JPS5829801A - Production of n-acylated chitosan - Google Patents
Production of n-acylated chitosanInfo
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- JPS5829801A JPS5829801A JP12759781A JP12759781A JPS5829801A JP S5829801 A JPS5829801 A JP S5829801A JP 12759781 A JP12759781 A JP 12759781A JP 12759781 A JP12759781 A JP 12759781A JP S5829801 A JPS5829801 A JP S5829801A
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- Prior art keywords
- chitosan
- anhydride
- solution
- compounds
- acylating agent
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、Ｎ−アシルキトサンの製造方法、特にキトサ
ンに種々の官能基をもつアシル化剤を反応させることに
より、反応性のあるキトサン誘導体を製造する方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing N-acyl chitosan, particularly a method for producing reactive chitosan derivatives by reacting chitosan with acylating agents having various functional groups. be.
キトサンは、えび、かになどの甲殻類の外皮の構成成分
であるキチンを濃度３０〜５０％のアルカリ水溶液、例
えば水酸化ナトリウム水溶液と共に６０℃以上の温度に
加熱する処理を繰り返すことによって得られる物質であ
り、Ｄ−グルコサミンを基本単位としたβ−（１−４）
結合の多糖類である。Chitosan is obtained by repeatedly heating chitin, which is a component of the outer skin of crustaceans such as shrimp and crabs, to a temperature of 60°C or higher with an aqueous alkaline solution with a concentration of 30 to 50%, such as an aqueous sodium hydroxide solution. β-(1-4) is a substance whose basic unit is D-glucosamine.
It is a conjugated polysaccharide.
このものは、セルロースと類似した化学構造を有してい
るが、セルロースが基本単位の２位の炭素原子に水酸基
をもつのに対し、アミノ基をもっている点で異なってい
る。ところで、このキトサンの２位の炭素原子に結合し
ているアミン基は１．３位及び６位の炭素原子に結合し
ている水酸基と比較してアシル化剤に対する反応性が大
きく、優先的にアシル化されてアミド結合を形成するの
で、これを利用して種々の誘導体を得ることができるこ
とが分った。This substance has a chemical structure similar to cellulose, but differs in that it has an amino group, whereas cellulose has a hydroxyl group at the 2nd-position carbon atom of the basic unit. By the way, the amine group bonded to the carbon atom at the 2nd position of chitosan has greater reactivity to the acylating agent compared to the hydroxyl group bonded to the 1st, 3rd and 6th carbon atoms, and is preferentially Since it is acylated to form an amide bond, it has been found that various derivatives can be obtained using this bond.
本発明者らは、このキトサンのアミン基の反応性を利用
して各種のＮ−アンル化誘導体を得る方法を開発するた
めに鋭意研究を重ねた結果、キトサンを粉粒状、繊維状
又はフィルム状に成形後、これを不活性溶剤中に分散さ
せ、アシル化剤と反応させることによりＮ−アシル化物
が得られること、この際官能基をもつアシル化剤を用い
れば任意の官能基を導入しうることを見出し、このよう
にして形成されたアミド結合は化学的安定性が優れてい
るので、この知見に基づいて本発明をなすに至った。The present inventors have conducted intensive research to develop a method for obtaining various N-anthrlated derivatives by utilizing the reactivity of the amine group of chitosan. After molding, it is dispersed in an inert solvent and reacted with an acylating agent to obtain an N-acylated product; in this case, if an acylating agent with a functional group is used, any functional group can be introduced. Since the amide bond thus formed has excellent chemical stability, the present invention was completed based on this finding.
すなわち、本発明に従えば、キトサンを酸に溶解し、次
いで得ら程だ溶液をアルカリ溶液と接触させて粉粒状、
繊維状又はフィルム状に凝固させ、この凝固物を不活性
溶剤中に分散させたのち、アシル化剤を反応させること
により、Ｎ−アシル化キトサンを製造することができる
。That is, according to the present invention, chitosan is dissolved in an acid, and then the resulting solution is brought into contact with an alkaline solution to form powder and granules.
N-acylated chitosan can be produced by coagulating it into a fiber or film, dispersing the coagulated product in an inert solvent, and then reacting it with an acylating agent.
