JPH0196215A - Production of transition metal ion-coordinated polymer complex - Google Patents
Production of transition metal ion-coordinated polymer complexInfo
- Publication number
- JPH0196215A JPH0196215A JP25388387A JP25388387A JPH0196215A JP H0196215 A JPH0196215 A JP H0196215A JP 25388387 A JP25388387 A JP 25388387A JP 25388387 A JP25388387 A JP 25388387A JP H0196215 A JPH0196215 A JP H0196215A
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- polycondensate
- polymer complex
- metal ion
- film
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920000642 polymer Polymers 0.000 title abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 title 1
- 150000003624 transition metals Chemical class 0.000 title 1
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 239000013256 coordination polymer Substances 0.000 claims description 18
- 229920001795 coordination polymer Polymers 0.000 claims description 18
- -1 iron ion Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 230000005294 ferromagnetic effect Effects 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 239000003570 air Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 230000005415 magnetization Effects 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000005291 magnetic effect Effects 0.000 description 5
- PMWXGSWIOOVHEQ-UHFFFAOYSA-N pyridine-2,6-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=N1 PMWXGSWIOOVHEQ-UHFFFAOYSA-N 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000005307 ferromagnetism Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003302 ferromagnetic material Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- RVUXIPACAZKWHU-UHFFFAOYSA-N sulfuric acid;heptahydrate Chemical compound O.O.O.O.O.O.O.OS(O)(=O)=O RVUXIPACAZKWHU-UHFFFAOYSA-N 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- GJMIMISVJLOUGG-UHFFFAOYSA-K iron(3+);triperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O GJMIMISVJLOUGG-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- IZEMHEXSGIOXDA-UHFFFAOYSA-N iron;hexahydrate Chemical compound O.O.O.O.O.O.[Fe] IZEMHEXSGIOXDA-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002907 paramagnetic material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- OYBLXLFKRJWZJG-UHFFFAOYSA-N pyridine-2,3-dicarbaldehyde Chemical compound O=CC1=CC=CN=C1C=O OYBLXLFKRJWZJG-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、遷移金属イオン配位高分子錯体の製造法に関
する。更に詳しくは、強磁性体膜を形成し得る遷移金属
イオン配位高分子錯体の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a transition metal ion coordination polymer complex. More specifically, the present invention relates to a method for producing a transition metal ion coordination polymer complex capable of forming a ferromagnetic film.
Ｊ、 Ａｍ、 Ｃｈｅｍ、 Ｓｏｅ、第７９巻第２７３
８頁（１９５７）には。J, Am, Chem, Soe, Vol. 79, No. 273
On page 8 (1957).
α、ω−ジアミノアルカンと２，６−ピリジンジカルボ
キシアルデヒドとを重縮合反応させることにより、次の
一般式で表わされ−る繰返し単位を有する重縮合物が得
られることが記載されている。It is stated that a polycondensation product having a repeating unit represented by the following general formula can be obtained by polycondensation reaction of α,ω-diaminoalkane and 2,6-pyridinedicarboxaldehyde. .
この重縮合反応は、例えば１，６−ジアミノヘキサンを
用い、そのエタノール溶液の還流液中に２，６−ピリジ
ンジカルボキシアルデヒドのエタノール溶液を滴下する
ことによって行われ、２０秒以内に反応生成物が析出す
るので、これを０刑し、熱エタノールで洗浄して重縮合
物を取得している。This polycondensation reaction is carried out, for example, by using 1,6-diaminohexane and dropping an ethanol solution of 2,6-pyridinedicarboxaldehyde into the reflux of the ethanol solution, and the reaction product is formed within 20 seconds. is precipitated, so this is boiled down and washed with hot ethanol to obtain a polycondensate.
