JPH02173150A - Polymer complex for adsorption and desorption of oxygen - Google Patents
Polymer complex for adsorption and desorption of oxygenInfo
- Publication number
- JPH02173150A JPH02173150A JP33532288A JP33532288A JPH02173150A JP H02173150 A JPH02173150 A JP H02173150A JP 33532288 A JP33532288 A JP 33532288A JP 33532288 A JP33532288 A JP 33532288A JP H02173150 A JPH02173150 A JP H02173150A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- complex
- adsorption
- polymer complex
- desorption
- 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.)
- Granted
Links
- 239000001301 oxygen Substances 0.000 title claims abstract description 93
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 93
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229920000642 polymer Polymers 0.000 title claims abstract description 24
- 238000001179 sorption measurement Methods 0.000 title abstract description 20
- 238000003795 desorption Methods 0.000 title abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 7
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- -1 vinyl aromatic amine Chemical class 0.000 claims description 18
- 239000003463 adsorbent Substances 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 7
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 208000022177 perioral myoclonia with absences Diseases 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 150000004982 aromatic amines Chemical group 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PWTUTKMPGPPDPN-UHFFFAOYSA-N 2-ethenyl-1h-imidazole;2-ethenylpyridine Chemical compound C=CC1=NC=CN1.C=CC1=CC=CC=N1 PWTUTKMPGPPDPN-UHFFFAOYSA-N 0.000 description 1
- 208000019693 Lung disease Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 238000002664 inhalation therapy Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Oxygen, Ozone, And Oxides In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、医療分野、燃焼用ガスなどの酸素富化プロセ
スに使用される酸素吸脱着剤に関し、更に詳しく言えば
、酸素を迅速且つ可逆的に吸脱着できる特性を有する新
規な高分子錯体に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an oxygen adsorbent/desorbent used in the medical field and in oxygen enrichment processes for combustion gas, etc. This invention relates to a novel polymer complex that can be adsorbed and desorbed.
酸素は、例えば肺疾子、患者への酸素吸入療法などで用
いられ、医療分野において極めて用途の広い物質である
。また、鉄鋼などの金属製造処理、ガラス製造、化学酸
化処理、燃焼処理、排水処理などに関与して、工業分野
においても最も広範囲に使用されている化学物質の一つ
である。このような酸素を低エネルギーで空気から濃縮
するプロセスの開発は、極めて重要な課題であり、且つ
その波及効果が大きい、空気からの酸素濃縮法としては
、従来深冷法、膜分離法などが工業的に行われているが
、今後省エネルギー的な観点から特に小型汎用装置の要
請を想定した場合には吸着法が主流になると考えられて
いる。Oxygen is used, for example, in lung diseases, oxygen inhalation therapy for patients, etc., and is an extremely versatile substance in the medical field. It is also one of the most widely used chemical substances in the industrial field, involved in metal manufacturing processes such as steel, glass manufacturing, chemical oxidation treatment, combustion treatment, wastewater treatment, etc. The development of a process to condense oxygen from air using low energy is an extremely important issue and has a large ripple effect. Conventional methods for concentrating oxygen from air include cryogenic methods and membrane separation methods. Although it is practiced industrially, it is thought that the adsorption method will become mainstream in the future from an energy-saving perspective, especially when considering the demand for small general-purpose equipment.
この吸着法の課題としては、共存する空気中の窒素に対
して酸素（または逆に窒素）を選択的に効率よく吸着で
きる材料の開発が挙げられる。現在、空気から窒素を吸
着して、残存する酸、素の濃度を高められる吸着剤とし
て合成ゼオライト（モレキュラーシープ）が用いられ、
一部は実用化されている。これらの吸着剤が装填された
圧力スイング装置によれば、多基基プロセスを組み入れ
ることにより、３０％酸素濃度の酸素富化空気を得てい
る。しかし、ゼオライトは（１）窒素吸着剤であるため
に装置が煩雑になる、（ｉｉ ）吸着容量が小さい、（
ｉｉｉ ）吸着選択比は大きくても５以下である、とい
う欠点を有しており、このためゼオライトを用いた酸素
富化装置は大型化し、また経済性は必ずしも良くなかっ
た。A challenge to this adsorption method is the development of a material that can selectively and efficiently adsorb oxygen (or conversely, nitrogen) relative to nitrogen present in the air. Currently, synthetic zeolite (Molecular Sheep) is used as an adsorbent that can absorb nitrogen from the air and increase the concentration of remaining acids and elements.
