JPS6270401A - Production of carboxyalkylchitosan granule - Google Patents
Production of carboxyalkylchitosan granuleInfo
- Publication number
- JPS6270401A JPS6270401A JP60210731A JP21073185A JPS6270401A JP S6270401 A JPS6270401 A JP S6270401A JP 60210731 A JP60210731 A JP 60210731A JP 21073185 A JP21073185 A JP 21073185A JP S6270401 A JPS6270401 A JP S6270401A
- Authority
- JP
- Japan
- Prior art keywords
- granules
- chitosan
- chitin
- carboxyalkyl
- particles
- 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
Abstract
Description
本発明は、粒状体のカルボキシアルキル＋ １− ’Ｉ
ｔンの製造方法に関し、本発明による粒状体は、酵素固
定化用担体，蛋白質等の分別１製剤、両性イオン交換体
，重金属イオン等の吸着剤等としての用途に優れた機能
を有するものである。The present invention provides carboxyalkyl + 1-'I of granules
Regarding the method for producing ton, the granules according to the present invention have excellent functions as a carrier for enzyme immobilization, a fraction 1 preparation for proteins, etc., an amphoteric ion exchanger, an adsorbent for heavy metal ions, etc. be.
【従来の技術１
従来、キチンを架橋化した後に該架橋キチンをカルボキ
シアルキル化させ、次いで脱アセチル化してカルボキシ
アルキルキトサンを得る方法は特開昭５５−１３４６４
６号公報に開示されている。又特開昭５６−６１４０１
号公報にもキチンを架橋化させ架橋力ルポキシアルキル
キヂンとし、脱アセチル化してカルボキシアルキルキト
サンを得る方法が開示されている。
キチンを出発原料としてカルボキシアルキルキトサンを
製造覆る場合、キチンの持つ耐溶媒性により、キチンを
粒状体に成形した後、脱アセチル化してカルボキシアル
キルキトサン粒状体を作ることは極めて困難であり、又
、キチンをカルボキシアルキル化した後に粒状体に成形
することも考えられるが、この場合には水に対する溶解
度が増大するため粒状の形態を維持させることは困難で
ある。
従って、特開昭５５−１３４６４６号の方法は、キチン
を架橋化反応させ、架橋キチンをカルボキシアルキル化
したゲル状物をアルコール類で洗浄後減圧下で乾燥し、
粒状物でなく粉末のカルボキシアルキルキチンとし、こ
れを脱アセチル化した後凍結乾燥して粉末のカルボキシ
アルキルキトサンを得るものであって、得られるものは
粉末状のものであり、用途によっては粉末状のものは好
ましくない場合がある。又、特開昭５６−６１４０１号
の方法によって得られるキチン系成形材も、架橋後、カ
ルボキシアルキル化させたゲル状物であって、固定され
た形状を有する微粒体ではない。そして、該ゲル状物を
乾燥して粒状物としている。従って、粒径を自由に選択
してカルボキシアルキルキトサンの粒状体を￥Ｊ、造す
ることはできないという欠点があった。
【発明が解決しようとする問題点】
従来は、出発原料をキチンとしているために粒径を任意
に選定して、所定の粒径の粒状のカルボキシアルキルキ
トサンを得ることができなかったのに対し、本発明は低
分子量のキトサンが優れた造粒性を示す点に着目してな
された新規な製造法である。本発明は、低分子量のキト
サンを用いて任意の粒径を有する粒状体に一旦成形して
おき、その形態を保持したままでカルボキシアルキルキ
トサンとする方法であって、このようにすることによっ
て、所望の粒径を有するカルボキシアルキルキトサン粒
状体を得ることができる。