この際、アシル化剤として官能基例えばノ・ロゲン原子
、カルボキシル基、カルボニル基、不飽和基などをもつ
ものを用いれば、反応性のＮ−アシル化キトサンが得ら
れる。In this case, if an acylating agent having a functional group such as a norogen atom, a carboxyl group, a carbonyl group, or an unsaturated group is used, a reactive N-acylated chitosan can be obtained.
本発明で用いるキトサンは、前記したように、キチンを
濃アルカリと加熱して脱アセチル化した物質であるが、
ポリビニル硫酸カリウム水溶液を用いるコロイド滴定法
によって測定したアミン基の値が、４．３７〜６．２０
（ミリ当量／キ、トサン乾燥重量２）の範囲内にある
ものが好適である。As mentioned above, the chitosan used in the present invention is a substance obtained by deacetylating chitin by heating it with a concentrated alkali.
The value of amine group measured by colloid titration method using polyvinyl potassium sulfate aqueous solution is 4.37 to 6.20.
(milliequivalent/ki, dry weight of tosan 2) is preferable.
本発明の方法においては、キトサンを例えば酢酸、塩酸
、リン酸などの酸の水溶液にまず溶解する。この酸性水
溶液の酸度は特に重要ではなく、キトサンの溶液を形成
すればよい。通常は、例えば０．５〜１５．０重量％の
酢酸水溶液、０．４〜７．２重量％の塩酸水溶液、０．
４〜１０．０重量％のリン酸水溶液程度の酸性水溶液が
用いられる。キトサンの溶ｇは、そのまま次のアルカリ
接触処理に用いてもよいが、非イオン性界面活性剤を添
加し、分散乳化させて用いるのが有利である。In the method of the invention, chitosan is first dissolved in an aqueous solution of an acid such as acetic acid, hydrochloric acid, phosphoric acid, or the like. The acidity of this acidic aqueous solution is not particularly important, as long as it forms a chitosan solution. Usually, for example, 0.5 to 15.0% by weight acetic acid aqueous solution, 0.4 to 7.2% by weight hydrochloric acid aqueous solution, 0.
An acidic aqueous solution such as a 4 to 10.0% by weight phosphoric acid aqueous solution is used. Although the chitosan melt may be used as it is for the next alkali contact treatment, it is advantageous to add a nonionic surfactant and use it after dispersing and emulsifying it.
キトサンの酸性水溶液又は乳化液は、次いで、例えば０
，１〜５重量重量子ルカリ水溶液と接触させてキトサン
を析出させ、粉粒状又は繊維状に凝固させる。この場合
、キトサン液は、はげしくかきまぜながら、アルカリ水
溶液中に注加することが望ましい。また、キトサンのフ
ィルム状の凝固は、キトサン溶液をガラスなどの平板上
に塗布し、乾燥させたものをアルカリ水溶液中に浸せき
して容易に得ることができる。The acidic aqueous solution or emulsion of chitosan is then, for example, 0
, 1 to 5 weight molecules of alkali aqueous solution to precipitate chitosan and coagulate it into powder or fibers. In this case, it is desirable to pour the chitosan solution into the alkaline aqueous solution while stirring vigorously. Furthermore, chitosan can be easily coagulated in the form of a film by applying a chitosan solution onto a flat plate such as glass, drying the plate, and immersing the plate in an alkaline aqueous solution.
キトサンの析出、凝固に用いるアルカリ性水溶液は、例
えば水酸化ナトリウム水溶液、水酸化カリウム水溶液又
はアンモニア水などが好都合に用いられる。As the alkaline aqueous solution used for precipitation and coagulation of chitosan, for example, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, or aqueous ammonia is conveniently used.
