JPH03181333A - Catalyst for oxidation with oxygen - Google Patents
Catalyst for oxidation with oxygenInfo
- Publication number
- JPH03181333A JPH03181333A JP1320068A JP32006889A JPH03181333A JP H03181333 A JPH03181333 A JP H03181333A JP 1320068 A JP1320068 A JP 1320068A JP 32006889 A JP32006889 A JP 32006889A JP H03181333 A JPH03181333 A JP H03181333A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- formula
- catalyst
- polyurethane
- phthalocyanine
- 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
- 239000001301 oxygen Substances 0.000 title claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 claims abstract description 16
- 239000004814 polyurethane Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 abstract description 23
- 229920005749 polyurethane resin Polymers 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 2
- 229920003240 metallophthalocyanine polymer Polymers 0.000 abstract 3
- 238000006243 chemical reaction Methods 0.000 description 16
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000036284 oxygen consumption Effects 0.000 description 4
- -1 phthalocyanine dicarboxylic acid derivative Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LHYQAEFVHIZFLR-UHFFFAOYSA-L 4-(4-diazonio-3-methoxyphenyl)-2-methoxybenzenediazonium;dichloride Chemical compound [Cl-].[Cl-].C1=C([N+]#N)C(OC)=CC(C=2C=C(OC)C([N+]#N)=CC=2)=C1 LHYQAEFVHIZFLR-UHFFFAOYSA-L 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YKENVNAJIQUGKU-UHFFFAOYSA-N tetraazaporphin Chemical group C=1C(C=N2)=NC2=NC(NN2)=NC2=CC(C=C2)=NC2=CC2=NC=1C=C2 YKENVNAJIQUGKU-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Catalysts (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本発明は、２−メルカプトエタノールの酸素酸化反応を
触媒し、例えば消臭剤として利用可能な酸素酸化触媒に
関するものである。The present invention relates to an oxygen oxidation catalyst that catalyzes the oxygen oxidation reaction of 2-mercaptoethanol and can be used, for example, as a deodorant.
従来、金属フタロシアニンは堅牢性の高いブルー、グリ
ーン系の顔料や染料として広く用いられてきた。この金
属フタロシアニンは、テトラアザポリフィリン骨格を持
つ極めて安定な大環状平面配位子の金属錯体である。大
きな−Ｔ（電子系を有する特殊な電子環境の中に、金属
含量が極めて少量に６拘らず、触媒、電子、光エネルギ
変換、生理機能などの機能材料として、近年特に注目さ
れている。
このような機能を有するフタロシアニンをポリマと結合
すれば、ポリマに上記の各機能を付与することが出来１
例えば触媒機能を持つポリマをはじめ、消臭性ポリマや
導電性ポリマのような様々な機能を持つ材料設計が可能
になる。特開昭６２１０４８０７号公報には金属フタロ
シアニン誘導体を高分子化合物に結合させた高分子金属
錯体、特開昭６３−２７３６３８号公報には金属フタロ
シアニン環を主鎖に含むポリエステルが開示されている
。Conventionally, metal phthalocyanines have been widely used as highly fast blue and green pigments and dyes. This metal phthalocyanine is an extremely stable macrocyclic planar ligand metal complex with a tetraazaporphyrin skeleton. In recent years, it has attracted particular attention as a functional material for catalysts, electrons, photo energy conversion, physiological functions, etc., despite its extremely small metal content in a special electronic environment with a large -T (electronic system). By combining phthalocyanine with such functions with a polymer, it is possible to impart each of the above functions to the polymer1.
For example, it will become possible to design materials with various functions, such as polymers with catalytic functions, deodorizing polymers, and conductive polymers. JP-A-62104807 discloses a polymeric metal complex in which a metal phthalocyanine derivative is bonded to a polymer compound, and JP-A-63-273638 discloses a polyester containing a metal phthalocyanine ring in the main chain.