（問題点を解決するための千１９１
本発明は、
（ａ）低分子量キトサンを酸性水溶液に溶解し、該溶液
を塩基性溶液中に落下してキトサン粒状体を形成し、こ
れをＮ−アセチル化して再生キチン粒状体とし、該粒状
体を架橋剤で処理した後カルボキシアルキル化してノ］
ルポキシアルキルキチン粒状体とし、しかる後肢粒状体
を脱アセチル化することにより、カルボキシアルキルキ
トサン粒状体を得る。
（ｂ）低分子量キトサンを酸性水溶液に溶解し、該溶液
を塩基性溶液中に落下してキトサン粒状体を形成し、該
粒状体を架橋剤で処理した後Ｎ−アセチル化して再生架
橋キチン粒状体とし、更に該粒状体をカルボキシアルキ
ル化してカルボキシアルキルキチン粒状体とし、しかる
後肢粒状体を脱アセチル化することによりカルボキシア
ルキルキトサン粒状体を得る。
の何れかの方法によってカルボキシアルキルキトサン粒
状体を製造するものである。
本発明においては平均分子量が１００００〜２３０００
０の低分子量キトサンが用いられる。低分子量キトサン
は、酢酸、ジクロル酢酸、＠酸等の単独若しくは混合物
の水溶液に溶解し、キトサン酸性水溶液とするが、キト
サンが低分子量であるので粘度が低く、濃度は２〜２０
％の範囲で自由に選択できる。該酸性水溶液を例えば孔
径０，１〜０．２５ ｍ／ｍのノズルより圧力下で次の
塩基性凝固浴中に一定量ずつ落下させ、粒状キトサンを
得る。凝固浴には水酸化ナトリウム、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、エチレン
ジアミン等のアルカリ性物質水溶液が用いられ、メタノ
ール、エタノール等の極性を有するアルコール類を加え
ることもできる。キトサンは凝固液中を沈降しながら球
状体に形成される。粒状体の大きさは、キトサン酸性水
溶液の濃度、ノズルの孔径を任意に選択することによっ
て所望の粒径とすることができる。キトサンを再生キチ
ンとするためのＮ−アセチル化は、例えばエタノール中
で無水酢酸を用いて行うことができる。再生キチン粒状
体、又はキトサン粒状体の架橋反応は極性溶媒中で行う
が、架橋剤としてエピクロルヒドリン。
２．３−ジブロム−プロパノール、１−クロル−２，３
−エピチオプロパン及び４，４′ −シフ■ニルメタン
ジイソシアネート、ヘキサメチレンジイソシアネート、
キシリレンジイソシアネート等の有機ジイソシアネート
が好ましいものとして挙げられる。力ルボキシアルキル
化を行うためのカルボキシアルキル化剤としては、モノ
クロル酢酸、モノブロム酢酸、２−クロルプロピオン酸
、モノクロル酪酸が好ましいものとして挙げられる。カ
ルボキシアルキル化は極性溶媒中でＯ℃〜３０°Ｃで２
４時間程度反応させることによって行われる。カルボキ
シアルキルキヂンの架橋度はグルコサミン１単位当り０
．０１以上が良い。即ち、０．０１未満では粒状形態を
維持できず水に可溶で本願の発明の目的を達成し得な９
＼。０．０１以上であれば、粒状体の強度は充分となる
。
上記カルボキシアルキル化によってキチン粒状体に陰性
の解＠基であるカルボキシル基が導入できるのて゛ある
が、該カルボキシアルキル０、１５ Ｊ！下の場合はカ
ルボキシル基の効果は少なく、一方、０．９以上である
と脱アセチル化した場合に、アミン基量との釣合いがと
れず、陰イオンの効果が大き過ぎて好ましくない。
更にカルボキシアルキルキチン粒状体は高ｍｌのアルカ
リ水溶液中で常法により脱アセチル化してカルボキシア
ルキルキトサン粒状体とする。脱アセデル化度は、０、
２以下ではアミン基数が少な過ぎる欠点があり、脱アセ
デル化度０．６以上０．９位迄が好ましく、この範囲で
あればカルボキシル基とアミン基の両性のイオン能をキ
トサン粒状体に保有ゼしめることができる。
（実 施 例］
以下、実施例よって本発明を更に説明するが、架橋度は
元素分析器、カルボキシメチル化度は赤外分光分析器と
元素分析器及び脱アセデル化度は赤外分光分析器と元素
分析器によって測定し求め１ご 。
実施例１
平均分子量４３０００のキトサン７０ｇを３５％酢酸水
溶液９３０ ９中に溶解した。この溶液の粘度は１５０
０Ｃｐ （２０℃）であった。これをＮａＯ８１０％，
水６０％。
ＣＨｚＯｌ１３０％から成る凝固浴中に落下し、０．１
ｍ／ｍφの球状に成型した後、中性になる迄水洗しキト
サン粒状体を得た。
この粒状体２５蛇をエタノール２５威で３回洗い、エタ
ノール中でキトザン残基当り３倍量の無水酢酸と２４時
間反応させた後に水洗を３回行い、再生キチン粒状体を
得た。
