JPH0394842A - Cation-exchange carbon body and its production - Google Patents
Cation-exchange carbon body and its productionInfo
- Publication number
- JPH0394842A JPH0394842A JP1229859A JP22985989A JPH0394842A JP H0394842 A JPH0394842 A JP H0394842A JP 1229859 A JP1229859 A JP 1229859A JP 22985989 A JP22985989 A JP 22985989A JP H0394842 A JPH0394842 A JP H0394842A
- Authority
- JP
- Japan
- Prior art keywords
- cation
- precursor
- carbon body
- resin
- polycarbodiimide resin
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 18
- 238000005341 cation exchange Methods 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 230000001180 sulfating effect Effects 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 229920001519 homopolymer Polymers 0.000 claims abstract description 4
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 229950011008 tetrachloroethylene Drugs 0.000 abstract description 4
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ZBVOEVQTNYNNMY-UHFFFAOYSA-N O=P1=CCCC1 Chemical class O=P1=CCCC1 ZBVOEVQTNYNNMY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- IOSIDVPNBKUUFA-UHFFFAOYSA-N 1-ethyl-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound CCP1(=O)CCC=C1 IOSIDVPNBKUUFA-UHFFFAOYSA-N 0.000 description 1
- YUQUHJGNZFFDAA-UHFFFAOYSA-N 1-phenyl-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound C=1C=CC=CC=1P1(=O)CCC=C1 YUQUHJGNZFFDAA-UHFFFAOYSA-N 0.000 description 1
- JXGNHEUFHNJWDY-UHFFFAOYSA-N 2,5-dihydro-1h-phosphole Chemical class C1PCC=C1 JXGNHEUFHNJWDY-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- STUPVELWKGXMQS-UHFFFAOYSA-N CC1=CP(=O)CC1 Chemical compound CC1=CP(=O)CC1 STUPVELWKGXMQS-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- MPRCWBFYAMJUTK-UHFFFAOYSA-N [As].S(O)(O)(=O)=O Chemical compound [As].S(O)(O)(=O)=O MPRCWBFYAMJUTK-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はポリカルボジイミド樹脂を涼科として得られる
カチオン交換炭素体及びその製造力法に関するものであ
る．
（従来の技術及び発明が解決しようヒする問題点）
従来より、石炭、木炭、炭素黒、炭素繊維等の炭素資材
料を硫酸で加熱処理すると、カチオン交換体となるこヒ
が知られている．
一方、フィルム状の炭素質材料としては、黒鉛フィルム
が作られていて、これを前記ヒ同様に処理すれば、カチ
オン交換体ヒなることるは容易に予想されるが、殆どｌ
． Ｏ Ｏ％の炭素よりなる黒鉛は、硫酸ヒ加熱処理す
るε、交換基が十分に導入される以前に材科目体が劣化