Some of them have been put into practical use. A pressure swing device loaded with these adsorbents provides oxygen-enriched air with a 30% oxygen concentration by incorporating a multi-base process. However, zeolite (1) is a nitrogen adsorbent, which makes the equipment complicated, (ii) its adsorption capacity is small, (
iii) It has the disadvantage that the adsorption selectivity is at most 5 or less, and for this reason, oxygen enrichment devices using zeolite have become large in size and are not necessarily economical.
（発明が解決しようとする課題］
医療及び工業分野で有用性の高い高酸素濃度空気を簡便
な圧力スイングによる吸脱着法（Ｐ ＳＡ法）で得るた
めには、酸素吸脱着剤が酸素を選択的に吸着し、加えて
吸脱着が迅速且つ可逆的であることが不可欠の要件とな
る。(Problem to be solved by the invention) In order to obtain high oxygen concentration air, which is highly useful in the medical and industrial fields, by a simple pressure swing adsorption/desorption method (PSA method), it is necessary to select oxygen as the oxygen adsorption/desorption agent. It is essential that the adsorption and desorption be rapid and reversible.
一方、従来コバルトシッフ塩基などの特定の金属錯体（
共役系配位子と低酸化数金属イオンからなる錯体）は、
酸素分子を可逆的に吸脱着できることが知られている。On the other hand, conventionally certain metal complexes such as cobalt Schiff bases (
A complex consisting of a conjugated ligand and a low oxidation number metal ion) is
It is known that oxygen molecules can be adsorbed and desorbed reversibly.
しかし、この可逆的な吸脱着、これらの金属錯体を適当
な溶媒に溶解した場合にのみ実現しており、固相状態で
は吸着の速度が著しく低下するため、実用的な酸素の可
逆的な吸脱着剤として利用するのは無理であった。しか
も、溶液状態においても、多量の空気を処理する際に（
ｉ）溶媒が蒸散する、（ｉｉ ）金属錯体が不可逆的に
酸化して吸脱着剤としての寿命は著しく短い、という欠
点を有している。また、この種の金属錯体は酸素を選択
的に吸脱着することはできるが、雰囲気の酸素分圧に応
して吸着した酸素を脱着するためには酸素親和性（酸素
結合定数）が適当な大きさを有していなければならない
、特に大気圧下の空気（７６０ａｗＨｇ、酸素分圧とし
ては１５０ｍｍＨｇ）を対象として、比較的容易な減圧
度（例えば、約２００ ｍ Ｈｇ、酸素分圧としては４
０ ａｍ Ｈｇ ）で吸着酸素を脱着するためには、酸
素親和性Ｐ （１／２） （吸着剤の半量が酸素を吸
着する酸素分圧）が８Ｑ ａｓ Ｈｇから１２０ａｌ＋
Ｈｇの範囲になければならない、しかし、この種の金属
錯体の中で、この要件を満足して実用に供することがで
きるものは知られていない。このように、従来の金属錯
体を酸素吸脱着法に通用するには多くの問題点が解決で
きないままとなっている。However, this reversible adsorption and desorption is only possible when these metal complexes are dissolved in an appropriate solvent, and the rate of adsorption is significantly reduced in the solid phase state, making it difficult to achieve practical reversible adsorption of oxygen. It was impossible to use it as a desorbent. Moreover, even in the solution state, when processing large amounts of air (
It has the following drawbacks: i) the solvent evaporates, and (ii) the metal complex is irreversibly oxidized, resulting in an extremely short life as an adsorbent/desorbent. In addition, although this type of metal complex can selectively adsorb and desorb oxygen, it is necessary to have an appropriate oxygen affinity (oxygen binding constant) in order to desorb the adsorbed oxygen depending on the oxygen partial pressure of the atmosphere. In particular, it is necessary to have a relatively easy depressurization degree (e.g., about 200 m Hg, oxygen partial pressure of 4
In order to desorb adsorbed oxygen at 0 am Hg), the oxygen affinity P (1/2) (oxygen partial pressure at which half of the adsorbent adsorbs oxygen) must be changed from 8Q as Hg to 120al+
However, there is no known metal complex of this type that satisfies this requirement and can be put to practical use. As described above, many problems remain unsolved in order to apply conventional metal complexes to oxygen adsorption/desorption methods.