この再生キチン粒状体を４８°ＢδＮａＯＨに一晩Ｏ℃
の状態に浸潤した後、Ｎ’ａ叶を除去し、■ピクロルヒ
ドリン３グを含むインプロピルアルコール中に投入し、
０℃，２４時間放置して架橋をさせた。
この分散液中に２ｇのモノクロル酢酸を含む２０ｄのイ
ンプロピルアルコールを加え、室温で２４ＦＲ間反応さ
せた後に、水洗，中和，水洗の処理を施して再生架橋カ
ルボキシメチルキチンを得た。これを１１Ｎ−Ｎａ叶で
１００℃，２時間処理することにより、目的物である架
橋カルボキシメチルキトサンを得た。
得られたものは架橋度０．３，カルボキシメチル化度０
．９，脱アセチル化度は０．８の粒径的０．１ｍ／ｍの
球状のカルボキシメチルキトサン粒状体であり、水に不
溶であった。
上記架橋化処理において同様にエピクロルヒドリン３ｆ
ｊを含むイソプロピルアルコール中に再生キチン粒状体
を投入し、０℃で反応時間を１時間。
４時間，１２時間，４８時間と変化させ、他は同様な処
理をした処、第１表に示づ−如く１時間処理を行ったも
のは架橋度が０．０１未満で水に溶解してしまった。他
のものは水に不溶であった。
以下余白
第１表
一１１一
実施例２
平均分子ｆｉ１２６０００のキトサン２５ｇを１２．５
％酢酸水溶液９７５ｇ中に溶解し粘度４０００Ｃｐ （
２０℃）の溶液を得た。この溶液をＮａ０１０％、水６
０％、エタノール３０％からなる凝固浴中に落下さ１±
０．１ｍ／ｍφの球状に成形し、中性になるまで水洗し
、キトサン粒状体を得た。
この粒状体２５蛇をジメチルフォルムアミド２５威で４
回洗浄した後、２ｇのへキサメチレンジイソシアネート
を溶解したジメチルフォルムアミド溶液中で１時間反応
させて、洗浄して架橋キトサン粒状体を得た。
この粒状体をエタノール中に分散させ、キトザン残基当
り３倍塁の無水酢酸と２４時間反応させ、再生架橋キチ
ン球状体を得た。
これを４８°Ｂ’６Ｎａ叶に浸漬し、０℃で２４時間反
応させ過剰のＮａ叶を除去した後、２ｑのモノクロル酢
酸を含むイソプロピルアルコール２５７を加えて、室温
で２４時間反応させ、再生架橋カルボキシメチルキチン
粒状体を得た。これを１１Ｎ−ＮａＯＨ，１００℃で２
時間処理し、球径的０．１ｍ／ｍの球状の架橋カルボキ
シメチルキトサンを得た。キトサン粒状体の架橋処理に
ついてヘキサメチレンジイソシアネート添加量が２ｇの
場合を上述したが、同様な方法でヘキサメチレンジイソ
シアネート添加量を０．０１ ｇ、 ０．１ｇ、Ｉｇ
と変化させた結果も第２表に示した。０．０１ ｇの架
橋剤へキサメチレンジイソシアネートを用いた場合、架
橋度が０．０１未満で水に対し１時膨潤するもののすぐ
溶解してしまうが、他の条件のものは凡て水に溶解しな
かった。
尚、得られた架橋カルボキシメチルキトサン球状体のカ
ルボキシメチル化度は０．６．脱アセデル化度は０．６
であった。
以下余白
第２表
ト
［
ト
Ｉ発明の効果）
本発明はキトサンを低分子化し、平均分子量を１０００
０〜２３００００とすることによりキトザン酸性水溶液
の粘度を低く保ちながら濃度を高め、塩基性溶液中での
粒状体形成能力を向上させると共に反応性をも向上する
ものである。本発明は、キト４ノンを任意の大きさの粒
状体とした後に、キトザン粒状体をＮ−アセチル化して
再生キチン粒状体とした後に架橋するか、又はキトザン
粒状体を先に架橋化した後にトアセヂル化して再生架橋
キチン粒状体にしてからカルボキシアルキル化してカル
ボキシアルキルキチン粒状体とし、これを脱アセチル化
してカルボキシアルキルキトサン粒状体とするもので、
粒状体の形態を変えずに一連の化学処理を行うものであ
る。従って、粒状体の大きさを用途に応じ自由に選定し
て目的とするカルボキシアルキルキトサン粒状体を製造
できる利点がある。
本発明によって得られたカルボキシアルキルキトサン粒
状体は、強度も高く、しかも両性或いは陽イオンを保持
したままで全ｐＨ域で耐水性を有し、酵素固定化用担体
、蛋白質等の分別精製剤、両性・イオン交換体２重金属
イオンの吸着剤等の用途に適したものである。[Prior art 1] Conventionally, a method of crosslinking chitin, carboxyalkylating the crosslinked chitin, and then deacetylating it to obtain carboxyalkyl chitosan was disclosed in Japanese Patent Application Laid-Open No. 55-13464.
