JP2002097193A - Method for purifying organophosphonic acid - Google Patents
Method for purifying organophosphonic acidInfo
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- JP2002097193A JP2002097193A JP2000285427A JP2000285427A JP2002097193A JP 2002097193 A JP2002097193 A JP 2002097193A JP 2000285427 A JP2000285427 A JP 2000285427A JP 2000285427 A JP2000285427 A JP 2000285427A JP 2002097193 A JP2002097193 A JP 2002097193A
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- ppm
- aqueous solution
- phosphonic acid
- organic phosphonic
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有機ホスホン酸の
精製方法に関するものである。TECHNICAL FIELD The present invention relates to a method for purifying an organic phosphonic acid.
【０００２】[0002]
【従来の技術】有機ホスホン酸類は、金属イオンのキレ
ート化剤として周知であり、スケール除去剤や微量の金
属の存在により分解する過酸化物の安定化剤として広く
用いられているほか、そのキレート化能を利用して多様
な分野に応用されている。2. Description of the Related Art Organic phosphonic acids are well known as chelating agents for metal ions, and are widely used as descaling agents and stabilizers for peroxides decomposed by the presence of trace amounts of metals. It has been applied to various fields using chemical abilities.
【０００３】有機ホスホン酸の製造方法としては、塩酸
酸性下、アンモニアまたはアミン、アルデヒドまたはケ
トンおよびホスホン酸からアミノアルキレンホスホン酸
を得る方法（米国特許３,２８８,８４６号、Journal of
Organic Chemistry 第３１巻１６０３頁）などが知ら
れている。As a method for producing an organic phosphonic acid, a method for obtaining an aminoalkylenephosphonic acid from ammonia or an amine, an aldehyde or a ketone and a phosphonic acid under hydrochloric acid acidity (US Pat. No. 3,288,846, Journal of Japan)
Organic Chemistry, Vol. 31, p. 1603) and the like are known.
【０００４】しかしながら、一般的な方法により製造し
た場合や市販品として入手した有機ホスホン酸は、原料
や反応装置から持ちこまれる金属として、Ｆｅなどの重
金属、Ｎａなどのアルカリ金属、Ｃａなどのアルカリ土
類金属などの不純物を少ない場合でも１ｐｐｍ以上、多
い場合には１００ｐｐｍ以上含んでいることがほとんど
である。このような微量の金属不純物を含む有機ホスホ
ン酸は、電子工業や医療関連分野などのある特定の用途
に使用する上で、金属不純物により悪影響を受ける場合
がある。[0004] However, organic phosphonic acids produced by a general method or obtained as a commercial product include heavy metals such as Fe, alkali metals such as Na, and alkaline earths such as Ca as metals brought in from raw materials and reactors. In most cases, impurities such as metals are contained at least 1 ppm, and at most 100 ppm or more. Organic phosphonic acids containing such trace amounts of metal impurities may be adversely affected by metal impurities when used in certain applications such as the electronics industry and medical-related fields.
【０００５】有機ホスホン酸から金属を除去する手段と
して、有機ホスホン酸水溶液に酸を加え、有機ホスホン
酸を固体の酸として晶出分離する方法が可能である。し
かし、多くの有機ホスホン酸は種々の金属との親和性が
非常に高く、すでに述べたような微量の金属不純物を除
去することは困難であり、有効な方法は提案されていな
い。As a means for removing the metal from the organic phosphonic acid, there is a method in which an acid is added to an aqueous solution of the organic phosphonic acid, and the organic phosphonic acid is crystallized and separated as a solid acid. However, many organic phosphonic acids have very high affinity for various metals, and it is difficult to remove a trace amount of metal impurities as described above, and no effective method has been proposed.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、従来技術に
おける上記のような問題を解決し、金属不純物含量が極
めて少ない有機ホスホン酸を提供することにある。An object of the present invention is to solve the above-mentioned problems in the prior art and to provide an organic phosphonic acid having a very low content of metal impurities.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、有機ホス
ホン酸を強酸性陽イオン交換樹脂に接触させることによ
り、微量の金属不純物を除去できることを見出し、本発
明に到達した。すなわち、本発明は、分子内に１つ以上
のホスホン酸基またはその塩を有する有機ホスホン酸を
強酸性陽イオン交換樹脂に接触させることを特徴とする
有機ホスホン酸の精製方法に関するものである。また、
さらに精製度を上げるために、有機ホスホン酸水溶液を
電気透析させる工程と組み合わせてもよい。Means for Solving the Problems The present inventors have found that trace amounts of metal impurities can be removed by bringing an organic phosphonic acid into contact with a strongly acidic cation exchange resin, and have reached the present invention. That is, the present invention relates to a method for purifying an organic phosphonic acid, which comprises contacting an organic phosphonic acid having at least one phosphonic acid group or a salt thereof in a molecule with a strongly acidic cation exchange resin. Also,
In order to further increase the degree of purification, the organic phosphonic acid aqueous solution may be combined with a step of electrodialysis.
【０００８】[0008]
【発明の実施の形態】本発明の有機ホスホン酸は、分子
内に少なくとも１つ以上のホスホン酸基またはその塩を
含む化合物であり、具体的には、メチルジホスホン酸、
エチリデンジホスホン酸、１−ヒドロキシエチリデン−
１，１−ジホスホン酸、１−ヒドロキシプロピリデン−
１，１−ジホスホン酸、１−ヒドロキシブチリデン−
１，１−ジホスホン酸、エチルアミノビス（メチレンホ
スホン酸）、ドデシルアミノビス（メチレンホスホン
酸）、エチレンジアミンビス（メチレンホスホン酸）、
アミノトリ（メチレンホスホン酸）、エチレンジアミン
テトラ（メチレンホスホン酸）、１，２−プロピレンジ
アミンテトラ（メチレンホスホン酸）、ヘキサメチレン
ジアミンテトラ（メチレンホスホン酸）、シクロヘキサ
ンジアミンテトラ（メチレンホスホン酸）、グリコール
エーテルジアミンテトラ（メチレンホスホン酸）、ジエ
チレントリアミンペンタ（メチレンホスホン酸）、トリ
エチレンテトラミンヘキサ（メチレンホスホン酸）、ト
リ（２−アミノエチル）アミンヘキサ（メチレンホスホ
ン酸）、テトラエチレンペンタミンヘプタ（メチレンホ
スホン酸）、ペンタエチレンヘキサミンオクタ（メチレ
ンホスホン酸）、および、これらの塩、並びに、これら
の酸化体が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The organic phosphonic acid of the present invention is a compound containing at least one phosphonic acid group or a salt thereof in a molecule, and specifically includes methyldiphosphonic acid,
Ethylidene diphosphonic acid, 1-hydroxyethylidene-
1,1-diphosphonic acid, 1-hydroxypropylidene-
1,1-diphosphonic acid, 1-hydroxybutylidene-
1,1-diphosphonic acid, ethylaminobis (methylenephosphonic acid), dodecylaminobis (methylenephosphonic acid), ethylenediaminebis (methylenephosphonic acid),
Amino tri (methylene phosphonic acid), ethylene diamine tetra (methylene phosphonic acid), 1,2-propylene diamine tetra (methylene phosphonic acid), hexamethylene diamine tetra (methylene phosphonic acid), cyclohexane diamine tetra (methylene phosphonic acid), glycol ether diamine Tetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), tri (2-aminoethyl) aminehexa (methylenephosphonic acid), tetraethylenepentaminehepta (methylenephosphonic acid), Pentaethylenehexamine octa (methylene phosphonic acid), and salts thereof, and oxidized forms thereof are included.
【０００９】有機ホスホン酸は、一般に水溶液として強
酸性陽イオン交換樹脂に接触させる。有機ホスホン酸の
水への溶解度はそれぞれの化合物で異なり、広範囲にわ
たるが、有機ホスホン酸が沈殿しない均一な溶液である
ことが好ましい。[0009] The organic phosphonic acid is generally brought into contact with a strongly acidic cation exchange resin as an aqueous solution. The solubility of the organic phosphonic acid in water is different for each compound and is wide, but a homogeneous solution in which the organic phosphonic acid does not precipitate is preferable.
【００１０】強酸性陽イオン交換樹脂は、機械的、化学
的に安定な母体により構成されていることが好ましく、
たとえば、スチレン−ジビニルベンゼン共重合体を母体
としたものを好適に用いることができる。そして、強酸
性陽イオン交換樹脂は、スルホン酸基またはその塩に代
表される強酸性基を有するものであり、市販品として、
オルガノ株式会社製のアンバーライトＩＲ１２０Ｂ、２
０１Ｂや三菱化学株式会社製のダイヤイオンＳＫ１Ｂ、
ＰＫ２１２がある。The strongly acidic cation exchange resin is preferably composed of a mechanically and chemically stable matrix.
For example, a material based on a styrene-divinylbenzene copolymer can be suitably used. And a strongly acidic cation exchange resin has a strongly acidic group represented by a sulfonic acid group or a salt thereof, and as a commercially available product,
Organo Corporation Amberlite IR120B, 2
01B and Diaion SK1B manufactured by Mitsubishi Chemical Corporation,
There is a PK212.
【００１１】これらの強酸性陽イオン交換樹脂は、一般
に、酸性基がナトリウム塩の形態で市販されているた
め、酸の水溶液と接触させて酸性基を水素型に変換し、
水洗した後に有機ホスホン酸と接触させる。用いる酸の
種類および濃度、水洗方法に特に制限はなく、塩酸や硫
酸などの酸の水溶液と強酸性陽イオン交換樹脂をバッチ
式または流通式で接触させた後、同様の方法で水と強酸
性陽イオン交換樹脂を接触させればよい。このとき、水
洗に用いる水が金属を含んでいると、金属はイオン交換
樹脂に吸着され、水素型の酸性基が金属塩型に変化する
ため、イオン交換水や超純水のように金属含量が極めて
低いものを用いることが好ましい。Since these strongly acidic cation exchange resins are generally available in the form of a sodium salt in the form of an acidic group, they are brought into contact with an aqueous solution of an acid to convert the acidic group into a hydrogen form.
After washing with water, it is brought into contact with an organic phosphonic acid. There are no particular restrictions on the type and concentration of the acid to be used, and the method of washing with water is not particularly limited. What is necessary is just to contact a cation exchange resin. At this time, if the water used for washing contains a metal, the metal is adsorbed by the ion exchange resin, and the acidic group of the hydrogen type is changed to the metal salt type. Is preferably used.
【００１２】有機ホスホン酸と強酸性陽イオン交換樹脂
を接触させる方法としては、（１）有機ホスホン酸水溶
液に強酸性陽イオン交換樹脂を浸漬する方法、（２）強
酸性陽イオン交換樹脂を充填した充填塔に有機ホスホン
酸水溶液を通液する方法等がある。The method for bringing the organic phosphonic acid into contact with the strongly acidic cation exchange resin includes (1) a method of dipping the strongly acidic cation exchange resin in an aqueous solution of the organic phosphonic acid, and (2) a filling of the strongly acidic cation exchange resin. And a method of passing an organic phosphonic acid aqueous solution through a packed column.
【００１３】（１）の方法では有機ホスホン酸水溶液や
強酸性陽イオン交換樹脂を撹拌等の方法で流動させ、両
者の接触効率を高くすることができる。（２）の方法で
は通液速度に特に制限はないが、空間速度０．５から５
０／時間で通液することが好ましい。In the method (1), an organic phosphonic acid aqueous solution or a strongly acidic cation exchange resin is caused to flow by a method such as stirring, so that the contact efficiency between the two can be increased. In the method (2), the liquid passing speed is not particularly limited, but the space velocity is 0.5 to 5
It is preferable to pass the solution at 0 / hour.
【００１４】いずれの方法においても、接触させる場合
の温度に制限はないが、有機ホスホン酸は一般に水溶液
として強酸性陽イオン交換樹脂と接触させるため、１０
〜９０℃で接触させることが好ましい。In any of the methods, the temperature for contacting is not limited. However, since organic phosphonic acid is generally brought into contact with a strongly acidic cation exchange resin as an aqueous solution, it is difficult to use an organic phosphonic acid.
It is preferred that the contact be made at a temperature of up to 90 ° C.
【００１５】強酸性陽イオン交換樹脂は、使用に伴い金
属吸着能が低下する。その場合、酸の水溶液と接触さ
せ、金属塩となった酸性基を水素型に変換した後、水洗
して、繰り返し使用できる。酸の水溶液を接触させる方
法、用いる酸の種類および濃度、水洗方法に特に制限は
なく、市販の強酸性陽イオン交換樹脂を水素型に変換す
る場合と同様の方法で行うことができる。[0015] The use of a strongly acidic cation exchange resin decreases the metal adsorption capacity with use. In that case, after contacting with an aqueous solution of an acid to convert the acidic group that has become a metal salt into a hydrogen form, it can be washed with water and used repeatedly. There is no particular limitation on the method of contacting the aqueous acid solution, the type and concentration of the acid used, and the washing method, and the method can be carried out in the same manner as in the case of converting a commercially available strongly acidic cation exchange resin into a hydrogen form.
【００１６】[0016]
【実施例】以下に本発明を実施例によって詳細に説明す
るが、本発明は実施例によって制限されるものでない。
なお、有機ホスホン酸水溶液中の金属濃度はＩＣＰ発光
分析により求めた。EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to the examples.
The metal concentration in the organic phosphonic acid aqueous solution was determined by ICP emission analysis.
【００１７】実施例１ 強酸性陽イオン交換樹脂アンバーライトＩＲ１２０Ｂを
５０ｍＬ充填したカラムに１Ｎ硫酸水溶液を空間速度５
／時間で３時間通液して水素型に変換した後、イオン交
換水を通液し水洗した。その後、樹脂を取り出し、５．
０重量％のアミノトリ（メチレンホスホン酸）水溶液３
００ｍＬ中に浸漬、静置した。樹脂と接触させる前の水
溶液は、ナトリウム０．４０ｐｐｍ、カルシウム１．３
３ｐｐｍ、マグネシウム０．１８ｐｐｍを含んでいた。
２４時間経過した後の水溶液は、ナトリウム０．０８ｐ
ｐｍ、カルシウム０．０７ｐｐｍを含み、マグネシウム
濃度は０．０５ｐｐｍ以下であった。Example 1 A 1N aqueous sulfuric acid solution was charged at a space velocity of 5 into a column packed with 50 mL of strongly acidic cation exchange resin Amberlite IR120B.
/ Hour for 3 hours to convert to the hydrogen form, and then ion-exchanged water was passed through and washed. Thereafter, the resin is taken out.
0% by weight aqueous aminotri (methylenephosphonic acid) solution 3
It was immersed in 00 mL and allowed to stand. The aqueous solution before contact with the resin was 0.40 ppm sodium, 1.3% calcium.
It contained 3 ppm and 0.18 ppm of magnesium.
After 24 hours, the aqueous solution contains sodium 0.08p
pm, containing 0.07 ppm of calcium and a magnesium concentration of 0.05 ppm or less.
【００１８】実施例２ 強酸性陽イオン交換樹脂アンバーライトＩＲ１２０Ｂを
５０ｍＬ充填したカラムに１Ｎ硫酸水溶液を空間速度５
／時間で３時間通液して水素型に変換した後、イオン交
換水を通液し水洗した。その後、５．０重量％のアミノ
トリ（メチレンホスホン酸）水溶液３００ｍＬを空間速
度１０／時間で通液した。通液前の水溶液は、ナトリウ
ム０．４０ｐｐｍ、カルシウム１．３３ｐｐｍ、マグネ
シウム０．１８ｐｐｍを含んでいた。通液後の水溶液の
ナトリウム、カルシウム、マグネシウム濃度は、いずれ
も０．０５ｐｐｍ以下であった。Example 2 A column filled with 50 mL of strongly acidic cation exchange resin Amberlite IR120B was charged with a 1N aqueous sulfuric acid solution at a space velocity of 5%.
/ Hour for 3 hours to convert to the hydrogen form, and then ion-exchanged water was passed through and washed. Thereafter, 300 mL of a 5.0% by weight aqueous solution of aminotri (methylenephosphonic acid) was passed at a space velocity of 10 / hour. The aqueous solution before the passage contained 0.40 ppm of sodium, 1.33 ppm of calcium, and 0.18 ppm of magnesium. The sodium, calcium, and magnesium concentrations of the aqueous solution after the passage were all 0.05 ppm or less.
【００１９】実施例３ 強酸性陽イオン交換樹脂ダイヤイオンＰＫ２１２を５０
ｍＬ充填したカラムに１Ｎ硫酸水溶液を空間速度５／時
間で３時間通液して水素型に変換した後、イオン交換水
を通液し水洗した。その後、５．０重量％のアミノトリ
（メチレンホスホン酸）水溶液３００ｍＬを空間速度１
０／時間で通液した。通液前の水溶液は、ナトリウム
０．４０ｐｐｍ、カルシウム１．３３ｐｐｍ、マグネシ
ウム０．１８ｐｐｍを含んでいた。通液後の水溶液のナ
トリウム、カルシウム、マグネシウム濃度は、いずれも
０．０５ｐｐｍ以下であった。EXAMPLE 3 50 strongly acidic cation exchange resin DIAION PK212
After a 1N aqueous sulfuric acid solution was passed through the column packed with mL at a space velocity of 5 / hour for 3 hours to convert to a hydrogen form, ion-exchanged water was passed through and washed with water. Thereafter, 300 mL of a 5.0 wt% aqueous solution of aminotri (methylenephosphonic acid) was added at a space velocity of 1%.
The solution was passed at 0 / hour. The aqueous solution before the passage contained 0.40 ppm of sodium, 1.33 ppm of calcium, and 0.18 ppm of magnesium. The sodium, calcium, and magnesium concentrations of the aqueous solution after the passage were all 0.05 ppm or less.
【００２０】比較例１ 三菱化学株式会社製の弱酸性陽イオン交換樹脂ダイヤイ
オンＷＫ４０を５０ｍＬ充填したカラムにイオン交換水
を通液し水洗した。その後、５．０重量％のアミノトリ
（メチレンホスホン酸）水溶液３００ｍＬを空間速度１
０／時間で通液した。通液前の水溶液は、ナトリウム
０．４０ｐｐｍ、カルシウム１．３３ｐｐｍ、マグネシ
ウム０．１８ｐｐｍを含んでいた。通液後の水溶液は、
ナトリウム０．３１ｐｐｍ、カルシウム１．３５ｐｐ
ｍ、マグネシウム０．１８ｐｐｍを含んでいた。Comparative Example 1 Ion-exchanged water was passed through a column packed with 50 mL of weakly acidic cation exchange resin Diaion WK40 manufactured by Mitsubishi Chemical Corporation to wash it. Thereafter, 300 mL of a 5.0 wt% aqueous solution of aminotri (methylenephosphonic acid) was added at a space velocity of 1%.
The solution was passed at 0 / hour. The aqueous solution before the passage contained 0.40 ppm of sodium, 1.33 ppm of calcium, and 0.18 ppm of magnesium. After passing the aqueous solution,
0.31 ppm of sodium, 1.35 pp of calcium
m, 0.18 ppm of magnesium.
【００２１】比較例２ 三菱化学株式会社製のキレート樹脂ダイヤイオンＣＲ１
１を５０ｍＬ充填したカラムに１Ｎ硫酸水溶液を空間速
度５／時間で３時間通液して水素型に変換した後、イオ
ン交換水を通液し水洗した。その後、５．０重量％のア
ミノトリ（メチレンホスホン酸）水溶液３００ｍＬを空
間速度１０／時間で通液した。通液前の水溶液は、ナト
リウム０．４０ｐｐｍ、カルシウム１．３３ｐｐｍ、マ
グネシウム０．１８ｐｐｍを含んでいた。通液後の水溶
液は、ナトリウム０．２５ｐｐｍ、カルシウム１．１５
ｐｐｍ、マグネシウム０．１４ｐｐｍを含んでいた。Comparative Example 2 Chelate resin Diaion CR1 manufactured by Mitsubishi Chemical Corporation
1N sulfuric acid aqueous solution was passed through a column packed with 50 mL of 1 at a space velocity of 5 / hour for 3 hours to convert into a hydrogen form, and then ion-exchanged water was passed through and washed with water. Thereafter, 300 mL of a 5.0% by weight aqueous solution of aminotri (methylenephosphonic acid) was passed at a space velocity of 10 / hour. The aqueous solution before the passage contained 0.40 ppm of sodium, 1.33 ppm of calcium, and 0.18 ppm of magnesium. The aqueous solution after the passage was 0.25 ppm of sodium and 1.15 ppm of calcium.
ppm and 0.14 ppm of magnesium.
【００２２】実施例４ 強酸性陽イオン交換樹脂アンバーライトＩＲ１２０Ｂを
５０ｍＬ充填したカラムに１Ｎ硫酸水溶液を空間速度５
／時間で３時間通液して水素型に変換した後、イオン交
換水を通液し水洗した。その後、２．０重量％のエチレ
ンジアミンテトラ（メチレンホスホン酸）水溶液３００
ｍＬを空間速度１０／時間で通液した。通液前の水溶液
は、ナトリウム０．２７ｐｐｍ、カルシウム０．５９ｐ
ｐｍを含んでいた。通液後の水溶液のナトリウム、カル
シウム濃度は、いずれも０．０５ｐｐｍ以下であった。Example 4 A 1N aqueous sulfuric acid solution was charged at a space velocity of 5 into a column packed with 50 mL of strongly acidic cation exchange resin Amberlite IR120B.
/ Hour for 3 hours to convert to the hydrogen form, and then ion-exchanged water was passed through and washed. Thereafter, a 2.0% by weight aqueous solution of ethylenediaminetetra (methylenephosphonic acid) 300
mL was passed at a space velocity of 10 / hour. The aqueous solution before passing was 0.27 ppm of sodium and 0.59 p of calcium.
pm. The sodium and calcium concentrations of the aqueous solution after the passage were both 0.05 ppm or less.
【００２３】実施例５ 強酸性陽イオン交換樹脂アンバーライトＩＲ１２０Ｂを
５０ｍＬ充填したカラムに１Ｎ硫酸水溶液を空間速度５
／時間で３時間通液して水素型に変換した後、イオン交
換水を通液し水洗した。その後、５．０重量％のジエチ
レントリアミンペンタ（メチレンホスホン酸）水溶液３
００ｍＬを空間速度１０／時間で通液した。通液前の水
溶液は、ナトリウム３．２３ｐｐｍ、カルシウム４．４
７ｐｐｍ、マグネシウム０．２１ｐｐｍ、亜鉛０．０９
ｐｐｍを含んでいた。通液後の水溶液のナトリウム、カ
ルシウム、マグネシウム、および亜鉛濃度は、いずれも
０．０５ｐｐｍ以下であった。Example 5 A column filled with 50 mL of strongly acidic cation exchange resin Amberlite IR120B was charged with a 1N aqueous solution of sulfuric acid at a space velocity of 5 mL.
/ Hour for 3 hours to convert to the hydrogen form, and then ion-exchanged water was passed through and washed. Thereafter, a 5.0% by weight aqueous solution of diethylenetriaminepenta (methylenephosphonic acid) 3
00 mL was passed at a space velocity of 10 / hour. The aqueous solution before passing was 3.23 ppm sodium and 4.4 calcium.
7 ppm, magnesium 0.21 ppm, zinc 0.09
ppm. The sodium, calcium, magnesium, and zinc concentrations of the aqueous solution after the passage were all 0.05 ppm or less.
【００２４】[0024]
【発明の効果】本発明の方法により、金属不純物含量が
極めて少ない有機ホスホン酸を得ることができる。According to the method of the present invention, an organic phosphonic acid having a very low content of metal impurities can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 仁藤 祥一 東京都葛飾区新宿６丁目１番１号 三菱瓦 斯化学株式 会社 東京研究所内 Ｆターム(参考） 4H050 AA02 AD17 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shoichi Nito 6-1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Research Laboratory F-term (reference) 4H050 AA02 AD17
Claims (2)
その塩を有する有機ホスホン酸を強酸性陽イオン交換樹
脂に接触させることを特徴とする有機ホスホン酸の精製
方法。1. A method for purifying an organic phosphonic acid, comprising contacting an organic phosphonic acid having at least one phosphonic acid group or a salt thereof in a molecule with a strongly acidic cation exchange resin.
ホスホン酸）、エチレンジアミンテトラ（メチレンホス
ホン酸）、１，２−プロピレンジアミンテトラ（メチレ
ンホスホン酸）、またはジエチレントリアミンペンタ
（メチレンホスホン酸）である請求項１記載の精製方
法。2. The organic phosphonic acid is aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), 1,2-propylenediaminetetra (methylenephosphonic acid) or diethylenetriaminepenta (methylenephosphonic acid). Purification method as described.
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| JP2000285427A JP4508394B2 (en) | 2000-09-20 | 2000-09-20 | Purification method of organic phosphonic acid |
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| JP4508394B2 JP4508394B2 (en) | 2010-07-21 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006055441A1 (en) * | 2004-11-12 | 2006-05-26 | Monsanto Technology Llc | Recovery of noble metals from aqueous process streams in the synthesis of glyphosate using adsorption media such as ion exchange resins |
| JP2007022956A (en) * | 2005-07-15 | 2007-02-01 | Mitsubishi Gas Chem Co Inc | Method for producing high purity aminomethylene phosphonic acid |
| JP2007291002A (en) * | 2006-04-24 | 2007-11-08 | Mitsubishi Gas Chem Co Inc | Method for producing high-purity aminomethylenephosphonic acid |
| JP2012206950A (en) * | 2011-03-29 | 2012-10-25 | Kemikurea:Kk | Method for purifying horner-wadsworth-emmons reagent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4197254A (en) * | 1976-05-03 | 1980-04-08 | Monsanto Company | Derivatives of N-phosphonomethylglycine |
-
2000
- 2000-09-20 JP JP2000285427A patent/JP4508394B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006055441A1 (en) * | 2004-11-12 | 2006-05-26 | Monsanto Technology Llc | Recovery of noble metals from aqueous process streams in the synthesis of glyphosate using adsorption media such as ion exchange resins |
| US7687663B2 (en) | 2004-11-12 | 2010-03-30 | Monsanto Technology Llc | Recovery of noble metals from aqueous process streams |
| JP2007022956A (en) * | 2005-07-15 | 2007-02-01 | Mitsubishi Gas Chem Co Inc | Method for producing high purity aminomethylene phosphonic acid |
| JP2007291002A (en) * | 2006-04-24 | 2007-11-08 | Mitsubishi Gas Chem Co Inc | Method for producing high-purity aminomethylenephosphonic acid |
| JP2012206950A (en) * | 2011-03-29 | 2012-10-25 | Kemikurea:Kk | Method for purifying horner-wadsworth-emmons reagent |
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