アルカリ水溶液によって凝固した粉粒状又は繊維状のキ
トサンはこれを分離し、通常水洗、乾燥したのち、不活
性溶剤中に分散さ・せる。その場合凝固したキトサンを
分離し、乾燥することなく、よく水洗してアルカリを除
去し、アルコールなどの水溶性溶剤で洗浄して水を置換
したのち、分散剤
させようとする不活性溶剤で洗浄するか、該ｒに浸せき
して溶剤置換し、このキトサンを不活性溶剤に分散させ
てもよい。不活性溶剤は、次工程のアシル化反応におい
て、アシル化剤や反応生成物に対して全く活性を示さず
、アシル化反応に何ら影響を与えない溶剤であって、一
般、に非プロトン性のアミド化合物、脂肪族エーテル化
合物、芳香族炭化水素化合物及び脂肪族塩素化合物など
が包含され、代表的なものとして、例えばジメチルホル
ムアミド、ジメチルアセトアミド、Ｎ−メチルピロリド
ン、ベンゼン、トルエン、キシレン。The powdery or fibrous chitosan coagulated by the alkaline aqueous solution is separated, usually washed with water, dried, and then dispersed in an inert solvent. In that case, the coagulated chitosan is separated, washed thoroughly with water to remove the alkali without drying, washed with a water-soluble solvent such as alcohol to replace the water, and then washed with an inert solvent to be used as a dispersant. Alternatively, the chitosan may be dispersed in an inert solvent by immersing it in the solvent and replacing the solvent. An inert solvent is a solvent that shows no activity toward the acylating agent or reaction product in the next step of the acylation reaction, and does not affect the acylation reaction in any way, and is generally an aprotic solvent. These include amide compounds, aliphatic ether compounds, aromatic hydrocarbon compounds, and aliphatic chlorine compounds, and typical examples include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, benzene, toluene, and xylene.
ジエチルエーテル、ジイソプロピルエーテル、ジｎ−ブ
チルエーテル、ジオキサン、テトラヒドロフラン、クロ
ロホルム、四塩化炭素を挙げることができる。これらの
溶剤類は単独でも２種以上を混合して使用することもで
き、さらにアルコール類を併用してもよい。それらのア
ルコール類。好ましいものとしては、例えばメタノール
、エタノール、ｎ−プロパツール及ヒインプロパノ−／
Ｌ４どが挙げられる。不活性溶剤中に低級アルコール類
を存在させると、上記キトサンのアルカリ水溶液による
析出、凝固処理後、粉粒状あるいは繊維状物を水洗した
のちアルコールで置換してそｏ２ま不活性溶剤中に投入
分散させることができるので甚だ好都合であるばかりで
なく、キトサジ＼の水酸基のアシル化を抑制する効果が
ある。Mention may be made of diethyl ether, diisopropyl ether, di-n-butyl ether, dioxane, tetrahydrofuran, chloroform, and carbon tetrachloride. These solvents may be used alone or in combination of two or more, and alcohols may also be used in combination. those alcohols. Preferred examples include methanol, ethanol, n-propanol and hinpropanol.
Examples include L4. When lower alcohols are present in an inert solvent, after the above-mentioned chitosan is precipitated with an alkaline aqueous solution and coagulated, the powdery or fibrous material is washed with water, replaced with alcohol, and then poured into the inert solvent and dispersed. Not only is this extremely convenient, but it also has the effect of suppressing the acylation of the hydroxyl group of Chitosazi\.
次に、不活性溶剤中に分散させたキトサンは所定のアシ
ル化剤によりアシル化処理される。本発明の方法妊おい
ては、アシル化剤は、カルボン酸無水物又はカルボン酸
塩化物が有利に用いられ、それらの代表的なものとして
は、例えば無水酢酸。Next, the chitosan dispersed in the inert solvent is acylated using a predetermined acylating agent. In the method of the present invention, carboxylic acid anhydrides or carboxylic acid chlorides are advantageously used as the acylating agent, typical examples of which include acetic anhydride.
無水モノクロル酢酸、無水ジクロル酢酸、無水プロピオ
ン酸、無水酪酸、無水アクリル酸、無水メタクリル酸、
無水安息香酸、塩化アセチル、塩化アクロイル、塩化メ
タクリロイルなどを挙げることができる。Monochloroacetic anhydride, dichloroacetic anhydride, propionic anhydride, butyric anhydride, acrylic anhydride, methacrylic anhydride,
Examples include benzoic anhydride, acetyl chloride, acroyl chloride, and methacryloyl chloride.
