JPS5910723B2 - Method for producing macrocyclic hexamines containing polystyrene - Google Patents
Method for producing macrocyclic hexamines containing polystyreneInfo
- Publication number
- JPS5910723B2 JPS5910723B2 JP18388680A JP18388680A JPS5910723B2 JP S5910723 B2 JPS5910723 B2 JP S5910723B2 JP 18388680 A JP18388680 A JP 18388680A JP 18388680 A JP18388680 A JP 18388680A JP S5910723 B2 JPS5910723 B2 JP S5910723B2
- Authority
- JP
- Japan
- Prior art keywords
- polystyrene
- macrocyclic
- hexamines
- heavy metal
- containing polystyrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明はポリスチレンを有する大環式ヘキサアミン類の
製造方法に関し、詳しくは重金属イオンの吸着剤として
有効な特定の大環状ジアミドテトラアミン類に、ポリス
チレンを導入し、さらに還元処理することによつて、水
に対して不溶な大環状ヘキサアミン類を製造する方法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing macrocyclic hexaamines containing polystyrene, and more specifically, polystyrene is introduced into specific macrocyclic diamidetetraamines that are effective as adsorbents for heavy metal ions, and further reduction is performed. The present invention relates to a method for producing water-insoluble macrocyclic hexamines by treatment.
従来から廃水中に含まれる銅、ニッケル、水銀などの重
金属イオンを除去するために用いられている重金属イオ
ン吸着剤としては、活性炭、けいそう土、イオン交換樹
脂あるいはキレート樹脂などがあげられる。しかし、こ
れらのうち活性炭、けいそう土、イオン交換樹脂は重金
属イオンに対する選択性に劣り、またキレート樹脂は特
に重金属イオン間の選択性に劣るという欠点があつた。
本発明者らは特定の新規な大環状ヘキサアミン類が重金
属イオンに対して極めてすぐれた選択吸着性能を有する
ことを見出した。本発明者らはさらにこの大環状ヘキサ
アミン類を水に対して不溶なものとし、より利用価値の
高い化合物とすべく研究を重ね、本発明を完成するに至
つた。すなわち本発明は、式
o□o
C)
(N」 ・・・(1)
で表わされる大環状ジアミドテトラアミン類に、官能基
含有ポリスチレンを極性溶媒中で反応させ、次いで得ら
れた生成物を還元することを特徴とするポリスチレンを
有する大環状ヘキサアミン類の製造方法を提供するもの
である。Heavy metal ion adsorbents conventionally used to remove heavy metal ions such as copper, nickel, and mercury contained in wastewater include activated carbon, diatomaceous earth, ion exchange resins, and chelate resins. However, among these, activated carbon, diatomaceous earth, and ion exchange resins have a disadvantage in that they have poor selectivity toward heavy metal ions, and chelate resins have particularly poor selectivity among heavy metal ions.
The present inventors have discovered that certain new macrocyclic hexamines have extremely excellent selective adsorption performance for heavy metal ions. The present inventors further conducted research to make these macrocyclic hexamines insoluble in water, thereby making them more useful compounds, and finally completed the present invention. That is, the present invention involves reacting a macrocyclic diamidetetraamine represented by the formula o□o C) (N''...(1) with functional group-containing polystyrene in a polar solvent, and then reacting the resulting product with The present invention provides a method for producing macrocyclic hexamines containing polystyrene, which is characterized by being reduced.
本発明の方法において原料として用いる式(I)で表わ
される大環状ジアミドテトラアミン類は、18−N6−
ジアミド(正しくは、2、6−ジオキソ一1,4,7,
10,13,16−ヘキサアザ−シクロオクタデカン)
であり、その環の大きさは18であつて、そのうち窒素
原子の数は6個である。The macrocyclic diamidetetraamines represented by formula (I) used as raw materials in the method of the present invention are 18-N6-
diamide (correctly, 2,6-dioxo-1,4,7,
10,13,16-hexaaza-cyclooctadecane)
The size of the ring is 18, of which the number of nitrogen atoms is 6.
ここで環員数を18とするのは、壊内部に重金属イオン
を捕捉するのに適した大きさとなるからであり、また壌
を構成する窒素原子を6個とする理由は、ウラニル錯体
のX線回折によれば6個の配位子の中心にウラン原子が
配置した構造が示されており、錯体として安定であると
考えられるからである。本発明の方法では上記の大環状
ジアミドテトラアミン類に、まず官能基を含有するポリ
スチレンを反応させる。The reason why the number of ring members is set to 18 is that the size is suitable for trapping heavy metal ions inside the ring, and the reason why the number of nitrogen atoms that make up the ring is set to 6 is that the X-rays of the uranyl complex This is because diffraction shows a structure in which a uranium atom is placed at the center of six ligands, and it is considered to be stable as a complex. In the method of the present invention, the macrocyclic diamidetetraamines described above are first reacted with polystyrene containing a functional group.