It is disclosed in Publication No. 6. Also, Japanese Patent Publication No. 56-61401
The publication also discloses a method in which chitin is crosslinked to form lupoxyalkyl chitosan with crosslinking strength, and then deacetylated to obtain carboxyalkyl chitosan. When manufacturing carboxyalkyl chitosan using chitin as a starting material, it is extremely difficult to form carboxyalkyl chitosan granules by molding chitin into granules and then deacetylating them due to the solvent resistance of chitin. Although it is possible to carboxyalkylate chitin and then mold it into granules, in this case it is difficult to maintain the granular form because the solubility in water increases. Therefore, the method of JP-A-55-134646 involves subjecting chitin to a cross-linking reaction, washing the cross-linked chitin with carboxyalkylated gel, washing it with alcohol, and then drying it under reduced pressure.
The carboxyalkyl chitosan is not a granular material but a powder, which is deacetylated and then freeze-dried to obtain a powdered carboxyalkyl chitosan. may not be desirable. Furthermore, the chitin-based molding material obtained by the method of JP-A-56-61401 is also a gel-like material that is crosslinked and then carboxyalkylated, and is not a fine particle having a fixed shape. The gel-like material is then dried to form granules. Therefore, there is a drawback that it is not possible to freely select the particle size and produce carboxyalkyl chitosan granules. [Problems to be solved by the invention] Conventionally, since the starting material was chitin, it was not possible to arbitrarily select the particle size and obtain granular carboxyalkyl chitosan with a predetermined particle size. The present invention is a novel manufacturing method that focuses on the fact that low molecular weight chitosan exhibits excellent granulation properties. The present invention is a method of forming carboxyalkyl chitosan by using low molecular weight chitosan and forming it into a granular material having an arbitrary particle size while retaining its shape. Carboxyalkyl chitosan particles having a desired particle size can be obtained. (1,191 to solve the problems) The present invention provides: (a) Dissolving low molecular weight chitosan in an acidic aqueous solution, dropping the solution into a basic solution to form chitosan granules, and dissolving them into N-acetyl to obtain regenerated chitin granules, which are treated with a crosslinking agent and then carboxyalkylated.]
The carboxyalkyl chitosan particles are obtained by converting them into lupoxyalkyl chitin particles and deacetylating the hindlimb particles. (b) Dissolve low molecular weight chitosan in an acidic aqueous solution, drop the solution into a basic solution to form chitosan granules, treat the granules with a crosslinking agent, and then N-acetylate them to form regenerated crosslinked chitin particles. The granules are further carboxyalkylated to obtain carboxyalkyl chitin particles, and the hind limb particles are deacetylated to obtain carboxyalkyl chitosan particles. The carboxyalkyl chitosan particles are produced by any one of the following methods. In the present invention, the average molecular weight is 10,000 to 23,000.
0 low molecular weight chitosan is used. Low molecular weight chitosan is dissolved in an aqueous solution of acetic acid, dichloroacetic acid, @acid, etc. alone or in a mixture to form an acidic chitosan aqueous solution.Since chitosan has a low molecular weight, its viscosity is low, and the concentration is 2 to 20.