粉粒状、繊維状又はテープ状ないしフィルム状のキトサ
ンの不活性溶剤分散液は、かきまぜに支障がなく、かつ
円滑なアシル化反応が可能である限り、分散質濃度には
特に制限はない。アシル化反応は、このキトサン分散液
にアシル化剤を加え好ましくは、緩和された温度条件下
でかきまぜながら行われる。アシル化剤の使用量は、所
望アシル化度に応じて異なるが、アミン基を対象とする
反応では、キトサンの構成要素であるＤ−グルコサミン
単位モルに対し、０５〜１５倍モル程度が使用される。There is no particular restriction on the dispersoid concentration of the inert solvent dispersion of chitosan in the form of powder, fibers, tape or film, as long as stirring is not hindered and smooth acylation reaction is possible. The acylation reaction is preferably carried out by adding an acylating agent to the chitosan dispersion and stirring under moderate temperature conditions. The amount of the acylating agent used varies depending on the desired degree of acylation, but in reactions targeting amine groups, the amount used is about 05 to 15 times the mole of D-glucosamine units, which is a component of chitosan. Ru.
２種以上のアシル化剤を用いる場合には、その合計量が
上記モル比範囲にあればよく、その場合、２種以上を混
合して反応に供してもよいし、１成分を添加し反応完結
後、他のアシル化成分を添加反応させ、所望特定成分の
アシル化度をコントロールすることができる。When using two or more types of acylating agents, their total amount should be within the above molar ratio range. In that case, two or more types may be mixed and subjected to the reaction, or one component may be added and subjected to the reaction. After completion, other acylated components can be added and reacted to control the degree of acylation of the desired specific component.
反応は加温下で行わせることもできるが、例えば３０℃
以下の穏やかな温度条件で、１０〜数１０時間反応させ
るのが有利である。The reaction can also be carried out under heating, for example at 30°C.
It is advantageous to carry out the reaction for 10 to several tens of hours under the following mild temperature conditions.
キトサンにアシル化剤を作用させてアシル化キトサンを
得る場合には、通常アシル化剤はキトサン中のアミン基
及び水酸基と反応し、それぞれアミド結合及びエステル
結合してアシル化物が形成されるが、不活性溶剤として
非プロトン性のアミド系化合物を用い、あるいは該化合
物と他の不活性溶剤との混合溶剤を用いると、キトサン
の水酸基のアシル化を抑制し、選択的にＮ−アシル化物
を得ることができる。When acylated chitosan is obtained by allowing an acylating agent to act on chitosan, the acylating agent usually reacts with the amine group and hydroxyl group in chitosan, forming an amide bond and an ester bond, respectively, to form an acylated product. When an aprotic amide compound is used as an inert solvent, or a mixed solvent of this compound and another inert solvent is used, acylation of the hydroxyl group of chitosan is suppressed and an N-acylated product is selectively obtained. be able to.
本発明の方法によシ製造されるＮ−アシル化を含むアシ
ル化キトサンのアシル基の置換度は、元素分析して炭素
元素に対する窒素元素の組成比（Ｎ１０値）を求めるこ
とによシ容易に算出できる。例えば、クロルアセチル化
キトサンについてのその置換度、すなわちアセチル化度
（ＤＳ）は、次式によシ算出される。The degree of substitution of acyl groups in acylated chitosan containing N-acylation produced by the method of the present invention can be easily determined by elemental analysis to determine the composition ratio of nitrogen element to carbon element (N10 value). It can be calculated as follows. For example, the degree of substitution for chloroacetylated chitosan, ie, the degree of acetylation (DS), is calculated according to the following formula.
ＤＳ＝ （０，５８３，１／（Ｎ／Ｃり ） −３
（式中の数字０．５８３１は、アシル化剤の種類により
決定される。）
また、アシル化キトサンは、赤外線吸収スペクトルによ
りそのアシル化を確認することができる。DS = (0,583,1/(N/Cri) -3
(The number 0.5831 in the formula is determined by the type of acylating agent.) Furthermore, the acylation of acylated chitosan can be confirmed by an infrared absorption spectrum.