ここで用いるポリスチレンは、重合度等について特に制
限はなく、水に対して不溶性のものであればよい。また
このポリスチレンには、スチレンのホモポリマーのみな
らず、スチレンージビニルベンゼンコポリマ一なども包
含される。さらにポリスチレンに結合する官能基として
は、−CH,Cl,−Cl,−Br,−CO2H,−C
O2R.−SO,R(Rはアルキル基を示す。)などが
あり、特にクロロメチル基(−CH2Cj)が好ましい
。上記の大環状ジアミドテトラアミン類を官能基を含有
するポリスチレンの反応は、クロロホルム等の極性溶媒
中で、常圧下、室温〜加温の条件で1〜3日間撹拌する
ことにより行なえばよい。The polystyrene used here is not particularly limited in terms of degree of polymerization, etc., as long as it is insoluble in water. Moreover, this polystyrene includes not only a styrene homopolymer but also a styrene-divinylbenzene copolymer and the like. Furthermore, the functional groups bonded to polystyrene include -CH, Cl, -Cl, -Br, -CO2H, -C
O2R. Examples include -SO, R (R represents an alkyl group), and chloromethyl group (-CH2Cj) is particularly preferred. The reaction of polystyrene containing a functional group with the above-mentioned macrocyclic diamidetetraamines may be carried out by stirring in a polar solvent such as chloroform under normal pressure at room temperature to elevated temperature for 1 to 3 days.
本発明の方法では上述の反応によつて得られた生成物(
これは主として式(1)の大環状ジアミドテトラアミン
類にポリスチレンが導入されたもの、つまりN−ポリス
チリル−18−N6−ジアミドである。)を、さらに還
元剤等を用いて還元することにより、目的とするポリス
チレンを有する大還状ヘキサアミン類を製造する。この
方法によつて得られるポリスチレンを導入した大還状ヘ
キサアミン類は、反応に供する式(1)で表わされる大
還状ジアミドテトラアミン類とポリスチレンの使用割合
、さらにはポリスチレンに結合している官能基の割合な
どにより様々なものとなるが、例えば官能基としてクロ
ロメチル基(CH,Cl)を有するポリスチレンを用い
たときは、一般式
〔式中R1〜R6はそれぞれ水素原子または(ここで(
PS)はポリスチレンを示す。In the method of the present invention, the product obtained by the above reaction (
This is mainly a macrocyclic diamidetetraamine of formula (1) into which polystyrene has been introduced, that is, N-polystyryl-18-N6-diamide. ) is further reduced using a reducing agent or the like to produce the target large cyclic hexaamines having polystyrene. The large cyclic hexamines into which polystyrene has been introduced, obtained by this method, are determined by the ratio of the large cyclic diamidetetraamines represented by formula (1) to be subjected to the reaction and polystyrene, as well as the functionalities bonded to the polystyrene. Although it varies depending on the ratio of groups, for example, when polystyrene having chloromethyl groups (CH, Cl) as functional groups is used, the general formula [wherein R1 to R6 are hydrogen atoms or (where (
PS) indicates polystyrene.
)である。ただしR,〜R6のすべてが水素原子である
場合を除く。〕で表わされるものが得られる。前記一般
式()の化合物においてR1〜現のすべてが水素原子で
ある値換基の存在しない化合物であつても重金属イオン
に対してある程度の選択的捕捉特性を有するが、本発明
の方法によつて得られるポリスチレンを導入した大環状
ヘキサアミン類は、さらにすぐれた重金属イオンの選択
的捕捉特性を有し、また重金属イオン間における選択性
も大きい。そのうえ重金属イオンの捕捉速度が極めて大
きく、重金属イオンの捕捉、脱着が著しく容易である。
しかもポリマ一が導入されているため水に対しては不溶
であり、特に海水等を対象とする重金属イオン吸着剤と
しての利用価値が著しく大きい。叙上の説明から明らか
なように、本発明の方法によつて得られるポリスチレン
を有する大壌状ヘキサアミン類は重金属イオン吸着剤と
してすぐれた性能を示す全く新規な化合物である。). However, this excludes the case where all of R and ~R6 are hydrogen atoms. ] is obtained. In the compound of the general formula (), even a compound in which there is no substituent group in which all of R1 to R1 are hydrogen atoms has a certain degree of selective trapping property for heavy metal ions; The polystyrene-incorporated macrocyclic hexamines thus obtained have even better selective trapping properties for heavy metal ions, and also have high selectivity among heavy metal ions. Moreover, the capture rate of heavy metal ions is extremely high, and the capture and desorption of heavy metal ions is extremely easy.
Furthermore, since a polymer is introduced, it is insoluble in water, and its utility value is particularly great as a heavy metal ion adsorbent for seawater and the like. As is clear from the above description, the polystyrene-containing hexamines obtained by the method of the present invention are completely new compounds that exhibit excellent performance as heavy metal ion adsorbents.
特に重金属イオンに対する選択吸着性、捕捉あるいは脱
着速度に関して従来の吸着剤に比して著しくすぐれてお
り、また海水条件(PH8.2前後)での重金属イオン
捕捉率が非常に高いという特性を有する。従つて本発明
の方法によつて得られるポリスチレンを有する大環状ヘ
キサアミン類は廃水処理、金属精錬、濃縮等に好適に利
用することができる。次に本発明を参考例、合成例およ
び応用例によりさらに詳しく説明する。参考例
18−N6−ジアミド(2,6−ジオキソ一1,4,7
,10,13,16−ヘキサアザ−シクロオクタデカン
)の合成イミノジ酢酸ジエチルエステル18.91(0
.1モル)とテトラエチレンペンタアミン1869f1
(0.1モル)をエタノール111中に溶解し、撹拌下
に5日間加熱還流した。In particular, it is significantly superior to conventional adsorbents in terms of selective adsorption, capture or desorption rate for heavy metal ions, and also has the property of very high heavy metal ion capture rate under seawater conditions (pH around 8.2). Therefore, macrocyclic hexamines containing polystyrene obtained by the method of the present invention can be suitably used for wastewater treatment, metal refining, concentration, etc. Next, the present invention will be explained in more detail using reference examples, synthesis examples, and application examples. Reference example 18-N6-diamide (2,6-dioxo-1,4,7
, 10,13,16-hexaaza-cyclooctadecane) iminodiacetic acid diethyl ester 18.91 (0
.. 1 mol) and tetraethylenepentaamine 1869f1
(0.1 mol) was dissolved in ethanol 111 and heated to reflux with stirring for 5 days.
反応液よりエタノールを減圧留去し、残渣をベンゼン1
00w11で3回加熱抽出し、冷却後ベンゼンを減圧留
去して析出した結晶を再度ベンゼンから再結晶して無色
結晶4.01(収率15%)を得た。この結晶の分析結
果は次のとおりであつた。1融点130〜132たC
2元素分析値% Cl,H26O2N6
3マススペクトルのピーク
m/E286(M+)
243(M+−CONH)
4核磁気共鳴スペクトル(重クロロホルム溶媒、TMS
基準)5赤外線吸収スペクトル(KBr錠剤法)337
001n−1 (νNH)、1640(νCOO).1
550(ν00NH)以上の結果から得られた結晶は式
で表わされる18−N6−ジアミド(2,6−ジオキソ
一1,4,7,10,13,16−ヘキサアザ−シクロ
オクタデカン)であることがわかつた。Ethanol was distilled off from the reaction solution under reduced pressure, and the residue was diluted with benzene 1
00w11 was heated and extracted three times, and after cooling, benzene was distilled off under reduced pressure, and the precipitated crystals were recrystallized from benzene again to obtain colorless crystals 4.01 (yield: 15%). The analysis results of this crystal were as follows. 1 Melting point 130-132 C 2 element analysis value % Cl, H26O2N6 3 Mass spectrum peak m/E286 (M+) 243 (M+-CONH) 4 Nuclear magnetic resonance spectrum (deuterium chloroform solvent, TMS
Standard) 5 Infrared absorption spectrum (KBr tablet method) 337
001n-1 (νNH), 1640 (νCOO). 1
The crystal obtained from the result of 550 (ν00NH) or more is 18-N6-diamide (2,6-dioxo-1,4,7,10,13,16-hexaaza-cyclooctadecane) represented by the formula. I understand.
合成例
N−ポリスチリル−18−N6(p−〔1一(1,4,
7,10,13,16−ヘキサアザ−シクロオクタデシ
ル)アルキル〕スチレンとスチレンの共重合体)の合成
1クロロメチルポリスチレンの合成
攪拌装置を備えた丸底フラスコに精製した重合度160
0〜1800のポリスチレン20f!、クロロメチルメ
チルエーテル124TfL1(1.54モル)を加え、
室温で撹拌し溶解させた。Synthesis example N-polystyryl-18-N6 (p-[1-(1,4,
Synthesis of 7,10,13,16-hexaaza-cyclooctadecyl)alkyl (copolymer of styrene and styrene) 1 Synthesis of chloromethyl polystyrene Purified in a round bottom flask equipped with a stirring device Polymerization degree 160
0-1800 polystyrene 20f! , add chloromethyl methyl ether 124TfL1 (1.54 mol),
Stir to dissolve at room temperature.
無水塩化亜鉛の粉末3.14f1(0.023モノリを
加え,室温(200C)で10時間撹拌した。減圧下1
0℃で反応混合物より過剰のクロロメチルメチルエーテ
ルの大部分を留去した。残渣にクロロホルム150Tr
L1を加えて撹拌後、ろ過により不溶物を除いた。淵液
をメタノール300dに加え析出した沈澱を淵取し、4
0℃で48時間減圧乾燥したところクロロメチルポリス
チレン159を得た。得られたクロロメチルポリスチレ
ンを重クロロホルムに溶解し、NMRを測定した結果、
原料ポリスチレンのフエニル環に対するクロロメチル化
率は60%であつた。2N−ポリスチリル−18−N6
−ジアミドの合成1で合成したクロロメチルポリスチレ
ン3.951(0.02モル)をクロロホルム100d
に溶解後、クロロホルム50m1に溶かした18−N6
−ジアミド5.7f!(0.02モノ(へ)を加えて撹
拌しながら室温で48時間反応させた。Anhydrous zinc chloride powder 3.14f1 (0.023ml) was added and stirred at room temperature (200C) for 10 hours. Under reduced pressure 1
Most of the excess chloromethyl methyl ether was distilled off from the reaction mixture at 0°C. Chloroform 150Tr on the residue
After adding L1 and stirring, insoluble matters were removed by filtration. Add the bottom liquid to 300 d of methanol, filter out the precipitate, and add 4
After drying under reduced pressure at 0° C. for 48 hours, chloromethyl polystyrene 159 was obtained. As a result of dissolving the obtained chloromethyl polystyrene in deuterated chloroform and measuring NMR,
The chloromethylation rate of phenyl rings in the raw material polystyrene was 60%. 2N-polystyryl-18-N6
- 3.951 (0.02 mol) of chloromethyl polystyrene synthesized in Diamide Synthesis 1 was added to 100 d of chloroform.
18-N6 dissolved in 50ml of chloroform
-Diamide 5.7f! (0.02 mono(h)) was added and reacted at room temperature for 48 hours with stirring.
析出したポリマーを戸取し1規定塩酸水溶液で洗浄後、
続いて蒸留水、1%水酸化カリウム水溶液、蒸留水、エ
タノール、クロロホルム、アセトンで順次洗浄後減圧乾
燥して白色樹脂6.09を得た。分析結果を下記に示す
。0元素分析値(%) C2lH34O2N6Ol8−
N6−ジアミド(ミリモル)/ポリスチレン(9)=1
.300転化率(ポリスチレン固定化率)=48%0赤
外線吸収スペクトル(KBr錠剤法)3400α−1
(νNH),2920,2820(ν0H)1660(
νoェ0),1540(ν00NH),1460(δC
r)3N−ポリスチリル−18−N6ジアミドを還N−
ポリスチリル−18−N6−ジアミドを乳鉢で粉砕し、
この粉末69を少量ずつ冷却しながら大過剰のジポラン
のTHF溶液(0.4モル/′、200d)に加え、室
温で5時間攪拌後、更に5時間加熱した。After removing the precipitated polymer and washing it with 1N hydrochloric acid aqueous solution,
Subsequently, the resin was washed successively with distilled water, 1% potassium hydroxide aqueous solution, distilled water, ethanol, chloroform, and acetone, and dried under reduced pressure to obtain white resin 6.09. The analysis results are shown below. 0 elemental analysis value (%) C2lH34O2N6Ol8-
N6-diamide (mmol)/polystyrene (9) = 1
.. 300 Conversion rate (polystyrene immobilization rate) = 48% 0 Infrared absorption spectrum (KBr tablet method) 3400α-1
(νNH), 2920, 2820 (ν0H) 1660(
νoE0), 1540(ν00NH), 1460(δC
r) Reducing 3N-polystyryl-18-N6 diamide with N-
Grind polystyryl-18-N6-diamide in a mortar,
This powder 69 was added to a large excess of a THF solution of diporan (0.4 mol/', 200 d) while cooling little by little, stirred at room temperature for 5 hours, and then heated for an additional 5 hours.
ポリマーを戸取して、6規定塩酸200d中に加え、加
熱しながら10時間撹拌した。再度ポリマーを戸取し、
水洗後1%水酸化カリウム水溶液200d中に加え室温
で1時間中和反応を行なつた。The polymer was taken out, added to 200 d of 6N hydrochloric acid, and stirred for 10 hours while heating. Take the polymer again,
After washing with water, it was added to 200 d of a 1% aqueous potassium hydroxide solution and a neutralization reaction was carried out at room temperature for 1 hour.
続いて、蒸留水、クロロホルム、メタノールアセトンで
順次洗浄後、減圧乾燥して白色樹脂5.59を得た。Subsequently, the product was washed with distilled water, chloroform, and methanol acetone in this order, and then dried under reduced pressure to obtain a white resin 5.59.
O元素分析値(%) C2,H,8N6
Ol8−N6(mモノリ /ポリスチレン●)=1.3
00転化率(ポリスチレン固定化率)=47%O赤外線
吸収スペクトル(KBr錠剤法)3350CWL−1(
νNH),2920.2820(ν0H),1640(
δNH),1460(δ0H)O溶解性
N−ポリスチリル−18−N6−ジアミドと同様に有機
溶媒、鉱酸およびアルカリ水溶液に不溶。O elemental analysis value (%) C2, H, 8N6 Ol8-N6 (m monoly/polystyrene●) = 1.3
00 conversion rate (polystyrene immobilization rate) = 47% O infrared absorption spectrum (KBr tablet method) 3350CWL-1 (
νNH), 2920.2820(ν0H), 1640(
δNH), 1460(δ0H)O Solubility Similar to N-polystyryl-18-N6-diamide, insoluble in organic solvents, mineral acids, and aqueous alkaline solutions.
以上の結果から得られた結晶は、
一般式
〔式中(PS)はポリスチレンを示す〕
C表わされるN−ポリスチリル−18−N6(p〔1−
(1,4,7,10,13,16−ヘキナアザーシクロ
オクタデシル)アルキル〕スチレソとスチレンの共重合
体であることがわかつた。The crystals obtained from the above results have the following structure: N-polystyryl-18-N6 (p[1-
It was found to be a copolymer of (1,4,7,10,13,16-hequinaazalcyclooctadecyl)alkyl]styreso and styrene.
ム用例(金属捕捉試験)
1)酢酸ウラニルUO2(0C0CH,),水溶液とN
−ポリスチリル−18−N6の粉末を室温で混合振とう
し、済別した。Example of application (metal capture test) 1) Uranyl acetate UO2 (0C0CH,), aqueous solution and N
-Polystyryl-18-N6 powder was mixed and shaken at room temperature, and then evaporated.
Claims (1)
含有ポリスチレンを極性溶媒中で反応させ、次いで得ら
れた生成物を還元することを特徴とするポリスチレンを
有する大環状ヘキサアミン類の製造方法。 2 ポリスチレンの官能基が、−CH_2Cl、−Cl
、−Br、−CO_2H、−CO_2Rあるいは−SO
_3R(Rはアルキル基を示す。 )である特許請求の範囲第1項記載の方法。[Claims] 1. Macrocyclic diamidetetraamines represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ are reacted with functional group-containing polystyrene in a polar solvent, and the resulting product is then reduced. A method for producing macrocyclic hexamines containing polystyrene, characterized in that: 2 The functional groups of polystyrene are -CH_2Cl, -Cl
, -Br, -CO_2H, -CO_2R or -SO
The method according to claim 1, wherein _3R (R represents an alkyl group).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18388680A JPS5910723B2 (en) | 1980-12-26 | 1980-12-26 | Method for producing macrocyclic hexamines containing polystyrene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18388680A JPS5910723B2 (en) | 1980-12-26 | 1980-12-26 | Method for producing macrocyclic hexamines containing polystyrene |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2449278A Division JPS54130593A (en) | 1978-03-06 | 1978-03-06 | Macroocyclic hexamines |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS56100805A JPS56100805A (en) | 1981-08-13 |
JPS5910723B2 true JPS5910723B2 (en) | 1984-03-10 |
Family
ID=16143537
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP18388680A Expired JPS5910723B2 (en) | 1980-12-26 | 1980-12-26 | Method for producing macrocyclic hexamines containing polystyrene |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5910723B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5514588A (en) * | 1994-12-13 | 1996-05-07 | Exxon Research And Engineering Company | Surfactant-nutrients for bioremediation of hydrocarbon contaminated soils and water |
-
1980
- 1980-12-26 JP JP18388680A patent/JPS5910723B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS56100805A (en) | 1981-08-13 |
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