JPS63274457A - Method of manufacturing granular porous chitosan derivative having cation exchange group - Google Patents
Method of manufacturing granular porous chitosan derivative having cation exchange groupInfo
- Publication number
- JPS63274457A JPS63274457A JP62111093A JP11109387A JPS63274457A JP S63274457 A JPS63274457 A JP S63274457A JP 62111093 A JP62111093 A JP 62111093A JP 11109387 A JP11109387 A JP 11109387A JP S63274457 A JPS63274457 A JP S63274457A
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- granular porous
- porous chitosan
- acid
- pyridine
- 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
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 45
- 238000005341 cation exchange Methods 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 26
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 13
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000005342 ion exchange Methods 0.000 abstract description 9
- 238000006277 sulfonation reaction Methods 0.000 abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 6
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 6
- UFWWAKOWSBGGCP-UHFFFAOYSA-N pyridine;sulfurochloridic acid Chemical compound OS(Cl)(=O)=O.C1=CC=NC=C1 UFWWAKOWSBGGCP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 abstract description 3
- 229960005215 dichloroacetic acid Drugs 0.000 abstract description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000003929 acidic solution Substances 0.000 abstract 1
- 239000003637 basic solution Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 125000001174 sulfone group Chemical group 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- XXMBEHIWODXDTR-UHFFFAOYSA-N 1,2-diaminoethanol Chemical compound NCC(N)O XXMBEHIWODXDTR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CUANPDVJYOCTJE-UHFFFAOYSA-N [S].O=O Chemical compound [S].O=O CUANPDVJYOCTJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- -1 dicarboxylic acid halide Chemical class 0.000 description 1
- 229960002442 glucosamine Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- GUAWMXYQZKVRCW-UHFFFAOYSA-N n,2-dimethylaniline Chemical compound CNC1=CC=CC=C1C GUAWMXYQZKVRCW-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IAUBZYYUBMBVPI-UHFFFAOYSA-N pyridine;sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O.C1=CC=NC=C1 IAUBZYYUBMBVPI-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Landscapes
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【発明の詳細な説明】
【産業上の利用分野】
本発明は、スルホン基を有するイオン交換樹脂或いはク
ロマトグラフィー用担体の製造方法に関するものである
。
Ｋ従来の技術】
近年、生化学関連分野の発展に伴い、分離、精製の目的
で使用されるイオン交換樹脂、クロマトグラフィー用担
体の役割は益々重要なものとなってきている。
キトサンをスルホン化する方法については、古くより文
献等に記載がある。例えば、エム・エル・’ｙ ｔ ル
ア ０ム（Ｈ，Ｌ、Ｗｏｌｆｒｏｍ）等の方法（Ｊ、Ａ
Ｉ。
Ｃｈｏｎ、Ｓｏｃ、、８１，１７６４（１９５８） ）
では、フレーク状のキトサンをピリジン中クロルスルホ
ン酸でスルホン化し、Ｎ、Ｏ−スルホン化物を与えてい
る。また、ナガサワ等は、澗ｒａ酸を使用してキトサン
のＮ−スルホン化を行っている（ＣｈｅＩｌ、Ｐｈａｒ
ｎ、Ｂｕｌｌ、。
２０、１５７．（１９７２））。更に、特開昭ｅｏ−２
ｏ３６ｏ２＠公報には、キトサンをｉ［及びクロルスル
ホン酸の混合物によりβ−Ｄ−（１，４）−グルコサミ
ンサブユニツ］・のＣ−６位の水Ｍｅ基に選択的スルフ
ェート化を行う方法が記載されている。
しかしながら、このような従来の方法では、使用される
キトサンは、殆どがフレーク状或いは粉状のキトサンで
あるため、スルホン化したものは水溶性となり、効率の
良い担体を得ることはできなかった。
Ｋ発明が解決しようとする問題点】
上記文献に記載のように、フレーク状キトサン、或いは
粉状キトサンをスルホン化した場合、スルホン基の導入
の増加に伴い、水溶性が増加する傾向があり、不溶性の
担体を得るには低いイオン交換容量のものにとどめなけ
ればならず、従って、高いイオン交換容量の担体を得る
ことは不可能であった。また、キトサンは酢酸、ジクロ
ル酢酸。
蟻酸等の水溶液に溶解するので、その用途、使用ｐＨよ
限られたものとなる。
以上の点を解決するため、本発明は耐酸、耐アルカリ性
で、しかもイオン交換容量も高い担体を青ることを目的
としてなされた。
Ｋ問題点を解決するための手段】
本発明は、架橋剤で架橋した粒状多孔質キトサン誘導体
をピリジン中クロルスルホン酸でスルホン化することに
より陽イオン交換基を有する担体を得る方法に係る。
本発明において用いる粒状多孔質キトサンは、特開昭６
１−４０３３７号に記載の方法によって得られる。当該
多孔質粒状キトサンは、架橋反応を行って全ｐＨ領域で
安定な粒状多孔質キトサン誘導体とする。
即ち、粒状多孔質キトサンは、平均分子、Ｉｉｏ、。
００〜２３０．０００の低分子化したキトサンを使用す
る。
この低分子量キトサンを酢酸、ジクロル酢酸、蟻酸等の
単独、或いは混合物に溶解して２〜１０％の水溶液とな
るように調製する。該キトサン酸性水溶液を水酸化ナト
リウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウ
ム、アンモニア、水酸化エチレンジアミン等のアルカリ
性物質を含む塩基性水溶液中に、０．１乃至Ｑ、２５ｉ
ｘ孔径のノズルより圧力下で落下させると、凝固再生し
、粒状多孔質キトサンが得られる。また、塩基性水溶液
中には、メタノール、エタノール等のアルコール類を使
用することも可能である。
上記のようにして得た粒状多孔質キトサンに架橋剤とし
てヘキサメチレンジイソシアネート、ジフェニルメタン
−４，４′−ジイソシアネート。
ジカルボン酸ハロゲン化物等を用い、粒状多孔質キトサ
ンのアミン基と反応させ、スルホン化に供する。スルホ
ン化剤としては、ピリジン中にクロルスルホン酸を滴下
して得たピリジン−クロルスルホンＵ複合体を用いる。
その他にも、ジクロルエタン中クロルスルホン酸を用い
る方法、ピリジン、ジオキサン、Ｎ、Ｎ’ −ジメチル
アニリンと無水硫酸との複合体を使用する方法、無水亜
ｆｔ酸。
無水硫酸の混合物を使用する方法、二酸化イオウ−Ｎ、
Ｎ’ −ジメチルホルムアミド複合体を使用する方法、
硫酸とりＯルスルホン酸の混合物を用いる方法等が考え
られるが、反応時間が比較的短時間である点、使用方法
、スルホン基導入量が調節し易い等の点からピリジン−
クロルスルホン酸複合体を使用する方法が好ましい。こ
の時、ピリジン中に滴下するクロルスルホン酸量を変化
させることにより、導入すべきスルホン基量を必要に応
じて適宜調節することができる。反応温度は６０１００
℃９反応時間は３０〜１２０分の範囲で任意に選択でき
る。得られたスルホン基を有する粒状多孔質キトサン誘
導体は充分水洗後、陽イオン交換体として使用すること
ができる。
に実 浦 例】
以下本発明を実施例により詳細に説明するが、本発明は
実施例記載の範囲に限定されるものではない。
また、陽イオン交換基を有する粒状多孔質キトサンの陽
イオン交換容量、比表面積、キトサンの酢酸水溶液の粘
度は、下記のようにして求めた。
◎陽イオン交換容量
試料的２０ｒｄを交換容量測定器に入れ、約１Ｎ硝酸約
１λを１時間かけて通液する。純水で中性を示すまで水
洗し、次に、約１Ｎ塩化ナトリウム水溶液を１時間かけ
て通液し、流出液を１１のメスフラスコに正しく取る。
これを試験液とし、このうちの５０ｄを採取し、フェノ
ールフタレイン溶液を指示薬としてＮ／１０水酸化ナト
リウムで中和滴定し、次式より求めた。 １ １０
００ａ：試験液５０ｄを中和するに要したＮ／１０水酸
化ナトリウム吊（成）
ｆ ：Ｎ／１０水酸化ナトリウムの力価ａＯＨ
Ｗ：試料（約２０−）の乾燥重量（ｇ）◎比表面積
比表面積測定装置を用いてＢＥＴ法で測定した。
◎粘 度
回転円筒形粘度計を用い２０℃にて測定した。
実施例１
脱アセチル化度７８％のキトサン７０ｇを３．５％酢酸
水溶液９３０ｇに溶解した。この時の粘度は３，２００
ｃｐであった。該溶液を８％の水酸化ナトリウム。
３０％のエタノール、６２％の水よりなる混合溶液中に
、０．１５ｎ／ｎ＋φの孔径のノズルから落下させて、
凝固再生させた後、中性になるまで水洗をし、平均粒径
１ｎ／Ｉｍの粒状多孔質キトサン０，９兎を得た。
こうして得られた粒状多孔質キトサン５０威（湿潤状態
）に２．３ｇのアジピン酸クロライド、 ２．５９の
トリエチルアミンを加え、ジメチルホルムアミド中至温
で１時間反応させ架橋した。ジメチルホルムアミドで洗
浄後、無水ピリジンで充分洗浄して、氷冷した無水ピリ
ジン１２Ｏｄ中にクロルスルホンＭ １２ｔｄを滴下し
たピリジン−クロルスルホン酸複合体を含む溶液を加え
、沸騰湯浴中１時間反応させＮ、Ｏ−スルホン化を行っ
た。反応終了後、１〜２Ｎ水酸化ナトリウム５００戴を
加えてからエタノールで洗浄、次いで水洗を充分行いス
ルホン基を有する粒状多孔質キトサン誘導体４８ｄを得
た。
このもののイオン交換容量は、３．３０Ｉｅｑ／ｇ、比
表面積は８７ＴＩｔ／ｇであった。また、該粒状多孔質
キトサン誘導体を０．１Ｎ酢酸水溶液、 ０．ＩＮ水
酸化ナトリウム水溶液に懸濁しても溶解する様なことは
なく全ｐｌ＋領域で安定な担体であった。
実施例２
実施例１で得られた粒状多孔質キトサン５０ｄ（湿潤状
態）に、３．３ｇのセバシン酸クロライド。
２．５ｇのトリエチルアミンを加え、ジメチルホルムア
ミド中室温で１１ｆｆ間反応させ架橋した。ジメチルホ
ルムアミドで洗浄後、無水ピリジンで充分洗浄して、氷
冷した無水ピリジン１２Ｏｄ中にクロルスルホン酸１２
−を滴下したピリジン−クロルスルホン酸複合体を含む
溶液を加え、沸騰湯浴中１時間反応させＮ、Ｏ−スルホ
ン化を行った。反応終了後１〜２Ｎ＊酸化ナトリウム５
００ｄを加えてからエタノールで洗浄、次いで水洗を充
分行い、スルホン基を有する粒状多孔質キトサン誘導体
４８ｍ１を得た。このもののイオン交換容量は３．２８
Ｉｅｑ／（１，比表面積は８５．５わ９であった。また
、該誘導体を０．１Ｎ酢酸水溶液、 ０．ＩＮ水酸化
ナトリウム水溶液に懸濁しても溶解する様なことはなく
、全ｐＨ領域で安定な担体であった。
実施例３
実施例１で得られた粒状多孔質キトサン５０ｄ（湿潤状
態）に２．１９のへキサメチレンジイソシアネートを加
え、ジメチルホルムアミド中室温で１時間反応させ架橋
した。ジメチルホルムアミドで洗浄後、無水ピリジンで
充分洗浄して氷冷した無水ピリジン１２０ｄ中にクロル
スルホン酸１２蛇を滴下したピリジン−クロルスルホン
酸複合体を含む溶液を加え、沸騰湯浴中１時間反応させ
Ｎ、０−スルホン化を行った。反応終了後１〜２Ｎ水酸
化ナトリウム５００ｄを加えてからエタノールで洗浄、
次いで水洗を充分行い、スルホン基を有する粒状多孔質
キトサン誘導体４８ｄを得た。このもののイオン交換容
量は３．３０１ｅＱ／（１，比表面積は８６Ｔｄ。
７ｇであった。また該誘導体を０，１Ｎ酢酸水溶液。
０．１Ｎ水酸化ナトリウム水溶液に懸濁しても溶解する
様なことはなく、全ｐＨ領域で安定な担体であった。ま
た、上記のようにして冑られた架橋反応後の粒状多孔質
キトサン誘導体にクロルスルホンＭＩ３ｄ、６−と変え
てスルホン化したところ、得られたスルホン化された粒
状多孔質キｌ−サン誘導体のイオン交換容量は、それぞ
れ１．２２１１８Ｑ／（］ 。
２．９４ｎｅｑ／（＋となり、クロルスルホンＭｆｆｉ
を変化させることによりスルホン基の導入量が変化し、
イオン交換容量の調節が可能であった。
【発明の効果］
本発明によれば、実施例に記載のように３．３ｍｅｑ／
ｇもの高い陽イオン交換容量を有する粒状多孔質キトサ
ン誘導体が得られる他、陽イオン交換容量を自由に調節
することが可能で、しかも、本発明によって得られる陽
イオン交換基を有する粒状多孔質キトサン誘導体は、ア
ルカリ性、酸性の全ｐＨ領域で溶解、膨潤等がなく、安
定な担体であり、イオン交換樹脂、クロマトグラフィー
用担体として極めて優れたものである。しかも、本発明
によって得られる担体は、粒状の多孔質キトサン誘導体
であるために比表面積が大きく、通液抵抗が少ないもの
であり、架橋反応を行うことによって充分な強度を有す
るので、工業的利用に好適である。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing an ion exchange resin or a chromatography carrier having a sulfone group. K. Prior Art In recent years, with the development of fields related to biochemistry, the role of ion exchange resins and chromatography carriers used for separation and purification purposes has become increasingly important. Methods for sulfonating chitosan have been described in literature for a long time. For example, the method (J, A
I. Chon, Soc, 81, 1764 (1958))
In this paper, flaky chitosan is sulfonated with chlorosulfonic acid in pyridine to give an N,O-sulfonated product. In addition, Nagasawa et al. performed N-sulfonation of chitosan using chelic acid (CheIl, Phar
n.Bull. 20, 157. (1972)). Furthermore, JP-A-Sho-eo-2
o36o2@ publication describes a method of selectively sulfating chitosan to the water Me group at the C-6 position of i [β-D-(1,4)-glucosamine subunit with a mixture of i[and chlorosulfonic acid]. Are listed. However, in such conventional methods, most of the chitosan used is flaky or powdered chitosan, and the sulfonated version becomes water-soluble, making it impossible to obtain an efficient carrier. K Problems to be Solved by the Invention] As described in the above-mentioned documents, when flaky chitosan or powdered chitosan is sulfonated, water solubility tends to increase as the number of sulfone groups introduced increases. In order to obtain an insoluble carrier, one must have a low ion exchange capacity, and it has therefore been impossible to obtain a carrier with a high ion exchange capacity. Also, chitosan is acetic acid and dichloroacetic acid. Since it dissolves in aqueous solutions such as formic acid, its uses and pH are limited. In order to solve the above-mentioned problems, the present invention was made for the purpose of producing a carrier that is acid- and alkali-resistant and also has a high ion exchange capacity. Means for Solving Problem K] The present invention relates to a method for obtaining a carrier having a cation exchange group by sulfonating a granular porous chitosan derivative crosslinked with a crosslinking agent with chlorosulfonic acid in pyridine. The granular porous chitosan used in the present invention is
It is obtained by the method described in No. 1-40337. The porous granular chitosan undergoes a crosslinking reaction to form a granular porous chitosan derivative that is stable in the entire pH range. That is, the granular porous chitosan has an average molecular weight, Iio. Chitosan with a low molecular weight of 00 to 230,000 is used. This low molecular weight chitosan is dissolved in acetic acid, dichloroacetic acid, formic acid, etc. alone or in a mixture to prepare a 2-10% aqueous solution. The chitosan acidic aqueous solution was added to a basic aqueous solution containing an alkaline substance such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, ethylenediamine hydroxide, etc. at a concentration of 0.1 to Q, 25 i.
When dropped under pressure from a nozzle with a hole diameter of x, solidification and regeneration occur to obtain granular porous chitosan. It is also possible to use alcohols such as methanol and ethanol in the basic aqueous solution. Hexamethylene diisocyanate and diphenylmethane-4,4'-diisocyanate were added to the granular porous chitosan obtained as described above as a crosslinking agent. A dicarboxylic acid halide or the like is used to react with the amine group of the porous granular chitosan to provide sulfonation. As the sulfonating agent, a pyridine-chlorosulfone U complex obtained by dropping chlorosulfonic acid into pyridine is used. Other methods include a method using chlorosulfonic acid in dichloroethane, a method using a complex of pyridine, dioxane, N,N'-dimethylaniline and sulfuric anhydride, and ftous anhydride. Method using a mixture of sulfuric anhydride, sulfur dioxide-N,
A method using N'-dimethylformamide complex,
A method using a mixture of sulfuric acid and sulfonic acid is considered, but pyridine-
A method using a chlorsulfonic acid complex is preferred. At this time, by changing the amount of chlorosulfonic acid added dropwise into the pyridine, the amount of sulfone groups to be introduced can be adjusted as necessary. Reaction temperature is 60100
C.9 reaction time can be arbitrarily selected within the range of 30 to 120 minutes. The obtained particulate porous chitosan derivative having a sulfone group can be used as a cation exchanger after being thoroughly washed with water. Example] The present invention will be explained in detail below with reference to examples, but the present invention is not limited to the scope described in the examples. Further, the cation exchange capacity and specific surface area of the granular porous chitosan having a cation exchange group, and the viscosity of an acetic acid aqueous solution of chitosan were determined as follows. ◎Cation Exchange Capacity Sample 20rd is placed in an exchange capacity measuring device, and about 1 λ of about 1N nitric acid is passed through it for 1 hour. Wash with pure water until it becomes neutral, then pass about 1N aqueous sodium chloride solution over 1 hour, and take the effluent into a volumetric flask (No. 11). This was used as a test solution, 50 d of it was sampled, and neutralization titration was performed with N/10 sodium hydroxide using phenolphthalein solution as an indicator, and the test solution was determined from the following formula. 1 10
00a: N/10 sodium hydroxide suspension required to neutralize 50d of test solution f: Titer of N/10 sodium hydroxide aOH W: Dry weight (g) of sample (approximately 20-) ◎Ratio The surface area ratio was measured by the BET method using a surface area measuring device. ◎Viscosity Measured at 20°C using a rotating cylindrical viscometer. Example 1 70 g of chitosan with a degree of deacetylation of 78% was dissolved in 930 g of a 3.5% acetic acid aqueous solution. The viscosity at this time is 3,200
It was cp. Add 8% sodium hydroxide to the solution. It was dropped into a mixed solution of 30% ethanol and 62% water through a nozzle with a hole diameter of 0.15n/n+φ,
After coagulation and regeneration, the mixture was washed with water until it became neutral to obtain granular porous chitosan with an average particle size of 1 n/Im. 2.3 g of adipic acid chloride and 2.59 g of triethylamine were added to 50 g of the thus obtained granular porous chitosan (in a wet state), and the mixture was reacted in dimethylformamide at the lowest temperature for 1 hour to effect crosslinking. After washing with dimethylformamide and thoroughly washing with anhydrous pyridine, a solution containing a pyridine-chlorosulfonic acid complex in which chlorsulfone M 12td was added dropwise to ice-cooled anhydrous pyridine 12Od was added, and the mixture was allowed to react in a boiling water bath for 1 hour. N,O-sulfonation was performed. After the reaction was completed, 500 g of 1-2N sodium hydroxide was added, and the mixture was thoroughly washed with ethanol and then with water to obtain a granular porous chitosan derivative 48d having a sulfone group. The ion exchange capacity of this product was 3.30 Ieq/g, and the specific surface area was 87 TIt/g. Further, the granular porous chitosan derivative was mixed with a 0.1N acetic acid aqueous solution and 0.1N aqueous solution of acetic acid. Even when suspended in an aqueous IN sodium hydroxide solution, it did not appear to dissolve and was a stable carrier in the entire pl+ range. Example 2 3.3 g of sebacic acid chloride was added to the granular porous chitosan 50d obtained in Example 1 (wet state). 2.5 g of triethylamine was added, and the mixture was reacted in dimethylformamide at room temperature for 11 ff to effect crosslinking. After washing with dimethylformamide and thoroughly washing with anhydrous pyridine, chlorosulfonic acid 12 was added to ice-cooled anhydrous pyridine 12Od.
A solution containing a pyridine-chlorosulfonic acid complex to which - was added dropwise was added, and the mixture was reacted for 1 hour in a boiling water bath to perform N,O-sulfonation. After completion of reaction 1-2N*sodium oxide 5
After adding 00d, the mixture was thoroughly washed with ethanol and then with water to obtain 48 ml of a granular porous chitosan derivative having a sulfone group. The ion exchange capacity of this product is 3.28
Ieq/(1, the specific surface area was 85.5×9. Also, even when the derivative was suspended in a 0.1N acetic acid aqueous solution or a 0.IN aqueous sodium hydroxide solution, it did not appear to dissolve, and the total pH Example 3 2.19 hexamethylene diisocyanate was added to the granular porous chitosan 50d (wet state) obtained in Example 1, and the mixture was reacted in dimethylformamide at room temperature for 1 hour to cause crosslinking. After washing with dimethylformamide, a solution containing a pyridine-chlorosulfonic acid complex in which chlorsulfonic acid was added dropwise to 120d of anhydrous pyridine that had been thoroughly washed with anhydrous pyridine and cooled on ice was added, and the solution was placed in a boiling water bath for 1 hour. The reaction was carried out to perform N,0-sulfonation. After the reaction was completed, 500 d of 1-2N sodium hydroxide was added, and then washed with ethanol.
Next, the mixture was thoroughly washed with water to obtain a granular porous chitosan derivative 48d having a sulfone group. The ion exchange capacity of this product was 3.301eQ/(1), and the specific surface area was 86Td. In addition, when the granular porous chitosan derivative after the crosslinking reaction completed as described above was sulfonated by replacing it with chlorsulfone MI3d,6-, the carrier was obtained. The ion exchange capacity of the sulfonated granular porous xyl-san derivative is 1.22118Q/(]. 2.94neq/(+), and the chlorsulfone Mffi
By changing the amount of sulfone group introduced,
It was possible to adjust the ion exchange capacity. [Effect of the invention] According to the present invention, as described in the examples, 3.3 meq/
In addition to obtaining a granular porous chitosan derivative having a high cation exchange capacity of as much as 100 g, the cation exchange capacity can be freely adjusted, and the granular porous chitosan having a cation exchange group obtained by the present invention The derivative is a stable carrier that does not dissolve or swell in all pH ranges, both alkaline and acidic, and is extremely excellent as a carrier for ion exchange resins and chromatography. Moreover, since the carrier obtained by the present invention is a granular porous chitosan derivative, it has a large specific surface area and low resistance to liquid passage, and has sufficient strength by crosslinking reaction, so it is suitable for industrial use. suitable for
Claims (1)
クロロスルホン酸でスルホン化することを特徴とする陽
イオン交換基を有する粒状多孔質キトサン誘導体の製造
方法。A method for producing a granular porous chitosan derivative having a cation exchange group, which comprises crosslinking the granular porous chitosan with a crosslinking agent and then sulfonating the chitosan with chlorosulfonic acid in pyridine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62111093A JPH0667481B2 (en) | 1987-05-07 | 1987-05-07 | Process for producing granular porous chitosan derivative having cation exchange group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62111093A JPH0667481B2 (en) | 1987-05-07 | 1987-05-07 | Process for producing granular porous chitosan derivative having cation exchange group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63274457A true JPS63274457A (en) | 1988-11-11 |
| JPH0667481B2 JPH0667481B2 (en) | 1994-08-31 |
Family
ID=14552203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62111093A Expired - Fee Related JPH0667481B2 (en) | 1987-05-07 | 1987-05-07 | Process for producing granular porous chitosan derivative having cation exchange group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0667481B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0920874A1 (en) * | 1997-12-05 | 1999-06-09 | SCA Mölnlycke | Superabsorbent material and method for producing said material |
| US8263763B2 (en) | 2004-06-18 | 2012-09-11 | Taiwan Hopax Chemicals Manufacturing Company, Ltd. | Chemically modified polyaminosaccharide by a hydrocarbyl sultone compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50155636A (en) * | 1974-06-07 | 1975-12-16 | ||
| JPS5635411A (en) * | 1979-08-31 | 1981-04-08 | Fujitsu Ltd | Epitaxial wafer of gallium arsenide and its manufacture |
| JPS6069012A (en) * | 1983-08-02 | 1985-04-19 | ブレンダツクス−ベルケ ア−ル．シユナイダ− ゲゼルシヤフト ミツト ベシユレンクテル ハフツンク ウント コンパニ− | Skin care composition |
| JPS6216409A (en) * | 1985-07-13 | 1987-01-24 | Kinkai Engiyou Kk | Beautifying agent containing sodium chloride |
-
1987
- 1987-05-07 JP JP62111093A patent/JPH0667481B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50155636A (en) * | 1974-06-07 | 1975-12-16 | ||
| JPS5635411A (en) * | 1979-08-31 | 1981-04-08 | Fujitsu Ltd | Epitaxial wafer of gallium arsenide and its manufacture |
| JPS6069012A (en) * | 1983-08-02 | 1985-04-19 | ブレンダツクス−ベルケ ア−ル．シユナイダ− ゲゼルシヤフト ミツト ベシユレンクテル ハフツンク ウント コンパニ− | Skin care composition |
| JPS6216409A (en) * | 1985-07-13 | 1987-01-24 | Kinkai Engiyou Kk | Beautifying agent containing sodium chloride |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0920874A1 (en) * | 1997-12-05 | 1999-06-09 | SCA Mölnlycke | Superabsorbent material and method for producing said material |
| WO1999029352A1 (en) * | 1997-12-05 | 1999-06-17 | Sca Hygiene Products Zeist B.V. | Superabsorbent material and method for producing said material |
| US8263763B2 (en) | 2004-06-18 | 2012-09-11 | Taiwan Hopax Chemicals Manufacturing Company, Ltd. | Chemically modified polyaminosaccharide by a hydrocarbyl sultone compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0667481B2 (en) | 1994-08-31 |
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