It can be freely selected within the range of %. A fixed amount of the acidic aqueous solution is dropped under pressure into the next basic coagulation bath through a nozzle with a pore diameter of 0.1 to 0.25 m/m, to obtain granular chitosan. The coagulation bath contains sodium hydroxide, potassium hydroxide,
An aqueous solution of an alkaline substance such as sodium carbonate, potassium carbonate, ammonia, or ethylenediamine is used, and polar alcohols such as methanol or ethanol may also be added. Chitosan is formed into spherical bodies while settling in the coagulation liquid. The size of the granules can be adjusted to a desired size by arbitrarily selecting the concentration of the chitosan acidic aqueous solution and the pore size of the nozzle. N-acetylation for converting chitosan into regenerated chitin can be performed, for example, using acetic anhydride in ethanol. The crosslinking reaction of regenerated chitin particles or chitosan particles is carried out in a polar solvent, and epichlorohydrin is used as a crosslinking agent. 2.3-dibromo-propanol, 1-chloro-2,3
- epithiopropane and 4,4'-Schiffnylmethane diisocyanate, hexamethylene diisocyanate,
Organic diisocyanates such as xylylene diisocyanate are preferred. Preferred carboxyalkylating agents for carboxyalkylation include monochloroacetic acid, monobromoacetic acid, 2-chloropropionic acid, and monochlorobutyric acid. Carboxyalkylation is carried out at 2°C to 30°C in polar solvents.
This is carried out by reacting for about 4 hours. The degree of crosslinking of carboxyalkylquidyne is 0 per unit of glucosamine.
．． 01 or higher is good. That is, if it is less than 0.01, it cannot maintain a granular form and is soluble in water, making it impossible to achieve the object of the present invention.
\. If it is 0.01 or more, the strength of the granules will be sufficient. The above carboxyalkylation can introduce a carboxyl group, which is a negative dissociative @ group, into the chitin particles, but the carboxyalkyl 0,15 J! In the case below, the effect of the carboxyl group is small, while in the case of 0.9 or more, when deacetylated, the balance with the amount of amine groups cannot be maintained and the effect of the anion is too large, which is not preferable. Further, the carboxyalkyl chitin granules are deacetylated in a high ml aqueous alkaline solution by a conventional method to obtain carboxyalkyl chitosan granules. The deacedelation degree is 0,
If it is less than 2, there is a disadvantage that the number of amine groups is too small, so the degree of deacetylation is preferably 0.6 or more and up to 0.9.With this range, the chitosan granules have the amphoteric ionic ability of carboxyl groups and amine groups. It can be tightened. (Example) Hereinafter, the present invention will be further explained with reference to Examples. and was determined using an elemental analyzer.Example 1 70g of chitosan with an average molecular weight of 43,000 was dissolved in a 35% acetic acid aqueous solution of 930%.The viscosity of this solution was 150%.
It was 0 Cp (20°C). Add this to NaO810%,
60% water. dropped into a coagulation bath consisting of 130% CHzOl, 0.1
After molding into a spherical shape of m/mφ, the mixture was washed with water until it became neutral to obtain chitosan granules. The granules were washed 3 times with 25 parts of ethanol, reacted with 3 times the amount of acetic anhydride per chitosan residue in ethanol for 24 hours, and then washed with water 3 times to obtain regenerated chitin granules. The regenerated chitin granules were placed in 48°BδNaOH overnight at 0°C.
After infiltrating to the state of
Crosslinking was allowed to occur at 0° C. for 24 hours. 20 d of inpropyl alcohol containing 2 g of monochloroacetic acid was added to this dispersion, and the mixture was reacted at room temperature for 24 FR, followed by water washing, neutralization, and water washing to obtain regenerated crosslinked carboxymethyl chitin. By treating this with 11N-Na leaves at 100°C for 2 hours, the target product, crosslinked carboxymethyl chitosan, was obtained. The obtained product has a degree of crosslinking of 0.3 and a degree of carboxymethylation of 0.
．． 9. The degree of deacetylation was 0.8, the particles were spherical carboxymethyl chitosan particles with a particle size of 0.1 m/m, and were insoluble in water. Similarly in the above crosslinking treatment, epichlorohydrin 3f
The regenerated chitin particles were placed in isopropyl alcohol containing J, and the reaction time was 1 hour at 0°C. When treated for 4 hours, 12 hours, and 48 hours, and the other treatments were the same, those treated for 1 hour as shown in Table 1 had a degree of crosslinking of less than 0.01 and were soluble in water. Oops. Others were insoluble in water. The following margins are Table 1-11-Example 2 25g of chitosan with an average molecular fi of 126,000 is 12.5
% acetic acid aqueous solution with a viscosity of 4000Cp (
20°C) solution was obtained. This solution was mixed with 10% Na and 6% water.