してしまうという欠点があった．
即ち、上記の事実から、特にカチオン交換炭素体の材料
ヒしては、１００％炭素の材料よりも、或る程度水素原
子を含有する炭素質のものが適当な材料であると思われ
るのである．以上のようなここから、カチオン交換炭素
体作成のための材料として、適当量の水素原子を含む炭
素質フィルムの開発、提供が待たれていた．
（問題点を解決するための手段）
本発明は、上述した従来技術の難点を解消するためにな
されたもので、本発明のカチオン交換炭素体は、ポリカ
ルボジイミド樹脂を加熱処理して得られる炭素化プレカ
ーサーを、硫酸化及び酸化して得られることを特徴とす
るものであり、又２その製造方法は、ポリカルボジイミ
ド樹脂を加熱処理して炭素化プレカーサーとなし、該炭
素化プレカーサーを硫酸化及び酸化することを特徴ヒす
るものである．
即ち、本発明の発明者らは、ポリ力ルポジイミド樹脂を
、例えば真空中或は不活性気体雰囲気中で５００乃至１
、５００℃に加熱処理するヒ強度の高い炭素化プレカー
サーになるここ、及び、この炭素化プレカーサーを、例
えば濃硫酸や発煙硫酸中で１００乃至２５０℃の温度に
加熱して硫酸化及び酸化すると、カチオン交換炭素体に
なることを見出して本発明を完成した．
以下本発明について更に詳細に説明する．本発明におい
て使用きれるポリカルボジイミド樹脂それ自体は、既知
のもの或は既知のものと同様にして製造するここができ
るものであって［米国特許第２．９４１，９６６号明細
書：特公昭４７−３３２９７号公報： Ｊ．Ｏｒｇ．Ｃ
ｈｅｍ．，２８、２０６９−２０７５（１９６３） ：
Ｃｈｅｍｉｃａｌ ＲｅｖＮｅｗ． １９８１．Ｖｏ
ｌ．８１，Ｎｏ．４．６１．９−６２１等今照］、例え
ば、有機ジイソシアネ一トの脱二酸化炭素を伴う縮合反
応により容易に製造することができる．
このポリカルボジイミド樹脂の製造に使用される有機ジ
イソシアネートは、脂肪系、脂環式系、芳香族系、芳香
一脂肪族系等いずれのタイプのものであってもよく、こ
れらは単独で用いても、又、２種以上組合せて用いて共
重合体としてもよい．
而して、本発明の方法において使用されるポリ力ルポジ
イミド樹脂には、式
（−Ｒ−Ｎ＝Ｃ＝Ｎ−），１ （１）で示される少な
くとも１種の繰り返し単位からむる単独共重合体又は共
重合体が包含され、又，上記式（１）における有機ジイ
ソシアネート残基Ｒとしては、数あるものの中でもとり
わけ芳香族ジイソシアネート残基が好適である［ここで
有機ジイソシアネート残基とは、有機ジイソシアネート
分子から２つのイソシアネート基（ＮＣＯ）を除いた残
りの部分をいう〕．
又、ポリカルボジイミド化のための触媒については、特
に制限がな《、従来より使用きれている１−フェニル−
２−ホスホレンー１−オキシド、３−メチル−２−ホス
ホレン−１−オキシド、１−エトルー３−メチル−２−
ホスホレン−１−オキシド、１−エチル−２−ホスホレ
ン−１−オキシド、或はこれらの３−ホスホレン異性体
等のホスホレンオキシドを例示するこヒができる．
このようにして得られるポリ力ルポジイミド樹脂の具体
例ヒしては次のものを挙げるこヒができる．
（本頁以下余白）
上記各式において、重合度ｎは！ロー１０， ０００の
範囲内、好ましくは５０−５， ０００の範囲である．
尚、前記ポリ力ルポジイミド樹脂の端末は、モノイソシ
アネート等を用いて封止されていてもよく、以上説明し
たポリカルボジイミド樹脂は、溶液のままの状態で、或
は、溶液から沈殿させた粉末として得ることができる．
次に、このよう番こして得たポリ力ルポジイミド樹脂を
フィルム状等の所望の形状に成形する．成形するには、
例えば、ポリカルホジイミド樹脂を重合終了後の溶液の
まま、或は一旦粉末として得てから、溶媒に溶解した溶
液ヒし、この溶液を、例えば平滑なガラス板上等にキャ
ストした後、．溶媒を除去する方法等を採ればよい．こ
の溶媒としては、テトラクロロエチレン、Ｅリクロロエ
チレン、テトラヒドロフラン、ジオキサン、モノクロロ
ベンゼン、ジクロロベンゼン、ジメチルホルムアミド、
Ｎ−メチル−２−ビロリドン、ジメチルアセトアミド、
ジメチルスルフオキシド等を使用することができる．．
又、粉末の場合は、圧縮成形、ロール成形、射出成形，
トランスファー戊形等によってもよい．これらにより成
形体として厚み０． １ｍｍ−３ｍｍ程度のものを容易
に得ることができる．そして、上記のような方法で製造
成形したポリカルボジイミド樹脂を加熱して、炭素化プ
レカーサ〜とする．この場合の加熱条件としては、既に
説明したように、真空中或は窒素ガス等の不活性気体雰
囲気中で、５００乃至ｌ．５００″ＣＭいう温度範囲を
例示することができる．
最後に、上記のようにして得られた炭素化プレカーサー
を、硫酸化及び酸化することにより、本発明カチオン交
換炭素体が得られるここになるが、この硫酸化及び酸化