実用的な酸素吸脱着剤として利用できる物質として金属
錯体を使用した場合、次の条件が要求される。即ち（ｉ
）金属錯体の酸素結合席（配位座）は、これを固相状態
で調製する際にしばしば共存する分子により、占有され
、酸素結合能を失うことになる。従って、固相状態にお
いても迅速に酸素を吸脱着できるようにするには、この
酸素吸着席（配位座）を（酸素を結合する前の段階では
）常に酸素分子を吸着できるように「空」を保つことが
不可欠である。（１１）金属錯体の酸素親和性は、酸素
吸着席（配位座）の金属を挟んでトランス位にある配位
分子の影響を強く受ける。従って、酸素親和性を目的と
するＰ （１／２） （８０〜１２０＋ｎｍＨｇ）に
設定するには、このトランス位配位分子の種類が問題と
なる。（ｉｉｉ ）実用的な酸素吸脱着剤としては、金
属錯体が不可逆酸化を受けず、しかもその酸素吸脱着剤
能を長時間保持していなければならない。このためには
金属錯体が各種の化学反応を受けにくくするように、固
相状態に置くことが有効である。またトランス位配位分
子が金属に強固に結合していることも不可欠の要件であ
る。When a metal complex is used as a material that can be used as a practical oxygen adsorbing/desorbing agent, the following conditions are required. That is, (i
) The oxygen-binding sites (coordination sites) of metal complexes are often occupied by coexisting molecules when they are prepared in the solid phase, resulting in loss of oxygen-binding ability. Therefore, in order to be able to adsorb and desorb oxygen rapidly even in the solid state, the oxygen adsorption sites (coordination sites) must be kept empty so that they can always adsorb oxygen molecules (before binding oxygen). ” is essential. (11) The oxygen affinity of a metal complex is strongly influenced by the coordination molecule located in the trans position across the metal at the oxygen adsorption site (coordination site). Therefore, in order to set the oxygen affinity to the desired value of P (1/2) (80 to 120+nmHg), the type of this trans-coordination molecule becomes a problem. (iii) As a practical oxygen adsorbing/desorbing agent, the metal complex must not undergo irreversible oxidation and must retain its oxygen adsorbing/desorbing ability for a long period of time. For this purpose, it is effective to place the metal complex in a solid phase so as to make it less susceptible to various chemical reactions. It is also essential that the trans-coordination molecule is firmly bound to the metal.
本発明は、固相状態で酸素を選択的に吸着し、加えて迅
速且つ可逆的に吸脱着を行うことができる酸素吸脱着剤
用高分子錯体を提供することを目的とする。An object of the present invention is to provide a polymer complex for an oxygen adsorbing/desorbing agent that can selectively adsorb oxygen in a solid phase state and, in addition, can adsorb and desorb rapidly and reversibly.
本発明に係る酸素吸脱着剤用高分子錯体は、ビニル芳香
族アミンとアルキルアクリレート又はアルキルメタアク
リレートとの共重合体と、メソ−テトラキス（α、α、
α、α−０−ピパルアミドフェニル）ポルフィナト金属
（ｎ ） ｔｉｔ体とから成ることを特徴とする。The polymer complex for oxygen adsorbing and desorbing agents according to the present invention comprises a copolymer of a vinyl aromatic amine and an alkyl acrylate or an alkyl methacrylate, and meso-tetrakis (α, α,
α,α-0-pipalamidophenyl)porfinatometal(n)tit body.
上記ビニル芳香族アミンの具体例としては、下記の構造
式を有するビニルイミダゾール、ビニルピリジンを挙げ
ることができる。Specific examples of the vinyl aromatic amine include vinyl imidazole and vinyl pyridine having the following structural formula.
Ｒ−の炭素数は３〜３０が適当である。The number of carbon atoms in R- is suitably 3 to 30.
Ｃ１（。C1(.