0% and 30% ethanol.
It was molded into a spherical shape of 0.1 m/mφ and washed with water until it became neutral to obtain chitosan granules. Add 25 parts of this granular material to 4 parts with 25 parts of dimethylformamide.
After washing twice, the mixture was reacted for 1 hour in a dimethyl formamide solution in which 2 g of hexamethylene diisocyanate was dissolved, and then washed to obtain crosslinked chitosan particles. The granules were dispersed in ethanol and reacted for 24 hours with acetic anhydride of 3 times the amount per chitozan residue to obtain regenerated crosslinked chitin spheres. This was immersed in a 48° B'6 Na leaf and reacted at 0°C for 24 hours to remove excess Na. After that, isopropyl alcohol 257 containing 2q of monochloroacetic acid was added and reacted at room temperature for 24 hours to regenerate crosslinking. Carboxymethyl chitin granules were obtained. This was mixed with 11N-NaOH at 100°C for 2
After treatment for several hours, spherical crosslinked carboxymethyl chitosan with a spherical diameter of 0.1 m/m was obtained. Regarding the crosslinking treatment of chitosan granules, the case where the amount of hexamethylene diisocyanate added was 2 g was described above, but the amount of hexamethylene diisocyanate added was changed to 0.01 g, 0.1 g, and Ig using the same method.
Table 2 also shows the results obtained by varying the values. When using 0.01 g of crosslinking agent hexamethylene diisocyanate, the degree of crosslinking is less than 0.01 and it swells in water for 1 hour but dissolves immediately, but all other conditions dissolve in water. I didn't. The degree of carboxymethylation of the obtained crosslinked carboxymethyl chitosan spheres was 0.6. The degree of deacetylation is 0.6
Met. Table 2 below (margin) [Effects of the invention] The present invention lowers the molecular weight of chitosan and lowers the average molecular weight to 1000.
By setting it to 0 to 230,000, the concentration of the chitozan acidic aqueous solution can be increased while keeping the viscosity low, and the ability to form granules in a basic solution is improved, as well as the reactivity. In the present invention, after making chito4non into granules of an arbitrary size, the chitozan granules are N-acetylated to form regenerated chitin granules and then crosslinked, or the chitozan granules are first crosslinked and then Toacedylation is performed to obtain regenerated crosslinked chitin granules, followed by carboxyalkylation to obtain carboxyalkyl chitin granules, which are then deacetylated to obtain carboxyalkyl chitosan granules,
A series of chemical treatments are performed without changing the form of the granules. Therefore, there is an advantage that the desired carboxyalkyl chitosan granules can be produced by freely selecting the size of the granules depending on the application. The carboxyalkyl chitosan granules obtained by the present invention have high strength and are water resistant in the entire pH range while retaining amphoteric or cationic properties, and can be used as a carrier for enzyme immobilization, a fractionation and purification agent for proteins, etc. It is suitable for use as an adsorbent for double metal ions as an amphoteric ion exchanger.
Claims (2)
を塩基性溶液中に落下してキトサン粒状体を形成し、こ
れをＮ−アセチル化して再生キチン粒状体とし、該粒状
体を架橋剤で処理した後カルボキシアルキル化してカル
ボキシアルキルキチン粒状体とし、しかる後該粒状体を
脱アセチル化することを特徴とするカルボキシアルキル
キトサン粒状体の製造方法。(1) Dissolve low molecular weight chitosan in an acidic aqueous solution, drop the solution into a basic solution to form chitosan granules, N-acetylate this to obtain regenerated chitin granules, and use the granules as a crosslinking agent. 1. A method for producing carboxyalkyl chitosan particles, which comprises treating the carboxyalkyl chitosan particles with carboxyalkylation to obtain carboxyalkyl chitin particles, and then deacetylating the particles.