この反応あるいはその滴下方法を逆にした反応では、い
ずれも反応生成物たる重縮合物が熱エタノールにも不溶
なため析出し、重縮合反応の生長反応を停止させてしま
う。このため、重合度が高くならず、赤外線吸収スペク
トルによる末端基定量法によれば、平均重合度が約２５
程度の重縮合物しか得られず、このような重縮合物は製
膜しても強度が低く、膜形状を保持することができない
。In this reaction or a reaction in which the dropping method is reversed, the polycondensate as a reaction product is insoluble even in hot ethanol and precipitates, stopping the growth reaction of the polycondensation reaction. Therefore, the degree of polymerization does not increase, and according to the terminal group determination method using infrared absorption spectrum, the average degree of polymerization is about 25.
Even if such a polycondensate is formed into a film, its strength is low and the film shape cannot be maintained.
１．６−ジアミツヘキサンと２，６−ピリジンジカルボ
キシアルデヒドとの重縮合物は、前記式（ｎ＝６）の繰
返し単位に示される如く１重金属とキレートを形成する
ことのできる配位子を主鎖に含み、重金属の捕集あるい
は排除に有用な高分子である。これを実際に工業的に利
用するためには、膜状あるいは繊維状などに成形する必
要があり、また高分子的特性である成形性、加工性など
を確保する上からも、この重縮合物の重合度を高めるこ
とが強く望まれている。The polycondensate of 1,6-diamithexane and 2,6-pyridinedicarboxaldehyde contains a ligand capable of forming a chelate with one heavy metal as shown in the repeating unit of the above formula (n=6). It is a polymer useful for collecting or eliminating heavy metals. In order to actually use it industrially, it is necessary to form it into a membrane or fiber form, and in order to ensure the moldability and processability, which are the characteristics of polymers, this polycondensate It is strongly desired to increase the degree of polymerization of
本出願人は、かかる課題の解決方法を求めて種々検討を
重ねた結果、１，６−ジアミツヘキサン、２゜６−ピリ
ジンジカルボキシアルデヒドおよびこれらの重縮合物に
共通する溶媒を選択して用いることにより、上記課題が
効果的に解決されることを先に見出した（特願昭６２−
号）。即ち、この解決方法では、重縮合物の製
造は、α、ω−ジアミノアルカンの塩素化炭化水素溶媒
溶液中に、２，６−ピリジンジカルボキシアルデヒドの
塩素化炭化水素溶媒溶液を滴下し、重縮合反応させるこ
とにより行われている。As a result of various studies in search of a solution to this problem, the applicant selected a solvent common to 1,6-diamithexane, 2゜6-pyridinedicarboxaldehyde, and their polycondensates. We have previously discovered that the above problems can be effectively solved by using
issue). That is, in this solution, the polycondensate is produced by dropping a solution of 2,6-pyridinedicarboxaldehyde in a chlorinated hydrocarbon solvent into a solution of α,ω-diaminoalkane in a chlorinated hydrocarbon solvent. It is carried out by a condensation reaction.
塩素化炭化水素溶媒としては、クロロホルム、１．１，
２．２−テトラクロルエタンなどが用いられる。As the chlorinated hydrocarbon solvent, chloroform, 1.1,
2.2-tetrachloroethane or the like is used.
これらの溶媒の使用は１重合度が高くならない最大の原
因である反応混合物中からの重縮合物の析出を有効に防
止させる。Use of these solvents effectively prevents precipitation of polycondensates from the reaction mixture, which is the main reason why the degree of monopolymerization does not increase.
重縮合反応は、いずれも濃度が約０．５〜１．５モルの
α、ω−ジアミノアルカン溶液中に当量の２，６−ピリ
ジンジカルボキシアルデヒド溶液を滴下し、室温乃至溶
媒の還流温度で約１〜Ｚ時間反応させることによって行
われる。一般に、この種のジアミンとジアルデヒドとの
重縮合反応は酸が触媒となって進行することが知られて
おり、逆に生成重縮金物の脱離水による加水分解反応も
酸として作用する可能性がある。In the polycondensation reaction, an equivalent amount of 2,6-pyridinedicarboxaldehyde solution is added dropwise to an α,ω-diaminoalkane solution having a concentration of about 0.5 to 1.5 mol, and the reaction is carried out at room temperature to the reflux temperature of the solvent. This is done by reacting for about 1 to Z hours. In general, it is known that this type of polycondensation reaction between diamines and dialdehydes proceeds with an acid as a catalyst, and conversely, there is a possibility that the hydrolysis reaction of the produced polycondensate due to the released water also acts as an acid. There is.
この方法においては、塩基性で水との親和性の高いジア
ミン溶液にジアルデヒド溶液を滴下し、ジアミン過剰の
雰囲気中で重縮合物の生長反応を円滑に進行させ、生成
重縮金物への水の付加反応を抑制することにより、重縮
合物の反応混合物からの非析出効果と相まって、より一
層の高分子化を達成させる。In this method, a dialdehyde solution is dropped into a diamine solution that is basic and has a high affinity for water, and the growth reaction of the polycondensate proceeds smoothly in an atmosphere containing excess diamine. By suppressing the addition reaction of the polycondensate, combined with the effect of preventing precipitation of the polycondensate from the reaction mixture, further polymerization can be achieved.
この方法により、膜強度の高い膜を製膜し得る高重合度
の重縮合物が得られる。この重縮合物は、鉄イオンなど
の遷移金属イオンを配位することによって磁性を保持せ
しめるようにすることができ、無機磁性体とは全く異な
る性質を有する。軽くて薄い有機磁性膜や分散性良好な
磁性流体として用いることができる。By this method, a polycondensate with a high degree of polymerization that can be used to form a film with high film strength can be obtained. This polycondensate can be made to retain magnetism by coordinating transition metal ions such as iron ions, and has properties completely different from those of inorganic magnetic materials. It can be used as a light and thin organic magnetic film or as a magnetic fluid with good dispersibility.
しかるに、遷移金属イオンの配位を従来法に従って行な
うと、反応溶液の液性が酸性でありかつ重縮合物自体加
水分解を受は易いという性質を有しているため分解して
しまい、膜形状を保持し得ないという問題がみられる。However, if the coordination of transition metal ions is carried out according to the conventional method, the reaction solution is acidic and the polycondensate itself is susceptible to hydrolysis, so it decomposes and the membrane shape deteriorates. The problem is that it is not possible to maintain the
即ち、前記Ｊ、 Ａｍ、 Ｃｈｅｗ、 Ｓｏｃ、記載の
方法に従えば、硫酸第１鉄・７水和物１．８ｇを純水２
５ｍ Ｑ中に溶かした水溶液を沸騰させた中に重縮合物
０．６５ｇを加えると、深赤色の粉体が得られ、この粉
体を回収し、洗浄するという方法がとられ、重縮合物の
膜状体にこの方法を適用すると、遷移金属イオンを含む
水溶液はその大多数が酸性であり、しかも遷移金属イオ
ン含有水溶液を煮沸条件下で用いないと強磁性を示す高
分子錯体が得られないので煮沸条件下で用いると、本来
加水分解を受は易い重縮合物は容易に分解され、膜形状
を保つことができないようになる。That is, according to the method described in J. Am. Chew, Soc, 1.8 g of ferrous sulfate heptahydrate is added to
When 0.65 g of the polycondensate is added to a boiling aqueous solution dissolved in 5m Q, a deep red powder is obtained, and this powder is collected and washed. When this method is applied to a film-like material, the majority of aqueous solutions containing transition metal ions are acidic, and a polymer complex that exhibits ferromagnetism cannot be obtained unless the aqueous solution containing transition metal ions is used under boiling conditions. Therefore, if used under boiling conditions, the polycondensate, which is inherently susceptible to hydrolysis, will be easily decomposed and the membrane will not be able to maintain its shape.
本発明者らは、かかる課題の解決を目的として種々検討
を重ねた結果、重縮合物に比較的低温で遷移金属イオン
を配位させた後、これを加熱することにより、その形状
を損なうことなく、強磁性体として有用な高分子錯体膜
状物が得られることを見出した。As a result of various studies aimed at solving this problem, the present inventors have discovered that by coordinating transition metal ions to a polycondensate at a relatively low temperature and then heating it, the shape of the polycondensate is impaired. It has been found that a film-like polymer complex useful as a ferromagnetic material can be obtained.
従って、本発明は遷移金属イオン配位高分子錯体の製造
法に係り、それの製造は、一般式で表わされる繰返し単
位を有する重縮合物に約４０℃以下で遷移金属イオンを
配位させた後、これを約４５〜１２０℃の温度に加熱す
ることにより行われる。Therefore, the present invention relates to a method for producing a transition metal ion coordination polymer complex, which is produced by coordinating a transition metal ion to a polycondensate having a repeating unit represented by the general formula at a temperature of about 40°C or less. This is then heated to a temperature of about 45-120°C.
上記一般式で表わされる繰返し単位を有する重縮合物は
、前記の如き方法で得られ、それは水銀プール上への溶
液キャスト法などによって製膜される。A polycondensate having a repeating unit represented by the above general formula is obtained by the method described above, and is formed into a film by a solution casting method onto a mercury pool.
重縮合物への遷移金属イオンの配位は、硫酸第１鉄・７
水和物、硫酸コバルト（ｎ）・７水和物、過塩素酸第２
鉄・６水和物などを純水中に約０．１〜１０重量％濃度
に溶解させた水溶液中に、約４０℃以下の温度、一般に
は室温条件下で約１０〜３０分間程度浸漬することによ
って行われる。この配位を煮沸条件下で行なうと、短時
間の内に分解が起り、また室温条件下では約１時間以上
、４０℃では約３０分間以上浸漬すると分解し始めるよ
うになる。The coordination of transition metal ions to the polycondensate is ferrous sulfate 7
Hydrate, cobalt (n) sulfate heptahydrate, perchloric acid 2
Immerse in an aqueous solution of iron hexahydrate, etc. dissolved in pure water at a concentration of approximately 0.1 to 10% by weight for approximately 10 to 30 minutes at a temperature of approximately 40°C or less, generally at room temperature. It is done by When this coordination is carried out under boiling conditions, decomposition occurs within a short period of time, and decomposition begins when immersed for more than about 1 hour at room temperature and for more than about 30 minutes at 40°C.
このようにして比較的低温で配位させたら、次に約４５
〜１２０℃に加熱する。加熱は、純水中または空気中、
窒素ガス中などで行なうことができる。After coordination at a relatively low temperature in this way, about 45
Heat to ~120°C. Heating is done in pure water or in air.
This can be done in nitrogen gas or the like.
約４５℃以下での加熱では、加熱処理による強磁性化効
果が発現せず、一方約１２０℃以上に加熱すると、重縮
合物の融点が１２０℃であるので、融解と同時に分解す
るようになる。If heated at temperatures below about 45°C, the ferromagnetic effect due to heat treatment will not occur, while if heated above about 120°C, the melting point of the polycondensate is 120°C, so it will decompose at the same time as it melts. .
本発明方法によれば１重縮合物に遷移金属イオンを配位
させる際の温度を比較的低温とすることにより重縮合物
の分解を抑制し、それが膜状物の場合にはその形状を保
持させることができ、得られた遷移金属イオン配位高分
子錯体に加熱処理を施すことによって、強磁性を示す有
機磁性体膜を得ることができる。According to the method of the present invention, the decomposition of the polycondensate is suppressed by keeping the temperature at which transition metal ions are coordinated to a relatively low temperature, and when the polycondensate is in the form of a film, its shape is By subjecting the obtained transition metal ion coordination polymer complex to a heat treatment, an organic magnetic film exhibiting ferromagnetism can be obtained.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例１
１．３モル濃度の１，６−ジアミツヘキサンのクロロホ
ルム溶液１４．Ｏｍｇの還流液中に、同濃度の２，６−
ピリジンジカルボキシアルデヒドのクロロホルム溶液１
４．Ｏｍｇを窒素雰囲気中で滴下し、約１時間反応させ
た。反応終了後、均一な溶液を形成している反応液を熱
メタノール中に滴下し、生成重縮金物を沈殿させた。Example 1 1.3 molar solution of 1,6-diamithexane in chloroform 14. The same concentration of 2,6-
Chloroform solution of pyridine dicarboxaldehyde 1
4. Omg was added dropwise in a nitrogen atmosphere, and the mixture was allowed to react for about 1 hour. After the reaction was completed, the reaction solution forming a homogeneous solution was dropped into hot methanol to precipitate the produced polycondensate.
この生成重縮金物は、赤外線吸収スペクトルでアルデヒ
ド基の存在が確認されなかったことから。This is because the presence of aldehyde groups was not confirmed in the infrared absorption spectrum of the produced polycondensed metal.
重縮合物鎖中のアゾメチン部と末端アルデヒド基の伸縮
振動のピーク強度比から求められる平均重合度は２００
以上と考えられる。これのクロロホルム溶液を用い、水
銀プール上への溶液キャスト法によって得られた膜は、
引張強度約１．４Ｋｇ／ｍｍ２、引張弾性率約１８Ｋｇ
／ｍｍ’であった。The average degree of polymerization determined from the peak intensity ratio of stretching vibrations between the azomethine moiety and the terminal aldehyde group in the polycondensate chain is 200.
This is considered to be the above. A film obtained by solution casting on a mercury pool using a chloroform solution of this
Tensile strength approximately 1.4Kg/mm2, tensile modulus approximately 18Kg
/mm'.
このようにして得られた重縮合物の膜状物０．１ｇを、
硫酸第１鉄・７水和物０．１４ｇを純水２０ｍ Ｑに溶
解させた水溶液中に浸漬し、窒素ガスを吹き込みながら
、室温下で１０分間反応させた。膜状物は、浸漬した瞬
間から着色し始め、１０分後には濃青紫色を呈するよう
になる。その時点で純水で洗浄し、反応を停止させた。0.1 g of the polycondensate film obtained in this way,
It was immersed in an aqueous solution in which 0.14 g of ferrous sulfate heptahydrate was dissolved in 20 mQ of pure water, and reacted for 10 minutes at room temperature while blowing nitrogen gas. The film-like material begins to be colored from the moment it is immersed, and becomes dark blue-purple after 10 minutes. At that point, the reaction was stopped by washing with pure water.
このような条件下で遷移金属イオンを配位させると、膜
状物はその形状が保持される。この配位された高分子錯
体は磁性を示さず、ＥＳＲスペクトルから常磁性体であ
ることが確認された。次に、これを純水中で窒素ガスを
通じながら１０分間煮沸したが、この途中での変色はみ
られなかった。その後、よく風乾した。When the transition metal ions are coordinated under such conditions, the membrane retains its shape. This coordinated polymer complex did not exhibit magnetism, and it was confirmed from the ESR spectrum that it was a paramagnetic material. Next, this was boiled for 10 minutes in pure water while passing nitrogen gas, but no discoloration was observed during the boiling. After that, it was air-dried thoroughly.
この配位高分子錯体について、振動試料型磁力計を用い
て磁化測定を行なうと、強磁性体特有のヒステリシス曲
線を示した（第１図参照）にの曲線から、それぞれ次の
ような磁気特性値が求められた。When we measured the magnetization of this coordination polymer complex using a vibrating sample magnetometer, it showed a hysteresis curve characteristic of ferromagnetic materials (see Figure 1), which revealed the following magnetic properties. value was found.
飽和磁化 Ｍｓ＝０．４ ｅｍｕ／ｇ
残留磁化 Ｍｒ＝０．０５ｅｍｕ／ｇ
保磁力Ｈｃ＝６００ｅ
比較例１
煮沸した硫酸第１鉄・７水和物の水溶液（０，１４ｇ／
２０ｎ＋Ｑ）に窒素ガスを通じながら、実施例１で用い
られた重縮合物膜０．１ｇを浸漬したところ、膜状物は
２分経過後から分解し始め、１０分後には殆んど分解し
て粉末状物質しか得られなかった。なお、この粉末状物
質も、磁性を示していた。Saturation magnetization Ms=0.4 emu/g Residual magnetization Mr=0.05 emu/g Coercive force Hc=600e Comparative example 1 Boiled aqueous solution of ferrous sulfate heptahydrate (0.14 g/g
When 0.1 g of the polycondensate film used in Example 1 was immersed in 20n+Q) while passing nitrogen gas, the film started to decompose after 2 minutes, and almost completely decomposed after 10 minutes. Only a powdery substance was obtained. Note that this powdery substance also exhibited magnetism.
実施例２
実施例１において、室温下での浸漬時間を２０分間およ
び３０分間に延長したが、膜状物はその形状を保持して
おり、煮沸処理された配位高分子錯体の磁気特性値にも
大きな違いはみられなかった。Example 2 In Example 1, the immersion time at room temperature was extended to 20 minutes and 30 minutes, but the film-like material retained its shape, and the magnetic property values of the boiled coordination polymer complex were There was no significant difference in either.
なお、室温浸漬時間を１時間に延長すると、膜状物が分
解し始めることが認められた。In addition, it was observed that when the room temperature immersion time was extended to 1 hour, the film-like material began to decompose.
実施例３ 実施例１〜２において、浸漬温度を４０℃に変更した。Example 3 In Examples 1 and 2, the immersion temperature was changed to 40°C.
浸漬時間１０分または２０分では、膜状物はその形状を
保持していたが、３０分にしてみると膜状物は分解し始
めた。When the soaking time was 10 or 20 minutes, the film retained its shape, but after 30 minutes, the film began to decompose.
実施例４
実施例１において、１，６−ジアミツヘキサンの代りに
同モル濃度の１，１２−ジアミノドデカンを用いて形成
された重縮合物の膜状物０．１ｇが用いられた。Example 4 In Example 1, 0.1 g of a polycondensate film formed using 1,12-diaminododecane at the same molar concentration instead of 1,6-diamithexane was used.
得られた配位高分子錯体膜は、強磁性を示した。The obtained coordination polymer complex film exhibited ferromagnetism.
飽和磁化 Ｍｓ＝０．３ ｅｍｕ／ｇ
残留磁化 計＝０．０３ｅｍｕ／ｇ
保磁力Ｈｃ＝４５０ｓ
実施例５
実施例１において、加熱処理を煮沸純水中ではなく、１
００℃のオーブン中で１０分間行なった。このようにし
て加熱処理された配位高分子錯体の磁気特性値は、実施
例１のそれと大きな違いはみられなかった。Saturation magnetization Ms = 0.3 emu/g Residual magnetization Total = 0.03 emu/g Coercive force Hc = 450 s Example 5 In Example 1, the heat treatment was performed in boiling pure water instead of in boiling pure water.
The test was carried out in an oven at 00°C for 10 minutes. The magnetic property values of the coordination polymer complex heat-treated in this manner were not significantly different from those of Example 1.
実施例６
実施例１で用いられた重縮合物の膜状物０．１ｇを、硫
酸コバルト（ｎ）・７水和物０．１４ｇを純水２０ｍ
Ｑに溶解させた水溶液中に浸漬し、窒素ガスを吹き込み
ながら、室温下で２０分間反応させた。膜状物は。Example 6 0.1 g of the polycondensate film used in Example 1 was added to 0.14 g of cobalt (n) sulfate heptahydrate in 20 m of pure water.
The sample was immersed in an aqueous solution containing Q and reacted at room temperature for 20 minutes while blowing nitrogen gas. The membrane-like substance.
浸漬後徐々に着色し始め、２０分後には赤色を呈するよ
うになる。その後、純水で洗浄し、よく風乾した。After immersion, the color gradually begins to change and becomes red after 20 minutes. Thereafter, it was washed with pure water and thoroughly air-dried.
得られたコバルトイオン配位高分子錯体は磁石に付着し
、鉄イオン配位高分子錯体と同様に強磁性体であった。The obtained cobalt ion coordination polymer complex adhered to the magnet and was ferromagnetic like the iron ion coordination polymer complex.
実施例７
実施例１で用いられた重縮合物の膜状物０．１ｇを、過
塩素酸第２鉄・６水和物０．４３ｇを純水２０ｍ Ａに
溶解させた水溶液中に浸漬し、窒素ガスを吹き込みなが
ら、室温下で１０分間反応させた。Example 7 0.1 g of the polycondensate film used in Example 1 was immersed in an aqueous solution in which 0.43 g of ferric perchlorate hexahydrate was dissolved in 20 mA of pure water. The reaction was carried out at room temperature for 10 minutes while blowing nitrogen gas.
得られた配位高分子錯体膜は、強磁性を示した。The obtained coordination polymer complex film exhibited ferromagnetism.
第１図は、実施例１の鉄イオン配位高分子錯体膜の磁化
曲線である。また、第２〜３図は、それぞれ実施例１の
鉄イオン配位高分子錯体膜の加熱処理前後におけるＥｓ
Ｒスペクトルである。
第１図
第２図
ｇ＝４．３１ ｇ＝２．ｏ。
Ｑ ＝ ２．０５
手続補装置（白銀
昭和６２年１２月２８日FIG. 1 is a magnetization curve of the iron ion coordination polymer complex film of Example 1. In addition, Figures 2 and 3 show the Ess of the iron ion coordination polymer complex film of Example 1 before and after heat treatment, respectively.
This is the R spectrum. Figure 1 Figure 2 g=4.31 g=2. o. Q = 2.05 Supplementary Procedure Device (December 28, 1988, Shirogane)
Claims (1)
１２） で表わされる繰返し単位を有する重縮合物に、約４０℃
以下で遷移金属イオンを配位させた後、これを約４５〜
１２０℃の温度に加熱することを特徴とする遷移金属イ
オン配位高分子錯体の製造法。 ２、重縮合物が膜状体である特許請求の範囲第１項記載
の遷移金属イオン配位高分子錯体の製造法。 ３、遷移金属イオンが鉄イオンである特許請求の範囲第
１項記載の遷移金属イオン配位高分子錯体の製造法。 ４、加熱処理が純水中で行われる特許請求の範囲第１項
記載の遷移金属イオン配位高分子錯体の製造法。 ５、加熱処理が空気中または窒素ガス中で行われる特許
請求の範囲第１項記載の遷移金属イオン配位高分子錯体
の製造法。[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, n = 2 ~
12) A polycondensate having a repeating unit represented by
After coordinating the transition metal ions below, this
A method for producing a transition metal ion coordination polymer complex, which comprises heating to a temperature of 120°C. 2. The method for producing a transition metal ion coordination polymer complex according to claim 1, wherein the polycondensate is in the form of a film. 3. The method for producing a transition metal ion coordination polymer complex according to claim 1, wherein the transition metal ion is an iron ion. 4. The method for producing a transition metal ion coordination polymer complex according to claim 1, wherein the heat treatment is performed in pure water. 5. The method for producing a transition metal ion coordination polymer complex according to claim 1, wherein the heat treatment is performed in air or nitrogen gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25388387A JPH0196215A (en) | 1987-10-09 | 1987-10-09 | Production of transition metal ion-coordinated polymer complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25388387A JPH0196215A (en) | 1987-10-09 | 1987-10-09 | Production of transition metal ion-coordinated polymer complex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0196215A true JPH0196215A (en) | 1989-04-14 |
Family
ID=17257449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25388387A Pending JPH0196215A (en) | 1987-10-09 | 1987-10-09 | Production of transition metal ion-coordinated polymer complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0196215A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698561A (en) * | 2021-09-01 | 2021-11-26 | 中国科学院宁波材料技术与工程研究所 | Main chain degradation type metal ion complexing poly Schiff base antifouling resin, preparation method and application |
-
1987
- 1987-10-09 JP JP25388387A patent/JPH0196215A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698561A (en) * | 2021-09-01 | 2021-11-26 | 中国科学院宁波材料技术与工程研究所 | Main chain degradation type metal ion complexing poly Schiff base antifouling resin, preparation method and application |
| CN113698561B (en) * | 2021-09-01 | 2024-04-09 | 中国科学院宁波材料技术与工程研究所 | Main chain degradation type metal ion complexing poly Schiff base antifouling resin, preparation method and application |
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