Ｃ１１，＝Ｃｌｌ−Ｃ００Ｉ？
Ｃ１１，、Ｃ−Ｃ０ＯＲアルキルアクリレ
ート アルキルメタアクリレート
ビニル芳香族アミンとアルキル（メタ）アクリレートと
の共重合体中のビニル芳香族アミンの含量は、１０〜８
０モル％が適当である。C11,=Cll-C00I?
C11,, C-C0OR Alkyl Acrylate Alkyl Methacrylate The content of vinyl aromatic amine in the copolymer of vinyl aromatic amine and alkyl (meth)acrylate is 10-8
0 mol% is suitable.
上記メソ−テトラキス（α、α、α、α−Ｏビバルアミ
ドフェニル）ポルフィナト金属（ＩＩ）錯体は、下記構
造式を有する。The meso-tetrakis(α,α,α,α-O bivalamidophenyl)porphinato metal(II) complex has the following structural formula.
ビニルイミダゾール ビニルピリジン（１）、（２）
式で、ＲはＨ−１ＣＨｓ−１ＣｚＨｓ−等であり、Ｈ−
１ＣＨ３−が好ましい。Vinylimidazole Vinylpyridine (1), (2)
In the formula, R is H-1CHs-1CzHs-, etc., and H-
1CH3- is preferred.
下記の構造式を有するアルキルアクリレート又はアルキ
ルメタアルキレートにおけるアルキル基Ｍは２価の金属
元素、好ましくはＣ０１Ｆｅである。The alkyl group M in the alkyl acrylate or alkyl metaalkylate having the following structural formula is a divalent metal element, preferably C01Fe.
なお、ポルフィリン錯体を構築する金属イオンと共重合
体中に含まれる芳香族アミン残基（配位子）との比は、
分子分散の観点から、１：ｌ・００の範囲内が適当であ
る。The ratio of the metal ions that construct the porphyrin complex to the aromatic amine residues (ligands) contained in the copolymer is as follows:
From the viewpoint of molecular dispersion, a range of 1:l·00 is suitable.
一例としてビニルイミダゾールとオクチルメタクリレー
トとの共重合体と、メソ−テトラキス（α、α、α、α
−０−ピバルアミドフェニル）ポルフィナトコバルト（
ＩＩ）とから成る酸素吸脱側用高分子錯体の立体構造式
を下記に示す。As an example, a copolymer of vinylimidazole and octyl methacrylate and meso-tetrakis (α, α, α, α
-0-pivalamidophenyl)porphinatocobalt (
The three-dimensional structural formula of the polymer complex for the oxygen adsorption/extraction side consisting of II) is shown below.
本発明に係る高分子錯体より成る吸脱着剤の作製方法は
、特に限定されないが、代表例は次の通りである。即ち
、メソ−テトラキス（α、α、α。The method for producing the adsorbent/desorbent made of the polymer complex according to the present invention is not particularly limited, but typical examples are as follows. That is, meso-tetrakis (α, α, α.
α−０−ピバルアミドフェニル）ポルフィナト金属（ｎ
） ｉｆ体（以下錯体と略す）及びビニル芳香族アミ
ンとアルキル（メタ）アクリレートとの共重合体（以下
共重合体と略す）をそれぞれ有機媒体に均一に溶解し、
十分脱酸素化した後、混合し、凍結乾燥を施すことによ
り高分子錯体より成る酸素吸脱着剤を得る。この場合、
錯体の含有割合は、１〜８０重量％重量％節囲内に選定
するのが適当である。なお、吸脱着剤の作製に当たって
は、十分に脱酸素してから行うことが望ましい。α-0-pivalamidophenyl)porfinato metal (n
) If form (hereinafter abbreviated as complex) and a copolymer of vinyl aromatic amine and alkyl (meth)acrylate (hereinafter abbreviated as copolymer) are each uniformly dissolved in an organic medium,
After sufficient deoxygenation, they are mixed and freeze-dried to obtain an oxygen adsorbing/desorbing agent made of a polymer complex. in this case,
The content of the complex is suitably selected within the range of 1 to 80% by weight. In addition, when preparing the adsorbent/desorbent, it is desirable to perform the process after sufficiently deoxidizing the adsorbent.
酸素吸脱着剤の形状は、特に限定されないが、通常は１
〜１０ｐｍ程度の壁厚を有する粉末が適当で、圧力スイ
ング吸脱着装置の型式などに応じて適宜選定する。この
ような本発明に係る酸素吸脱着剤を用いれば、例えば小
型ポンプを使用した圧力スイング吸着（ＰＳＡ）法によ
り、空気から酸素濃度４０％以上の酸素含有ガスを得る
ことが可能となる。The shape of the oxygen adsorbent/desorbent is not particularly limited, but is usually 1
A powder having a wall thickness of about 10 pm is suitable, and is appropriately selected depending on the type of pressure swing adsorption/desorption device. If such an oxygen adsorbent/desorbent according to the present invention is used, it becomes possible to obtain an oxygen-containing gas having an oxygen concentration of 40% or more from air by, for example, a pressure swing adsorption (PSA) method using a small pump.
本発明によれば、メソ−テトラキス（α α、α、α−
〇−ピバルアミドフェニル）ポルフィナト金属（■）錯
体は、面上に酸素結合を囲んで置換基が構築されている
ため、固相状態においても雰囲気の酸素分圧に対応して
極めて迅速に（ミリ秒程度）酸素を吸脱着できる性能を
有する・、また、ビニル芳香族アミンとアルキル（メタ
）アクリレートとの共重合体をポルフィリン金属のトラ
ンス位配分子として用いることにより、酸素親和性を約
１００１００ｆｆ１に設定することが可能になる。According to the invention, meso-tetrakis (α α, α, α-
The 〇-pivalamidophenyl)porfinato metal (■) complex has substituents built around oxygen bonds on the surface, so even in the solid state, it responds extremely quickly to the oxygen partial pressure in the atmosphere ( Also, by using a copolymer of vinyl aromatic amine and alkyl (meth)acrylate as the trans coordination molecule of the porphyrin metal, the oxygen affinity can be increased to approximately 100100ff1. It becomes possible to set it to .
また、ビニル芳香族アミンとアルキル（メタ）アクリレ
ートとの共重合体を用いることにより、芳香族アミン残
基のポルフィリン金属への結合は、いわゆる高分子効果
により強固に保持され、且つポリフィリン金属錯体が共
重合体上に分子分散して固定されるため、酸素吸脱着剤
として作用する寿命を飛躍的に向上させることができる
。同上の理由により、ポルフィリン金属錯体に対するト
ランス位配位分子のモル量を低減することができるため
、単位重量当りの錯体量、即ち錯体吸着容量を著しく高
めることができる。この結果、窒素に対する酸素の選択
比は１００を越え、前例を見ない優れた酸素選択吸着力
が得られる。更に、ビニル芳香族アミンとアルキル（メ
タ）アクリレートとの共重合体は高い気体透過性を有す
るため、ポルフィリン金属錯体の迅速な酸素吸着を損な
うことがない。また、この共重合体はポルフィリン金属
錯体を比較的高い濃度で含有した後も成形性を保持して
おり、吸着剤として任意の形状に成形することができる
。例えば、高速で大量の気体を処理するのに適した微粉
末として成形することが可能になる。Furthermore, by using a copolymer of vinyl aromatic amine and alkyl (meth)acrylate, the bond of the aromatic amine residue to the porphyrin metal is firmly maintained due to the so-called polymer effect, and the porphyrin metal complex is Since the molecules are dispersed and fixed on the copolymer, the lifespan of acting as an oxygen adsorption/desorption agent can be dramatically improved. For the same reason, the molar amount of trans-coordination molecules to the porphyrin metal complex can be reduced, so the amount of complex per unit weight, that is, the complex adsorption capacity can be significantly increased. As a result, the selectivity ratio of oxygen to nitrogen exceeds 100, providing unprecedented and excellent oxygen selective adsorption power. Furthermore, since the copolymer of vinyl aromatic amine and alkyl (meth)acrylate has high gas permeability, it does not impair the rapid oxygen adsorption of the porphyrin metal complex. Furthermore, this copolymer retains its moldability even after containing a porphyrin metal complex at a relatively high concentration, and can be molded into any shape as an adsorbent. For example, it becomes possible to form it into a fine powder suitable for processing a large amount of gas at high speed.
夫ｌ貰上
メソ−テトラキス（α、α、α、α−０−ピバルアミド
フェニル）ポルフィナトコバルトＮｌ）錯体を３０ｇ含
むベンゼン溶液と、ビニルイミダゾールとオクチルメタ
ブタリレートとの共重合体（ビニルイミダゾールを３５
モル％含有、以下ＰＯＭＡ １ｍと略記する）を７０ｇ
含むベンゼン溶液をそれぞれ調製した。A benzene solution containing 30 g of meso-tetrakis (α, α, α, α-0-pivalamidophenyl) porphynato cobalt Nl) complex and a copolymer of vinyl imidazole and octyl metabutyrate (vinyl 35 imidazole
70g of mol% (hereinafter abbreviated as POMA 1m)
benzene solutions containing each were prepared.
上記両温液を混合し、混合液をドライアイス−メタノー
ル溶液で凍結後、減圧下に保って乾燥した。得られた酸
素吸脱着剤用高分子錯体は、壁厚が約１μｍ程度の多孔
質形状を有し、これ、を粉砕して粉末にした。The above two warm liquids were mixed, and the mixed liquid was frozen with a dry ice-methanol solution and then dried by keeping it under reduced pressure. The obtained polymer complex for an oxygen adsorbing/desorbing agent had a porous shape with a wall thickness of approximately 1 μm, and was ground into powder.
この酸素吸脱着剤用高分子錯体への酸素の可逆的な吸脱
着は、可視スペクトル（酸素化： ５４５ｎｓ＋、脱酸
素化： ５２７ｎｓ＋ ）により確認した。Reversible adsorption and desorption of oxygen to this polymer complex for oxygen adsorption/desorption agent was confirmed by visible spectrum (oxygenation: 545ns+, deoxygenation: 527ns+).
得られた酸素吸脱着用高分子錯体１００ｇを第１図に示
す圧力スイング装置のチャンバー１内に充填した。そし
て、送気側の電磁弁２を開いてチャンバー１内に乾燥空
気を吹き込み、吸脱着剤７に酸素を吸着させた後、排気
側の電磁弁３を開いてチャンバー１内をポンプ４で１０
０〜１５０ｍ＋ｓ Ｈｇまで減圧した。ポンプ排気口よ
り１ 、 ５１ ／ｌ１ｉｎの流量で吹き出してくる気
体をタンク５に貯め、その酸素濃度を酸素センサー６で
測定した結果によると、４０％の酸素濃度の酸素富化空
気が得られた。チャンバー１内での空気の吹き込み及び
ポンプ４による減圧は各々１０秒で実施できた。これら
の値は、本発明に係る吸脱着剤が、迅速、且つ可逆的に
酸素を吸脱着し、極めて有効に酸素富化空気を供給でき
ることを示している。100 g of the obtained oxygen adsorption/desorption polymer complex was filled into the chamber 1 of the pressure swing device shown in FIG. Then, after opening the solenoid valve 2 on the air supply side and blowing dry air into the chamber 1 to cause the adsorption/desorption agent 7 to adsorb oxygen, the solenoid valve 3 on the exhaust side is opened and the inside of the chamber 1 is pumped with the pump 4 for 10 minutes.
The pressure was reduced to 0-150 m+s Hg. The gas blown out from the pump exhaust port at a flow rate of 1.51/l1 inch was stored in the tank 5, and the oxygen concentration was measured with the oxygen sensor 6. According to the results, oxygen-enriched air with an oxygen concentration of 40% was obtained. . Blowing air into the chamber 1 and reducing the pressure using the pump 4 could each be carried out in 10 seconds. These values indicate that the adsorbent/desorbent according to the present invention can adsorb and desorb oxygen rapidly and reversibly, and supply oxygen-enriched air extremely effectively.
同様にして、錯体を１０％含む高分子錯体を合成した後
、凍結乾燥法により粉末状の吸脱着剤として調製し、こ
れを圧力スイング装置で測定したところ、３０％の酸素
濃度の酸素富化空気が得られた。Similarly, after synthesizing a polymer complex containing 10% of the complex, it was prepared as a powdered adsorption/desorption agent by freeze-drying, and when measured with a pressure swing device, it was found that the oxygen enrichment with an oxygen concentration of 30% was obtained. Got some air.
同様にして、錯体を４５重量％含む高分子錯体を合成し
た後、これを凍結乾燥法により粉末状の吸脱着剤として
調製し、圧力スイング装置に装着して測定したところ、
４５％の酸素濃度の酸素富化空気が得られた。Similarly, after synthesizing a polymer complex containing 45% by weight of the complex, this was prepared as a powder adsorption/desorption agent by freeze-drying, and when it was attached to a pressure swing device and measured,
Oxygen-enriched air with an oxygen concentration of 45% was obtained.
ｌｌｌ主
実施例１におけるＰＯＭＡ ｒ■のビニルイミダゾール
の含量を３．７モル％とした以外は実施例１と同様にし
て合成した後、粉末状の吸脱着剤として調製し、第１図
に示す圧力スイング装置で酸素濃度の測定を行った。錯
体を１０重量％含む酸素吸脱着剤用高分子錯体では、３
０％の酸素濃度の酸素富化空気が得られた。After synthesizing in the same manner as in Example 1 except that the content of vinylimidazole in POMA r■ in Main Example 1 was changed to 3.7 mol%, it was prepared as a powder adsorbent and desorbent, and the mixture was prepared as shown in FIG. Oxygen concentration was measured using a pressure swing device. In a polymer complex for oxygen adsorption/desorption agent containing 10% by weight of the complex, 3
Oxygen-enriched air with an oxygen concentration of 0% was obtained.
また、実施例１におけるＰＯＭＡＩｍのビニルイミダゾ
ールの含量を５０モル％とした以外は実施例１と同様に
して合成した後、粉末状の吸脱着・剤として調製し、圧
力スイング装置で測定を行った。錯体を４５重量％含む
酸素吸脱着剤用高分子錯体では、４５％の酸素濃度の酸
素富化空気が得られた。In addition, it was synthesized in the same manner as in Example 1 except that the content of vinylimidazole in POMAIm in Example 1 was changed to 50 mol%, and then it was prepared as a powder adsorption/desorption agent and measured using a pressure swing device. . With a polymer complex for an oxygen adsorbent/desorbent containing 45% by weight of the complex, oxygen-enriched air with an oxygen concentration of 45% was obtained.
ＸＵＬｌ主
実施例１におけるＰＯＭＡ Ｉ−の代わりにヘキシルメ
タアクリレートとビニルピリジンの共重合体（ビニルピ
リジンを３５モル％含有）を用いた以外は実施例１と同
様にして合成した後、粉末状の吸脱着剤として調製し、
圧力スイング装置で測定を行った。ｔｆ体を３０重量％
含む酸素吸脱着剤用高分子錯体では、４０％の酸素濃度
の酸素富化空気が得られた。After synthesizing in the same manner as in Example 1 except that a copolymer of hexyl methacrylate and vinyl pyridine (containing 35 mol % of vinyl pyridine) was used in place of POMA I- in Main Example 1, powdered Prepared as an adsorption/desorption agent,
Measurements were made with a pressure swing device. 30% by weight of tf body
The oxygen-enriched air with an oxygen concentration of 40% was obtained with the polymer complex for an oxygen adsorbing/desorbing agent containing the above.
一実」Ｌ例〕ユ
実施例１におけるＰＯＭＡＩｍの代わりにブチルアクリ
レートとビニルピリジンの共重合体（ビニルピリジンを
３０モル％含有）を用いた以外は実施例１と同様にして
合成した後、粉末状の吸脱着剤として調製し、圧力スイ
ング装置で測定を行った。Kazumi'L Example] After synthesizing in the same manner as in Example 1 except that a copolymer of butyl acrylate and vinyl pyridine (containing 30 mol% vinyl pyridine) was used instead of POMAIm in Example 1, powder It was prepared as an adsorption/desorption agent and measured using a pressure swing device.
錯体を３０重量％含む酸素吸脱着剤用高分子錯体では、
４０％の酸素濃度の酸素富化空気が得られた。In the polymer complex for oxygen adsorption/desorption agent containing 30% by weight of the complex,
Oxygen-enriched air with an oxygen concentration of 40% was obtained.
本発明によれば、固相状態で酸素を選択的に吸着し、加
えて迅速且つ可逆的に吸脱着を行うことができる酸素吸
脱着剤用高分子錯体が得られる。According to the present invention, a polymer complex for an oxygen adsorbing/desorbing agent can be obtained which can selectively adsorb oxygen in a solid phase state and can also rapidly and reversibly adsorb and desorb oxygen.
第１図は実施例で使用する圧力スイング装置を示す構成
図である。
１・・・チャンバー ４・・・ポンプ、５・・・タンク
、６・・・酸素センサ。FIG. 1 is a configuration diagram showing a pressure swing device used in an example. 1...Chamber 4...Pump, 5...Tank, 6...Oxygen sensor.
Claims (4)
アルキルメタアクリレートとの共重合体と、メソ−テト
ラキス（α，α，α，α−ｏ−ピパルアミドフェニル）
ポルフィナト金属（II）錯体とから成ることを特徴とす
る酸素吸脱着剤用高分子錯体。(1) Copolymer of vinyl aromatic amine and alkyl acrylate or alkyl methacrylate and meso-tetrakis (α, α, α, α-o-pipalamidophenyl)
A polymer complex for use as an oxygen adsorbent/desorbent, characterized by comprising a porphinato metal (II) complex.
ニルピリジンである第１請求項記載の酸素吸脱着剤用高
分子錯体。(2) The polymer complex for an oxygen adsorbing/desorbing agent according to claim 1, wherein the vinyl aromatic amine is vinyl imidazole or vinyl pyridine.
ートのアルキル基の炭素数が３〜３０である第１請求項
又は第２請求項記載の酸素吸脱着剤用高分子錯体。(3) The polymer complex for an oxygen adsorbing/desorbing agent according to claim 1 or 2, wherein the alkyl group of the alkyl acrylate or alkyl methacrylate has 3 to 30 carbon atoms.
アミドフェニル）ポルフィナト金属（II）錯体の含有量
が１〜８０重量％である第１請求項〜第３請求項のいず
れかに記載の酸素吸脱着剤用高分子錯体。(4) Any one of claims 1 to 3, wherein the content of the meso-tetrakis(α,α,α,α-o-pipalamidophenyl)porfinato metal(II) complex is 1 to 80% by weight. A polymer complex for use as an oxygen adsorbing/desorbing agent according to the invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33532288A JP2738943B2 (en) | 1988-12-27 | 1988-12-27 | Polymer complex for oxygen adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33532288A JP2738943B2 (en) | 1988-12-27 | 1988-12-27 | Polymer complex for oxygen adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02173150A true JPH02173150A (en) | 1990-07-04 |
| JP2738943B2 JP2738943B2 (en) | 1998-04-08 |
Family
ID=18287224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33532288A Expired - Fee Related JP2738943B2 (en) | 1988-12-27 | 1988-12-27 | Polymer complex for oxygen adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2738943B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6630128B1 (en) | 1998-08-28 | 2003-10-07 | Destiny Pharma Limited | Porphyrin derivatives their use in photodynamic therapy and medical devices containing them |
| WO2005010101A1 (en) * | 2003-07-24 | 2005-02-03 | Kuraray Co., Ltd. | Oxygen-absorbing body, method for producing same, and packaging material using same |
| JP2010192887A (en) * | 2009-01-23 | 2010-09-02 | Sumitomo Chemical Co Ltd | Organic electroluminescent device |
-
1988
- 1988-12-27 JP JP33532288A patent/JP2738943B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6630128B1 (en) | 1998-08-28 | 2003-10-07 | Destiny Pharma Limited | Porphyrin derivatives their use in photodynamic therapy and medical devices containing them |
| WO2005010101A1 (en) * | 2003-07-24 | 2005-02-03 | Kuraray Co., Ltd. | Oxygen-absorbing body, method for producing same, and packaging material using same |
| JPWO2005010101A1 (en) * | 2003-07-24 | 2006-11-24 | 株式会社クラレ | Oxygen absorber, method for producing the same, and packaging material using the same |
| US7396865B2 (en) | 2003-07-24 | 2008-07-08 | Kuraray Co., Ltd. | Oxygen absorber, method for producing the same, and packaging material using the same |
| JP4726625B2 (en) * | 2003-07-24 | 2011-07-20 | 株式会社クラレ | Oxygen absorber, method for producing the same, and packaging material using the same |
| JP2010192887A (en) * | 2009-01-23 | 2010-09-02 | Sumitomo Chemical Co Ltd | Organic electroluminescent device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2738943B2 (en) | 1998-04-08 |
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