を塩基性溶液中に落下してキトサン粒状体を形成し、該
粒状体を架橋剤で処理した後Ｎ−アセチル化して再生架
橋キチン粒状体とし、更に該粒状体をカルボキシアルキ
ル化してカルボキシアルキルキチン粒状体とし、しかる
後該粒状体を脱アセチル化することを特徴とするカルボ
キシアルキルキトサン粒状体の製造方法。(2) Dissolve low molecular weight chitosan in an acidic aqueous solution, drop the solution into a basic solution to form chitosan granules, treat the granules with a crosslinking agent, and then N-acetylate them to form regenerated crosslinked chitin particles. 1. A method for producing carboxyalkyl chitosan granules, which comprises converting the granules into carboxyalkyl chitosan granules, further carboxyalkylating the granules to obtain carboxyalkyl chitin granules, and then deacetylating the granules.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60210731A JPS6270401A (en) | 1985-09-24 | 1985-09-24 | Production of carboxyalkylchitosan granule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60210731A JPS6270401A (en) | 1985-09-24 | 1985-09-24 | Production of carboxyalkylchitosan granule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6270401A true JPS6270401A (en) | 1987-03-31 |
| JPS6354286B2 JPS6354286B2 (en) | 1988-10-27 |
Family
ID=16594172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60210731A Granted JPS6270401A (en) | 1985-09-24 | 1985-09-24 | Production of carboxyalkylchitosan granule |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6270401A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992003480A1 (en) * | 1990-08-17 | 1992-03-05 | Drug Delivery System Institute, Ltd. | N-acetylcarboxymethylchitosan derivative and production thereof |
| US5541234A (en) * | 1991-12-20 | 1996-07-30 | Alliedsignal Inc. | Process for making low density hydrogel materials having high surface areas |
| WO1997041894A1 (en) * | 1996-05-09 | 1997-11-13 | Taisho Pharmaceutical Co., Ltd. | Micellar aqueous composition and method for solubilizing hydrophobic drug |
| US6252003B1 (en) | 1998-06-04 | 2001-06-26 | Kao Corporation | Polymer emulsion and process for producing the same |
| US6693188B2 (en) | 2001-08-08 | 2004-02-17 | Cargill Incorporated | N-acetyl-D-glucosamine and process for producing N-acetyl-D-glucosamine |
| US6972284B2 (en) | 2000-03-15 | 2005-12-06 | Cargill, Incorporated | Chitosan and method of preparing chitosan |
| US7488812B2 (en) | 2002-04-02 | 2009-02-10 | Cargill, Incorporated | Chitosan production |
| US7816514B2 (en) | 2001-02-16 | 2010-10-19 | Cargill, Incorporated | Glucosamine and method of making glucosamine from microbial biomass |
| US7923437B2 (en) | 2001-02-16 | 2011-04-12 | Cargill, Incorporated | Water soluble β-glucan, glucosamine, and N-acetylglucosamine compositions and methods for making the same |
| US8222232B2 (en) | 2001-02-16 | 2012-07-17 | Cargill, Incorporated | Glucosamine and N-acetylglucosamine compositions and methods of making the same fungal biomass |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55134646A (en) * | 1979-04-06 | 1980-10-20 | Kureha Chem Ind Co Ltd | Amphoteric ion exchanger |
| JPS55167048A (en) * | 1979-06-15 | 1980-12-26 | Kureha Chem Ind Co Ltd | Manufacture of spherical chitin molding |
| JPS5930163A (en) * | 1982-08-10 | 1984-02-17 | Yokogawa Hokushin Electric Corp | Numbering circuit |
| JPS5930722A (en) * | 1982-08-12 | 1984-02-18 | Japan Storage Battery Co Ltd | Manufacture of silver peroxide plate |
-
1985
- 1985-09-24 JP JP60210731A patent/JPS6270401A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55134646A (en) * | 1979-04-06 | 1980-10-20 | Kureha Chem Ind Co Ltd | Amphoteric ion exchanger |
| JPS55167048A (en) * | 1979-06-15 | 1980-12-26 | Kureha Chem Ind Co Ltd | Manufacture of spherical chitin molding |
| JPS5930163A (en) * | 1982-08-10 | 1984-02-17 | Yokogawa Hokushin Electric Corp | Numbering circuit |
| JPS5930722A (en) * | 1982-08-12 | 1984-02-18 | Japan Storage Battery Co Ltd | Manufacture of silver peroxide plate |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992003480A1 (en) * | 1990-08-17 | 1992-03-05 | Drug Delivery System Institute, Ltd. | N-acetylcarboxymethylchitosan derivative and production thereof |