【発明が解決しようとする課題］
本発明はフィルムや繊維などへの成形性に優れ、２−メ
ルカプトエタノールの酸素酸化反応の触媒として有効な
酸素酸化触媒を提供するものである。
【課題を解決するための手段】
前記の目的を達成するために本発明者らは、金属フタロ
シアニンを含むポリマの合成、性質１機能およびその応
用などの研究を進めた結果、金属フタロシアニンを主鎖
に含むポリウレタン樹脂が２−メルカプトエタノールの
酸素酸化反応の触媒として優れていることを見出し１本
発明を完成するに至った。
（以下余白）
即ち本発明の第１発明の酸素酸化触媒は、繰返
し単位が
［
］
式
で表わされる金属フタロシアニンを主鎖に含むポリ
ウレタンを含有している。
Ｍは金属原子である。
Ｘおよびｙは自然数であ
る。
また、
第２発明の酸素酸化触媒は、
繰返し単位
が［２］
式
で表わされる金属フタロシアニンを主鎖に含むポリウレ
タンを含有している。
Ｍは金属原子である。Ｘおよびｙは自然数である。
第１発明の酸素酸化触媒である金属フタロシアニンを主
鎖に含むポリウレタンは以下のように合成する。
金属フタロシアニンジカルボン酸誘導体を出発物質とし
、塩化チオニル（ＳＯＣｌｉｌ を用いて金属フタ・ロ
シアニン酸クロライドを合成する。なお金属フタロシア
ニンジカルボン酸の合成は、例えば特開昭６３−２７３
６３８号公報に記載されている。
合成した金属フタロシアニン酸クロライド誘導体に ｐ
、ｐ’−ビフェノールＨ□ｅ□Ｈを反応させて脱塩酸を
行ない、金属フクロシアニンビフェノールエステル誘導
体を得る。
その金属フタロシアニンビフェノールエステル誘導体に
１．６−ヘキサンジオール（ＨＯ−ｆｃｕ、ｌ ｓ−０
旧と１．６−ヘキサンジイソシアネートｆＯＣＮ−ｆｃ
ｌＩｘ） ５−ＮＣＯＩを所定のモル比で加え、窒素気
流下、ジメチルホルムアミド（ＤＭＦＩ中で加軌する。
すると金属フタロシアニンビフェノール誘導体のヒドロ
キシ基（−ＯＨ基）と１．６−ヘキサンジオールのヒド
ロキシ基（−０１１Ｍ ＋が夫々１．６−ヘキサンジイ
ソシアネートのイソシアネート基（−ＮＣＯＩ と重付
加反応を起こし、ウレタン結合（−００ＣＨＮ−１をつ
くり、ポリウレタンが得られる。
以下に反応経路を示す。
第２発明の酸素酸化触媒である金属フタロシアニンを主
鎖に含むポリウレタンは、出発物質を金属フタロシアニ
ンテトラカルボン酸に替えることにより、同様に合成す
ることが出来る。
以下に反応経路を示す。
ｃ以下余白）
なお、金属フタロシアニンを主鎖に含むポリウレタンは
酸素酸化触媒の総量に対して３０重量％以上含まれてい
ることが望ましい。[Problems to be Solved by the Invention] The present invention provides an oxygen oxidation catalyst that has excellent moldability into films, fibers, etc. and is effective as a catalyst for the oxygen oxidation reaction of 2-mercaptoethanol. [Means for Solving the Problems] In order to achieve the above object, the present inventors have carried out research on the synthesis of polymers containing metal phthalocyanine, property 1 function, and their applications, and as a result, the present inventors have developed a polymer containing metal phthalocyanine in the main chain. The present inventors have discovered that the polyurethane resin contained in 2-mercaptoethanol is excellent as a catalyst for the oxygen oxidation reaction of 2-mercaptoethanol, and have completed the present invention. (The following is a blank space) That is, the oxygen oxidation catalyst of the first aspect of the present invention contains a polyurethane whose main chain contains a metal phthalocyanine whose repeating unit is represented by the formula [ ]. M is a metal atom. X and y are natural numbers. Further, the oxygen oxidation catalyst of the second invention contains a polyurethane whose main chain contains a metal phthalocyanine whose repeating unit is represented by the formula [2]. M is a metal atom. X and y are natural numbers. The polyurethane containing metal phthalocyanine, which is the oxygen oxidation catalyst of the first invention, in its main chain is synthesized as follows. Using a metal phthalocyanine dicarboxylic acid derivative as a starting material, metal phthalocyanine acid chloride is synthesized using thionyl chloride (SOClil).The synthesis of metal phthalocyanine dicarboxylic acid is described, for example, in JP-A-63-273.
It is described in Publication No. 638. p to the synthesized metal phthalocyanine acid chloride derivative
, p'-biphenol H□e□H are reacted to remove hydrochloric acid to obtain a metal fucrocyanine biphenol ester derivative. The metal phthalocyanine biphenol ester derivative contains 1,6-hexanediol (HO-fcu, l s-0
Old and 1,6-hexane diisocyanate fOCN-fc
lIx) 5-NCOI is added at a predetermined molar ratio and heated in dimethylformamide (DMFI) under a nitrogen stream.Then, the hydroxy group (-OH group) of the metal phthalocyanine biphenol derivative and the hydroxy group of 1.6-hexanediol are added. (-011M + causes a polyaddition reaction with the isocyanate group (-NCOI) of 1.6-hexane diisocyanate, forming a urethane bond (-00CHN-1) to obtain polyurethane. The reaction route is shown below. Second invention A polyurethane containing metal phthalocyanine, which is an oxygen oxidation catalyst, in the main chain can be synthesized in the same way by changing the starting material to metal phthalocyanine tetracarboxylic acid.The reaction route is shown below. It is desirable that the polyurethane containing metal phthalocyanine in its main chain is contained in an amount of 30% by weight or more based on the total amount of the oxygen oxidation catalyst.
以下１本発明の実施例を詳細に説明する。
実施例１
乳鉢で良くすり潰したコバルトフタロシアニンジカルボ
ン酸２．００ｇに塩化チオニル２０ｍｆｆ１を加え、１
１０℃で２０時間加熱環流した。反応終了後、放冷した
のち、減圧エバポレーションを行ない乾固させた。この
固体生成物に石油エーテルを加えて、ガラスフィルタで
固形物を濾別した後、減圧乾燥し、コバルトフタロシア
ニンジカルボン酸クロライドを得た。
これに ｐ、ｐ’−ビフェノール１１．２８ｇを加え、
マグネットスタラーにて撹拌しながら１１０℃で１５時
間加ｐｔ４した１反応終了後、放冷し、減圧エバポレー
ションを行ない乾固させた。この固体生成物にアセトン
を加え、ガラスフィルタで固形物を濾別した後、減圧乾
燥し、コバルトフタロシアニンビフェノールエステル誘
導体２．７４ｇを得た。
得られたコバルトフタロシアニンビフェノールエステル
誘導体０．ｌＯｇ（１，ｏｘｌＯ−’モル）に、１．６
−ヘキサンジオール１．１６ｇ（９，９ｘｌＯ−”モル
）と１．６−ヘキサンジイソシアネート１．８２ｇ（１
，Ｉｘｌ（１−”モル）とを加え、窒素気流下、ジメチ
ルホルムアミドＩＤＭＦＩ中で１４０℃で１２時間、１
３０℃で３時間加軌撹拌した。
反応終了後、室温まで放冷な行なうと内容物がゲル状に
固化してくるので、再加熱を行なって熱い溶液状態で水
中に投じ、沈殿を生じさせた。３０分程撹拌した後、ガ
ラスフィルタで固形物を濾過した。濾別した固形物をメ
タノール中で５〜８時間撹拌した後、ガラスフィルタで
濾別して減圧乾燥を行ない、前述の式［１］で示される
コバルトフタロシアニンを主鎖に含むポリウレタン（フ
タロシアニンビフェノールエステル−２） ２．８１ｇ
を得た。収率は９１％であった。
実施例２
コバルトフタロシアニンジカルボン酸の替りにコバルト
フタロシアニンテトラカルボン酸を用いる他は実施例１
と同様にして前述の式［２］で示されるコバルトフタロ
シアニンを主鎖に含むポリウレタン（フタロシアニンビ
フェノールエステル−４） ２．６７ｇを得た。収率は
８６％であった。
実施例１および２で得られたポリウレタンについて、原
子吸光法を用いてコバルト含量（コバルトフタロシアニ
ン含量）を求めた。またＤＳＣ（示差走査Ｐｌ！ｌ計量
計定を行なって熱的性質を求めた。第１表に、得られた
各ポリウレタンのコバルトフタロシアニン（Ｃｏ−Ｐｃ
１含有率、収率、融点、分解温度を示す。
第 １ 表
上記実施例で得た２種のポリウレタンを用いて２−メル
カプトエタノール（ＨＯＣＨ，Ｃ１，ＳＨｌの酸素酸化
反応を行ない、この反応に伴う酸素消費濃度を測定した
。
θ１ｊ定にはワールブルク圧力計を使用する。摺合わせ
式の反応容器の主室側に、実施例１で合成したポリウレ
タン樹脂（フタロシアニンビフェノールエステル−２）
１．０３ｍｇを水１ｍｆｆ１と共に入れ、反応容器の
側室側に ０．５５ｍｏｌ／ｊの２−メルカプトエタノ
ール水溶液１ｍｊを入れる。２−メルカブトエタノール
水溶液は水酸化カリウムによりＰ）Ｉ＝７．０に調整し
、濃度をヨウ素滴定で決定したちのである。
反応容器を恒温槽に入れて温度を一定にした後、側室側
の２−メルカプトエタノール水溶液を主室側に注ぎ、１
３６ｒｐｍで撹拌、混合し、一定時間毎に〆自費される
酸素量をマノメータで読み取った。
さらに反応容器に２−メルカプトエタノールのみを入れ
て上記と同一条件における２−メルカプトエタノールの
自然酸化で消費される酸素量を求め、先に読み取った値
を補正して酸素消費濃度を求めた。
また、主室側に実施例２で合成したポリウレタン樹脂（
フクロシアニンビフェノールエステル−４） １．９８
ｍｇを水１ＩＩｌｊと共に入れ、実施例１と同様にして
酸素消費濃度を求めた。
第１図に各実施例の酸素消費濃度ｆｍｏｌ＃ｌの経時変
化を示す。
また、１５〜３５℃で得られた律速過程の反応速度定数
に５より、アレニウスの手法を用いて活性化エネルギー
を求めた。ここでのフタロシアニン濃度は１．０ｘｌＯ
−’ ｆｍｏｌ＃ｌ で一定とした。第２表に、反応に
おける活性化パラメータ（反応速度Ｖｍａｘ、ミカエリ
ス定１？ＲＫ、、反応速度定数に６、活性化エンタルピ
ーΔＨ１、活性化エンタルピー△Ｓｔ ）を示す。
第 ２ 表Hereinafter, one embodiment of the present invention will be described in detail. Example 1 20 mff1 of thionyl chloride was added to 2.00 g of cobalt phthalocyanine dicarboxylic acid well ground in a mortar, and 1
The mixture was heated under reflux at 10° C. for 20 hours. After the reaction was completed, the mixture was allowed to cool and then evaporated under reduced pressure to dryness. Petroleum ether was added to this solid product, solid matter was filtered out using a glass filter, and then dried under reduced pressure to obtain cobalt phthalocyanine dicarboxylic acid chloride. Add 11.28g of p,p'-biphenol to this,
After completion of one reaction in which pt4 was added at 110° C. for 15 hours while stirring with a magnetic stirrer, the mixture was allowed to cool and evaporated under reduced pressure to dryness. Acetone was added to this solid product, and the solid matter was filtered out using a glass filter, followed by drying under reduced pressure to obtain 2.74 g of a cobalt phthalocyanine biphenol ester derivative. The obtained cobalt phthalocyanine biphenol ester derivative 0. lOg (1, oxlO-'mol), 1.6
-hexanediol 1.16g (9,9xlO-"mol) and 1.82g (1
.
The mixture was stirred at 30° C. for 3 hours. After the reaction was completed, the contents solidified into a gel when left to cool to room temperature, so the contents were reheated and poured into water as a hot solution to form a precipitate. After stirring for about 30 minutes, solid matter was filtered through a glass filter. After stirring the filtered solid in methanol for 5 to 8 hours, it was filtered through a glass filter and dried under reduced pressure to obtain a polyurethane (phthalocyanine biphenol ester-2) containing cobalt phthalocyanine in the main chain represented by the above formula [1]. ) 2.81g
I got it. The yield was 91%. Example 2 Example 1 except that cobalt phthalocyanine tetracarboxylic acid is used instead of cobalt phthalocyanine dicarboxylic acid.
In the same manner as above, 2.67 g of polyurethane (phthalocyanine biphenol ester-4) containing cobalt phthalocyanine represented by the above formula [2] in the main chain was obtained. The yield was 86%. The cobalt content (cobalt phthalocyanine content) of the polyurethanes obtained in Examples 1 and 2 was determined using atomic absorption spectrometry. Thermal properties were also determined by DSC (differential scanning Pl!l metrology).Table 1 shows the cobalt phthalocyanine (Co-Pc) of each polyurethane obtained.
1 content, yield, melting point, and decomposition temperature. Table 1 Using the two types of polyurethanes obtained in the above examples, an oxygen oxidation reaction of 2-mercaptoethanol (HOCH, C1, SHI) was carried out, and the oxygen consumption concentration accompanying this reaction was measured. The Warburg pressure was used to determine θ1j. The polyurethane resin (phthalocyanine biphenol ester-2) synthesized in Example 1 was placed on the main chamber side of the sliding type reaction vessel.
1.03 mg was added together with 1 mff1 of water, and 1 mj of a 0.55 mol/j aqueous 2-mercaptoethanol solution was added to the side chamber of the reaction vessel. The 2-mercabutoethanol aqueous solution was adjusted to P)I=7.0 with potassium hydroxide, and the concentration was determined by iodometric titration. After placing the reaction container in a constant temperature bath and keeping the temperature constant, pour the 2-mercaptoethanol aqueous solution from the side chamber into the main chamber.
The mixture was stirred and mixed at 36 rpm, and the amount of oxygen consumed at regular intervals was read using a manometer. Further, only 2-mercaptoethanol was placed in the reaction vessel, and the amount of oxygen consumed by natural oxidation of 2-mercaptoethanol under the same conditions as above was determined, and the previously read value was corrected to determine the oxygen consumption concentration. In addition, the polyurethane resin synthesized in Example 2 (
Fuclocyanine biphenol ester-4) 1.98
mg was added together with 1IIIlj of water, and the oxygen consumption concentration was determined in the same manner as in Example 1. FIG. 1 shows changes over time in the oxygen consumption concentration fmol#l of each example. Furthermore, the activation energy was determined using the Arrhenius method based on the reaction rate constant of the rate-determining process obtained at 15 to 35°C. The phthalocyanine concentration here is 1.0xlO
-'fmol#l was kept constant. Table 2 shows activation parameters in the reaction (reaction rate Vmax, Michaelis constant 1?RK, reaction rate constant 6, activation enthalpy ΔH1, activation enthalpy ΔSt). Table 2
以上詳細に説明したように本発明の酸素酸化触媒は、２
−メルカプトエタノールの酸素酸化反応を触媒する。ま
た、この酸素酸化触媒はポリウレタンの性質も有してお
り、触媒としての機能を有したまま様々な形状に成形で
きる他、成形物の構成材料としてち使用可能である。As explained in detail above, the oxygen oxidation catalyst of the present invention has 2
- Catalyze the oxygen oxidation reaction of mercaptoethanol. Furthermore, this oxygen oxidation catalyst also has the properties of polyurethane, and can be molded into various shapes while retaining its catalytic function, and can also be used as a constituent material of molded products.
第１図は本発明の酸素酸化触媒の性能試験結果を示す図
である。FIG. 1 is a diagram showing the performance test results of the oxygen oxidation catalyst of the present invention.
Claims (1)
れる金属フタロシアニンを主鎖に含むポリウレタンを含
有する酸素酸化触媒。 ２、繰返し単位が下式、 ▲数式、化学式、表等があります▼［２］ （式中、Ｍは金属原子、ｘおよびｙは自然数）で表わさ
れる金属フタロシアニンを主鎖に含むポリウレタンを含
有する酸素酸化触媒。[Claims] 1. A metal phthalocyanine whose repeating unit is represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ [1] (In the formula, M is a metal atom, x and y are natural numbers) in the main chain Oxygen oxidation catalyst containing polyurethane. 2. Contains a polyurethane whose main chain contains a metal phthalocyanine whose repeating unit is represented by the following formula, ▲Mathematical formula, chemical formula, table, etc.▼[2] (In the formula, M is a metal atom, and x and y are natural numbers) Oxygen oxidation catalyst.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1320068A JPH03181333A (en) | 1989-12-08 | 1989-12-08 | Catalyst for oxidation with oxygen |
| US07/570,117 US5053464A (en) | 1989-12-08 | 1990-08-20 | Polyurethane containing metal phthalocyanine in the main chain |
| EP90116093A EP0431262B1 (en) | 1989-12-08 | 1990-08-22 | Polyurethane containing metal phthalocyanine in the main chain |
| DE69010852T DE69010852T2 (en) | 1989-12-08 | 1990-08-22 | Polyurethane in the main chain containing metal phthalocyanine. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1320068A JPH03181333A (en) | 1989-12-08 | 1989-12-08 | Catalyst for oxidation with oxygen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03181333A true JPH03181333A (en) | 1991-08-07 |
Family
ID=18117365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1320068A Pending JPH03181333A (en) | 1989-12-08 | 1989-12-08 | Catalyst for oxidation with oxygen |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03181333A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119158623A (en) * | 2023-06-19 | 2024-12-20 | 中国石油化工股份有限公司 | Preparation method of solid-supported low-carbon hydrocarbon alkali-free deodorization catalyst |
-
1989
- 1989-12-08 JP JP1320068A patent/JPH03181333A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119158623A (en) * | 2023-06-19 | 2024-12-20 | 中国石油化工股份有限公司 | Preparation method of solid-supported low-carbon hydrocarbon alkali-free deodorization catalyst |
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