の工程は、例えば硫酸や発煙硫酸中で上記炭素化プレカ
ーサーを加熱すれば良い．
（実施例）
以下に本発明の実施例について述べる．Ａ．ポリカルボ
ジイミド樹脂フイルムの製造２．１−１−リレンジイソ
シアネート／２，６トリレンミンイソシアネート（８０
／２０）の混合物５４ｇを、テトラクロ口エチレン５０
０ｍ１中で、カルボジイミド化触媒（１−フ山ニルー３
−メチルホスフォレン才キサイド）０４１２ｇｅ共に、
１２０℃で４時間反応さセ、ポリカルボジイミド溶液を
得た．この溶液から乾式法により厚さ１００μｍのポリ
力ルポジイミドフィルムを得た．
Ｄ，炭素化処理
上記ポリカルボジイミドフィルムを、室素気流中で所定
温度まで、５℃／分の昇温速度で加熱し、炭素化プレカ
ーサーを得た．
以下に、処理番号と処理温度を示す．
Ｂ−１ ５００℃
Ｂ−２ ７００℃
１３ − ３ ９ ０ ０℃
Ｂ−４ １，０００℃
Ｂ−５ １．５００℃
Ｂ−６ 未処理
Ｂ−７ ２。０００℃
Ｃ．カチオン交換炭素体化
上記の炭素化プレカーサーを、硫酸中で所定温度に加熱
した後、脱塩水で十分洗浄し、０．１％カセイソーダ溶
液を加えて、交換基をＮａ形にし、次いで４％塩酸溶液
でＩＪ形にし、脱塩水で十分洗浄し２た．２４時間放置
した後、上澄液中に塩素イオンが認められなくなった時
点で洗浄を終了した，
このようにして得られたカチオン交換炭素体につき、以
下の事項を測定した．
総交換容盟の測定：
風乾した試料１ｇをＯ．ＩＮカセイソ
ーダ溶液１００ｍｌに入れ、４８時間以上放置して、完
全にイオン交換を行なわせた．この上澄液中から２０ｒ
ｎＬをビベットで取り、０。ＩＮ塩酸溶液で滴定した．
（指示薬：メチルレッド）
滴定値と、試料の絶乾量から総交換容量（ｍ．ｅｑ／ｇ
）を算出した．
強酸交換容量の測定：
風乾した試料１ｇを４％塩化ナＬリウム溶液ＸＯＯｒｒ
ｈｌに入れ、４８時間以上放置し、完全にイオン交換を
行なわせた．この上澄液２０ｍｌを、０．ＩＮカセイソ
ーダ溶液で滴定した（指示薬；メチルレツドーメチレン
ブルー混合）ｎ
この滴定値ヒ試料の絶乾盟から強酸交換容ｉｔ （＋ｎ
ｅｑ／ｇ）を算出した．弱酸交襖容ｆｆｉ：
総交換容量と強酸交換容量との差を弱酸交換容ｔ，？ｔ
，た．
結果を以−：・の表１に示す．
Ｄ．ポリカルポジイミド樹脂フィルムの製造メチレンジ
フ品ニルジイソシアネート５０ｇを、テトラクロロエチ
レン８２０ｍｌ中で、カルボジイミド化触媒（１−フェ
ニル−３−メチルホスフォレン才キサイド）０．１３ｇ
と共に、１２０℃で６時間反応させた．この溶液な室温
に冷却するこヒにより、ポリカルボジイミドが沈殿した
．
この沈殿物を濾過し、ｌ００℃で４時間乾燥し、ポリ力
ルポジイミド粉末を得た．この粉末を、プレス温度１８
０℃、プレス圧ｓ ｏ ｋｇ／ｃｍ”でプレス成形し、
厚さ１００μｍのポリカルボジイミドフイルムを作成し
た．
作成したフイルムをＢａ同様な方法で炭素化した．
以下に、処理番号と処理温度を示す．
Ｄ−６ ５００℃
Ｄ−７ ７００℃
Ｄ−８ １，０００℃
Ｄ−９ ２，０００℃
得られたフイルムなＣと同様な方法でカチオン交換炭素
フイルム化した．
結果を以下の表２に示す．
（本頁以下余白）
（発明の効果）
以上のように、本発明はポリ力ルポジイミド樹脂を加熱
処理した炭素化プレヵーサーを使用しているから、本来
的に高い強度を具えており、しかも、或る程度の水素原
子を含んでいるため、硫酸化及び酸化により、劣化する
ことなしに交換基が十分に導入され、優れたカチオン交
換能を有しているものである．DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a cation-exchange carbon body obtained from a polycarbodiimide resin and a method for producing the same. (Problems to be solved by conventional technology and invention) It has been known that when carbon materials such as coal, charcoal, carbon black, and carbon fiber are heat-treated with sulfuric acid, they become cation exchangers. ．． On the other hand, as a film-like carbonaceous material, a graphite film is made, and if it is treated in the same manner as above, it is easily expected that it will become a cation exchanger.
．． Graphite, which is composed of O O% carbon, has the disadvantage that when heat treated with sulfuric acid arsenic, the material body deteriorates before sufficient exchange groups are introduced. In other words, from the above facts, it seems that carbonaceous materials containing a certain amount of hydrogen atoms are more appropriate materials than 100% carbon materials, especially for cation-exchanged carbon bodies. ．． Based on the above, the development and provision of a carbonaceous film containing an appropriate amount of hydrogen atoms as a material for creating cation-exchanged carbon bodies has been awaited. (Means for Solving the Problems) The present invention has been made to solve the above-mentioned difficulties of the prior art. It is characterized in that it is obtained by sulfating and oxidizing a carbonized precursor, and its manufacturing method includes heating a polycarbodiimide resin to form a carbonized precursor, and sulfating and oxidizing the carbonized precursor. It is characterized by its ability to oxidize. That is, the inventors of the present invention have prepared a polypropodiimide resin in a vacuum or in an inert gas atmosphere at a temperature of 500 to 1
This becomes a carbonized precursor with high strength when heated to 500°C, and when this carbonized precursor is heated to a temperature of 100 to 250°C in concentrated sulfuric acid or fuming sulfuric acid, for example, to sulfate and oxidize, The present invention was completed by discovering that it can become a cation-exchanged carbon body. The present invention will be explained in more detail below. The polycarbodiimide resin itself that can be used in the present invention is a known one or one that can be produced in a similar manner to a known one [U.S. Pat. Publication No. 33297: J. Org. C
hem. , 28, 2069-2075 (1963):
Chemical RevNew. 1981. Vo
l. 81, No. 4.61.9-621 etc.], for example, can be easily produced by a condensation reaction of an organic diisocyanate with removal of carbon dioxide. The organic diisocyanate used in the production of this polycarbodiimide resin may be of any type, such as aliphatic, alicyclic, aromatic, or mono-aromatic, and these may be used alone. Alternatively, two or more types may be used in combination to form a copolymer. Therefore, the polylupodiimide resin used in the method of the present invention includes a homopolymer comprising at least one repeating unit represented by the formula (-R-N=C=N-), 1 (1). Aromatic diisocyanate residues are particularly suitable as the organic diisocyanate residue R in the above formula (1). [Here, the organic diisocyanate residue refers to Refers to the remaining portion after removing two isocyanate groups (NCO) from a diisocyanate molecule]. In addition, there are no particular restrictions on the catalyst for polycarbodiimidation, and 1-phenyl-
2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethru-3-methyl-2-
Examples include phospholene oxides such as phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, and 3-phospholene isomers thereof. Specific examples of the polypropylene resin obtained in this manner are as follows. (Margin below this page) In each of the above formulas, the degree of polymerization n is! Low in the range of 10,000, preferably in the range of 50-5,000.
Note that the terminals of the polycarbodiimide resin may be sealed using monoisocyanate or the like, and the polycarbodiimide resin described above can be used as a solution or as a powder precipitated from the solution. Obtainable. Next, the polypropylene resin obtained by straining in this manner is molded into a desired shape such as a film. To form,
For example, a polycarphodiimide resin may be obtained as a solution after completion of polymerization or as a powder, and then dissolved in a solvent, and this solution is cast, for example, on a smooth glass plate. Any method that removes the solvent may be used. Examples of the solvent include tetrachloroethylene, E-lichloroethylene, tetrahydrofuran, dioxane, monochlorobenzene, dichlorobenzene, dimethylformamide,
N-methyl-2-pyrrolidone, dimethylacetamide,
Dimethyl sulfoxide etc. can be used. ．． In addition, in the case of powder, compression molding, roll molding, injection molding,
It is also possible to use a transfer method, etc. With these, the thickness of the molded product is 0. You can easily obtain one with a size of about 1mm to 3mm. The polycarbodiimide resin produced and molded by the method described above is then heated to form a carbonized precursor. In this case, the heating conditions are as described above, in a vacuum or in an inert gas atmosphere such as nitrogen gas, at a heating temperature of 500 l. For example, a temperature range of 500''CM can be exemplified.Finally, the cation-exchanged carbon body of the present invention can be obtained by sulfating and oxidizing the carbonized precursor obtained as described above. The sulfation and oxidation steps may be carried out by heating the carbonized precursor in, for example, sulfuric acid or fuming sulfuric acid. (Example) Examples of the present invention will be described below. A. Production of polycarbodiimide resin film 2 .1-1-lylene diisocyanate/2,6 tolylenmine isocyanate (80
54 g of a mixture of /20) and 50 g of tetrachlorethylene
In 0ml, carbodiimidization catalyst (1-F Mt. Ni-3
- Methylphosphorene dioxide) 0412ge together,
After reacting at 120°C for 4 hours, a polycarbodiimide solution was obtained. From this solution, a 100 μm thick polypropylene diimide film was obtained by a dry method. D. Carbonization Treatment The above polycarbodiimide film was heated to a predetermined temperature in a room air stream at a heating rate of 5° C./min to obtain a carbonized precursor. The processing numbers and processing temperatures are shown below. B-1 500°C B-2 700°C 13-3900°C B-4 1,000°C B-5 1.500°C B-6 Untreated B-7 2.000°C C. Cation exchange carbonization The above carbonization precursor was heated to a predetermined temperature in sulfuric acid, washed thoroughly with demineralized water, added with 0.1% caustic soda solution to convert the exchange group into Na form, and then 4% hydrochloric acid It was made into an IJ shape with a solution and thoroughly washed with demineralized water. After being left for 24 hours, washing was completed when no chloride ions were observed in the supernatant. The following items were measured for the cation-exchanged carbon body thus obtained. Measurement of total exchange volume: 1 g of air-dried sample was added to O. The sample was placed in 100 ml of IN caustic soda solution and left for more than 48 hours to allow complete ion exchange. 20r from this supernatant
Take nL with bibet and 0. Titrated with IN hydrochloric acid solution.
(Indicator: Methyl Red) From the titration value and the absolute dry weight of the sample, the total exchange capacity (m.eq/g
) was calculated. Measurement of strong acid exchange capacity: 1 g of air-dried sample was added to 4% sodium chloride solution XOOrr
HL and left for over 48 hours to allow complete ion exchange. 20 ml of this supernatant was added to 0.0 ml of this supernatant liquid. Titrated with IN caustic soda solution (indicator: mixed with methyl red and methylene blue) n This titration value is the sample's bone dry to strong acid exchange capacity (+n
eq/g) was calculated. Weak acid exchange capacity ffi: The difference between the total exchange capacity and the strong acid exchange capacity is the weak acid exchange capacity t,? t
,Ta. The results are shown in Table 1 below. D. Production of polycarposiimide resin film 50 g of methylene diisocyanate was added to 0.13 g of carbodiimidization catalyst (1-phenyl-3-methylphosphorene dioxide) in 820 ml of tetrachloroethylene.
The reaction was then carried out at 120°C for 6 hours. Polycarbodiimide was precipitated by cooling this solution to room temperature. This precipitate was filtered and dried at 100°C for 4 hours to obtain polylupodiimide powder. This powder was pressed at a temperature of 18
Press molded at 0°C and press pressure s o kg/cm.
A polycarbodiimide film with a thickness of 100 μm was created. The produced film was carbonized in the same manner as Ba. The processing numbers and processing temperatures are shown below. D-6: 500°C D-7: 700°C D-8: 1,000°C D-9: 2,000°C A cation-exchanged carbon film was formed in the same manner as the obtained film C. The results are shown in Table 2 below. (Margins below this page) (Effects of the invention) As described above, since the present invention uses a carbonized precursor made by heat-treating polypropylene posiimide resin, it inherently has high strength. Because it contains a certain amount of hydrogen atoms, exchange groups can be sufficiently introduced through sulfation and oxidation without deterioration, and it has excellent cation exchange ability.
Claims (1)
素化プレカーサーを、硫酸化及び酸化して得られること
を特徴とするカチオン交換炭素体。 ２ ポリカルボジイミド樹脂は、一般式 （−Ｒ−Ｎ＝Ｃ＝Ｎ−）＿ｎ で示される少なくとも一種の繰返し単位からなる単独重
合体又は共重合体である請求項１記載のカチオン交換炭
素体。 ３ 一般式 （−Ｒ−Ｎ＝Ｃ＝Ｎ−）＿ｎ において、Ｒが芳香族ジイソシアネート残基であること
を特徴とする請求項２記載のカチオン交換炭素体。 ４ 炭素化プレカーサーは、ポリカルボジイミド樹脂を
真空中或は不活性気体雰囲気中で ５００乃至１，５００℃に加熱処理して得られるもので
ある請求項１記載のカチオン交換炭素体。 ５ 炭素化プレカーサーがフィルム状に成形されたもの
である請求項１記載のカチオン交換炭素体。 ６ ポリカルボジイミド樹脂を加熱処理して炭素化プレ
カーサーとなし、該炭素化プレカーサーを硫酸化及び酸
化することを特徴とするカチオン交換炭素体の製造方法
。 ７ポリカルボジイミド樹脂は、一般式 （−Ｒ−Ｎ＝Ｃ＝Ｎ−）＿ｎ で示される少なくとも一種の繰返し単位からなる単独重
合体又は共重合体である請求項６記載のカチオン交換炭
素体の製造方法。 ８ 一般式 （−Ｒ−Ｎ＝Ｃ＝Ｎ−）＿ｎ において、Ｒが芳香族ジイソシアネート残基であること
を特徴とする請求項７記載のカチオン交換炭素体の製造
方法。 ９ 炭素化プレカーサーは、ポリカルボジイミド樹脂を
真空中或は不活性気体雰囲気中で ５００乃至１，５００℃に加熱処理して得られるもので
ある請求項６記載のカチオン交換炭素体の製造方法。 １０ 炭素化プレカーサーがフィルム状に成形されたも
のである請求項６記載のカチオン交換炭素体の製造方法
。[Scope of Claims] 1. A cation exchange carbon material obtained by sulfating and oxidizing a carbonization precursor obtained by heat treating a polycarbodiimide resin. 2. The cation exchange carbon body according to claim 1, wherein the polycarbodiimide resin is a homopolymer or copolymer consisting of at least one type of repeating unit represented by the general formula (-R-N=C=N-)_n. 3. The cation-exchanged carbon material according to claim 2, wherein in the general formula (-R-N=C=N-)_n, R is an aromatic diisocyanate residue. 4. The cation-exchanged carbon body according to claim 1, wherein the carbonized precursor is obtained by heat-treating a polycarbodiimide resin at 500 to 1,500°C in a vacuum or an inert gas atmosphere. 5. The cation exchange carbon body according to claim 1, wherein the carbonization precursor is formed into a film. 6. A method for producing a cation-exchanged carbon body, which comprises heat-treating a polycarbodiimide resin to form a carbonization precursor, and sulfating and oxidizing the carbonization precursor. 7. Production of a cation-exchanged carbon body according to claim 6, wherein the polycarbodiimide resin is a homopolymer or copolymer consisting of at least one type of repeating unit represented by the general formula (-R-N=C=N-)_n Method. 8. The method for producing a cation-exchanged carbon body according to claim 7, wherein in the general formula (-R-N=C=N-)_n, R is an aromatic diisocyanate residue. 9. The method for producing a cation-exchanged carbon body according to claim 6, wherein the carbonized precursor is obtained by heat-treating the polycarbodiimide resin at 500 to 1,500°C in a vacuum or an inert gas atmosphere. 10. The method for producing a cation-exchanged carbon body according to claim 6, wherein the carbonization precursor is formed into a film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1229859A JPH0394842A (en) | 1989-09-05 | 1989-09-05 | Cation-exchange carbon body and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1229859A JPH0394842A (en) | 1989-09-05 | 1989-09-05 | Cation-exchange carbon body and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0394842A true JPH0394842A (en) | 1991-04-19 |
Family
ID=16898814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1229859A Pending JPH0394842A (en) | 1989-09-05 | 1989-09-05 | Cation-exchange carbon body and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0394842A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007153762A (en) * | 2005-12-01 | 2007-06-21 | Nippon Oil Corp | Method for hydrating olefin |
| JP2010180074A (en) * | 2009-02-03 | 2010-08-19 | Nitto Shoji Kk | Carbon shaped body and manufacturing method therefor |
-
1989
- 1989-09-05 JP JP1229859A patent/JPH0394842A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007153762A (en) * | 2005-12-01 | 2007-06-21 | Nippon Oil Corp | Method for hydrating olefin |
| JP2010180074A (en) * | 2009-02-03 | 2010-08-19 | Nitto Shoji Kk | Carbon shaped body and manufacturing method therefor |
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