| US5541234A (en) * | 1991-12-20 | 1996-07-30 | Alliedsignal Inc. | Process for making low density hydrogel materials having high surface areas |
| WO1997041894A1 (en) * | 1996-05-09 | 1997-11-13 | Taisho Pharmaceutical Co., Ltd. | Micellar aqueous composition and method for solubilizing hydrophobic drug |
| US6252003B1 (en) | 1998-06-04 | 2001-06-26 | Kao Corporation | Polymer emulsion and process for producing the same |
| US6359032B1 (en) | 1998-06-04 | 2002-03-19 | Kao Corporation | Polymer emulsion and process for preparing the same |
| US6972284B2 (en) | 2000-03-15 | 2005-12-06 | Cargill, Incorporated | Chitosan and method of preparing chitosan |
| US7413881B2 (en) | 2000-03-15 | 2008-08-19 | Cargill, Incorporated | Chitosan and method of preparing chitosan |
| US7816514B2 (en) | 2001-02-16 | 2010-10-19 | Cargill, Incorporated | Glucosamine and method of making glucosamine from microbial biomass |
| US7923437B2 (en) | 2001-02-16 | 2011-04-12 | Cargill, Incorporated | Water soluble β-glucan, glucosamine, and N-acetylglucosamine compositions and methods for making the same |
| US8034925B2 (en) | 2001-02-16 | 2011-10-11 | Cargill, Incorporated | Glucosamine and method of making glucosamine from microbial biomass |
| US8222232B2 (en) | 2001-02-16 | 2012-07-17 | Cargill, Incorporated | Glucosamine and N-acetylglucosamine compositions and methods of making the same fungal biomass |
| US6693188B2 (en) | 2001-08-08 | 2004-02-17 | Cargill Incorporated | N-acetyl-D-glucosamine and process for producing N-acetyl-D-glucosamine |
| US7488812B2 (en) | 2002-04-02 | 2009-02-10 | Cargill, Incorporated | Chitosan production |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6354286B2 (en) | 1988-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4301067A (en) | Chitin containing poly-ion complex | |
| US4152170A (en) | Cross-linked pullulan | |
| US4833237A (en) | Process for producing granular porous chitosan | |
| US3275576A (en) | Cation-exchangers from cross-linked polyhydroxy materials | |
| DE2426988C2 (en) | Method for carrier binding of biologically active proteins | |
| US5169535A (en) | Method of removing endotoxin | |
| US3892731A (en) | Solvents for and purification of chitin | |
| JPS6228697B2 (en) | ||
| JPS6270401A (en) | Production of carboxyalkylchitosan granule | |
| EP0018131B1 (en) | Crosslinked, carboxyalkylated and deacetylated derivative of chitin, process for preparation thereof, and use thereof as an adsorbent material | |
| DE2505892A1 (en) | METHOD FOR PRODUCING ION EXCHANGERS BY ALKYLATION AND HYDROXY ALKYLATION OF POLYMERIC HYDROPHILIC ANION EXCHANGERS | |
| EP0176225B1 (en) | Porous chitin shaped article and production thereof | |
| Taher et al. | Development of smart alginate/chitosan grafted microcapsules for colon site-specific drug delivery | |
| EP0312242B1 (en) | Ion exchanger based on cross-linked glucomannan | |
| CN112961281A (en) | High-salt-tolerance super absorbent resin | |
| JP2631076B2 (en) | Method for producing regenerated crosslinked chitin porous microparticles | |
| CN113214504A (en) | Preparation method of semi-interpenetrating network antibacterial gel based on natural macromolecules | |
| JPH09165404A (en) | Chitosan molding with its surface being n-thiocarbamoylated and its production | |
| JPH075741B2 (en) | Process for producing granular porous chitosan derivative having sulfo group | |
| Afriani et al. | Synthesis and Characterization of Hydrogel Alginate/Poly (N-Vinyl-2-Pyrrolidone) with Double Ionic Cross-Bonded for Drug Delivery and Antibacterial Agent | |
| Achanya et al. | A Comprehensive Review on Use of Poly Electrolyte Complex PEC as an Adsorbent for the Removal of Heavy Metals From Aqueous Solution | |
| KR20010061109A (en) | Preparation of Insoluble Hydrogels Comprising Chitosan | |
| CN114904493A (en) | Ionic crosslinking beta-cyclodextrin polymer and preparation method and application thereof | |
| JPS586536B2 (en) | Cellulose inion | |
| CN115090267A (en) | Preparation method of copper ion imprinted cross-linked chitosan porous microspheres |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |