqueous formaldehyde solution was added dropwise in 120 minutes. Then, it stirred at 90 degreeC for 30 minutes. The cyan concentration of the reaction solution was 0.1%, and in order to eliminate residual cyan, 1.15 kg of 40% formaldehyde aqueous solution was added and stirred at 80 ° C. for 60 minutes. The yield of β-alanine-N, N-diacetic acid trisodium salt based on sodium glycine was 86%.
[0043]
【The invention's effect】
According to the present invention, an alkali metal salt of β-alanine-N, N-diacetic acid can be produced efficiently.
Claims (8)
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