アシル化により、アミン基から誘導されるアミド基に基
づ（１６３０〜１６７０ｍ−’の領域（アミド１）及び
１５３０〜１５５５ｃｒｎ−’の領域（アミド■）の吸
収帯、水酸基がアシル化されて形成されるエステル結合
のカルボニル（〉Ｃ−０）に基づ＜ １７２０〜１７５
０Ｃｒｎ−’領域の吸収帯が認められ、これ己吸収帯の
強度は、それぞれのアミノ基及び水酸基のアシル化度の
増大に比例して増大する。このことはキトサンのアシル
化は、キトサンの構成要素であるグルコサミン単位の２
位のアミン基がアシル化されてアミド基を形成す免反応
と６位の水酸基及び３位の水酸基がアシル化されてエス
テル結合を形成する反応が、通常同時に生起することを
示しているが、アミン基のアシル化度に対する水酸基の
アシル化度の割合は、アミド■の吸収強度１）＋６７０
に対するエステルカルボニル基の吸収強度Ｄ１７５゜の
比（ＤＩ７５０／Ｄ１６７０ ）の値から推定すること
ができる。Due to acylation, absorption bands in the 1630-1670 m-' region (amide 1) and 1530-1555 crn-' region (amide ■) are formed by acylation of the hydroxyl group based on the amide group derived from the amine group. Based on the carbonyl (>C-0) of the ester bond <1720-175
An absorption band in the 0 Crn-' region is observed, and the intensity of this self-absorption band increases in proportion to the increase in the degree of acylation of the respective amino groups and hydroxyl groups. This means that the acylation of chitosan involves the formation of two glucosamine units, which are the constituent elements of chitosan.
This indicates that the immune reaction in which the amine group at the position is acylated to form an amide group and the reaction in which the hydroxyl group at the 6-position and the hydroxyl group at the 3-position are acylated to form an ester bond usually occur simultaneously. The ratio of the degree of acylation of the hydroxyl group to the degree of acylation of the amine group is the absorption intensity of amide 1) + 670
It can be estimated from the value of the ratio (DI750/D1670) of the absorption intensity D175° of the ester carbonyl group to the ester carbonyl group.
本発明の方法によれば、キトサンに反応性の基、例エバ
クロルアセチル基、アクリロイル基、メタクリロイル基
などを所望に応じて導入することができ、それぞれの反
応性基の特性を利用して、例えばイオン交換樹脂、キレ
ート樹脂、触媒担持用樹脂などの中間体として、あるい
は酵素固定用樹脂やクロマトグラフィー用ゲルとして廟
用な物質を得ることができる。According to the method of the present invention, reactive groups such as evachloroacetyl group, acryloyl group, methacryloyl group, etc. can be introduced into chitosan as desired, and by utilizing the characteristics of each reactive group, For example, it can be used as an intermediate for ion exchange resins, chelate resins, and catalyst-supporting resins, or as enzyme-immobilizing resins and gels for chromatography.
以下実施例により、本発明をさらに詳細に説明する。The present invention will be explained in more detail with reference to Examples below.
実施例１
アミン基値５．９２ミリ当量／１゜ヤト−，−７６，２
８１を５％酢酸水溶液１０１に溶かし、この溶液に界面
活性剤スパン−６０（ソルビタン−モノステアレー）
） １．０％ベンゼン溶液３０ｍ１を加えて乳化液を調
製した。この乳化液を激しくかきまぜながら２．５％水
酸化ナトリウム水溶液２００ｍ１中に一度に加え、４０
分間、さらにかきまぜ続けた後、１時間静置してから、
濾過し、不溶分を捕集した。Example 1 Amine group value 5.92 milliequivalents/1° Yato, -76,2
81 was dissolved in 5% acetic acid aqueous solution 101, and the surfactant Span-60 (sorbitan monostearate) was added to this solution.
) 30 ml of 1.0% benzene solution was added to prepare an emulsion. Add this emulsion at once to 200ml of 2.5% sodium hydroxide aqueous solution while stirring vigorously.
After stirring for another minute, let it stand for 1 hour.
It was filtered to collect insoluble matter.
不溶性沈殿物は、アルコールで洗うことによって含有す
る活性剤（スパン−６０）を除き、中性になるまで水洗
を繰返しだ。次いで沈殿物はメタノールで洗ってから、
ジメチルアセトアミドで洗い、余分の溶剤をν過して除
いた。キトサンビーズは、ジメチルアセトアミドで湿潤
した沈殿物として４．５ｆ得られた。Insoluble precipitates are washed with alcohol to remove the active agent (Span-60) and washed repeatedly with water until neutral. The precipitate was then washed with methanol and then
It was washed with dimethylacetamide and excess solvent was removed by filtration. Chitosan beads were obtained as a dimethylacetamide wet precipitate at 4.5f.
ジメチルアセトアミドＩｏｎｌに、溶剤で湿潤したキト
サンビーズ２．２Ｌｉ−を加えて分散液をつくり、該分
散液をかきまぜながら無水モノクロル酢酸０．９１ 、
％を加え、室温で２６時間反応を行った。生成物は濾過
して溶剤から分離し、メタノールで洗い、続いて水洗を
中性になるまで繰返したのち、メタノールに置換し、次
いでベンゼンに置換シて、凍結乾燥を行った。生成物の
乾燥重量は０．１５８ ％であった。クロルアセチル化
度は１．１７、塩素含量は１５．４％、吸光度比Ｄ１７
５０ ／ＤＩ ６７０は０．２１であった。またジメチ
ルアセトアミドの代りにジメチルホルムアミドを用い、
その１０ｍ１中にキトサンビーズを分散し、無水モノク
ロル酢酸を４７時間反応させて、モノクロルアセチル化
度１．２２、塩素含量１５・５％、吸光度比Ｄ１７５０
／Ｄ１５７０カ０．４゜の反応生成物を得た。A dispersion was prepared by adding 2.2Li- of chitosan beads moistened with a solvent to dimethylacetamide Ionl, and while stirring the dispersion, 0.91Li of monochloroacetic anhydride was added.
% and the reaction was carried out at room temperature for 26 hours. The product was separated from the solvent by filtration, washed with methanol, and then washed with water repeatedly until neutral, then replaced with methanol, then benzene, and lyophilized. The dry weight of the product was 0.158%. Chloracetylation degree is 1.17, chlorine content is 15.4%, absorbance ratio D17
50/DI 670 was 0.21. Also, using dimethylformamide instead of dimethylacetamide,
Chitosan beads were dispersed in the 10ml, and monochloroacetic anhydride was reacted for 47 hours to obtain a monochloroacetylation degree of 1.22, a chlorine content of 15.5%, and an absorbance ratio of D1750.
A reaction product of /D1570/0.4° was obtained.
実施例２
実施例１で調製したキトサンビーズ２．２ ｆ （含溶
剤）をジメチルアセトアミド１ ”’Ｏｒｕｌに分散さ
せた液に無水モノクロル酢酸０．０８３ ｆ加えて、室
温で２２時間反応を行った。その後、反応液に無水酢酸
０．９６９％を添加して２６時間反応させた。反応性成
物は濾過して溶剤から分離しメタノールで洗い、続いて
水洗を繰返したのち、メタノールに置換し、次いでベン
ゼンに置換して、凍結乾燥を行った。Example 2 0.083 f of monochloroacetic anhydride was added to a solution in which 2.2 f (solvent-containing) chitosan beads prepared in Example 1 were dispersed in 1 ml of dimethylacetamide, and the reaction was carried out at room temperature for 22 hours. Thereafter, 0.969% acetic anhydride was added to the reaction solution and the reaction was allowed to proceed for 26 hours.The reactive components were separated from the solvent by filtration and washed with methanol, followed by repeated washing with water, and then replaced with methanol. Then, the mixture was replaced with benzene and freeze-dried.
生成物の乾燥重量は０．１３２７であり、そのクロルア
セチル基及びアセチル基の置換度は１．０８、塩素含量
は８．７％、吸光度比Ｄ１７５０／Ｄ１６７０は０．１
２であった。The dry weight of the product is 0.1327, the degree of substitution of chloroacetyl and acetyl groups is 1.08, the chlorine content is 8.7%, and the absorbance ratio D1750/D1670 is 0.1.
It was 2.
同様にして、ジメチルアセトアミドに分散させたキトサ
ンビーズに無水安息香酸０．８７９−を加え２３時間反
応すると、反応生成物のベンゾイル基の置換度は０．４
８であり、赤外線吸収スペクトルには１６５０ｚ ”と
１５４０ｃｒｎ−’にアミド基に基づく強い吸収が認め
られたが、エステル結合のカルボニル基による１７．２
０ ｃｍ−１附近の吸収は極めて弱いもので、ベンゾイ
ル基は、選択的にアミノ基と結合していることが確認で
きる。Similarly, when 0.879-benzoic anhydride was added to chitosan beads dispersed in dimethylacetamide and reacted for 23 hours, the degree of substitution of benzoyl groups in the reaction product was 0.4.
8, and strong absorption due to the amide group was observed at 1650z'' and 1540crn-' in the infrared absorption spectrum, but 17.2 due to the carbonyl group of the ester bond was observed.
The absorption near 0 cm-1 is extremely weak, confirming that the benzoyl group is selectively bonded to the amino group.
実施例３
キトサン０．２１７を５係酢酸水溶液に溶かした溶液に
２％スパン−６０のベンゼン溶液を３０ｍ１加え、振と
うして乳ｙヒ液を調製した。この乳化液を激しくかきま
ぜながら２．５％水酸化ナトリウム水溶液２００ｍ１！
に加え、さらに１時間かきまぜ続けたのち、１時間静置
した。これを沖過して沈殿物を集め、エタノールで洗っ
て活性剤を除いてから、洗浄液のｐＨが６．０になるま
で水洗を繰返した。その後回−びエタノールで洗い次い
でテトラヒドロフランで置換すると、６，８５７の湿潤
キトサンビーズが得られた。Example 3 30 ml of a 2% Span-60 benzene solution was added to a solution of 0.217 chitosan dissolved in a 5-functional acetic acid aqueous solution and shaken to prepare a milk solution. While vigorously stirring this emulsion, add 200ml of 2.5% sodium hydroxide aqueous solution!
In addition, the mixture was continued to be stirred for an additional hour, and then left to stand for an hour. The precipitate was collected by filtration, washed with ethanol to remove the activator, and then washed with water repeatedly until the pH of the washing solution reached 6.0. After subsequent washing with ethanol and displacement with tetrahydrofuran, 6,857 wet chitosan beads were obtained.
この湿潤キトサンビーズ２．７５５４をテトラヒ ドロ
フランに浸して溶剤置換したの、ち、テトラヒドロフラ
ン２０ｍ１に浮遊させたキトサンビーズ分散液に無水モ
ノクロル酢酸０．７９７を加え６６時間反応させた。反
応後、沈殿物を分離し、メタノールで洗い、水洗を繰返
し行ってからメタノール置換、ベンゼン置換し、凍結乾
燥を行った。得られた反応生成物の乾燥重量は０，１４
６７、クロルアセチル化度１．６７、塩素含量１７．９
％、吸光度比Ｄ１□５゜／Ｄ１６７０は０．６２であっ
た。The wet chitosan beads (2.755ml) were immersed in tetrahydrofuran to replace the solvent, and then 0.797ml of monochloroacetic anhydride was added to the chitosan bead dispersion suspended in 20ml of tetrahydrofuran and reacted for 66 hours. After the reaction, the precipitate was separated, washed with methanol and water repeatedly, then replaced with methanol and benzene, and freeze-dried. The dry weight of the reaction product obtained was 0.14
67, degree of chloroacetylation 1.67, chlorine content 17.9
%, and the absorbance ratio D1□5°/D1670 was 0.62.
実施例４
実施例３で調製した湿潤キトサンビーズの４．１０２を
ジオキサンに浸して溶剤置換したのち、ジオキサン２ｏ
ｒｎｌに浮遊させてその分散液に無水モノクロ酢酸０．
９０７を加えて６６時間反応させた。反応後、沈殿物を
メタノールで洗い、水洗を繰返したのちメタノール置換
、次いでベンゼン置換して凍結乾燥を行った。得られた
反応生物の乾燥重量は０．１７１１、クロルアセチル化
度１．４３、塩素含量１２．７％、吸光度比Ｄ１７５０
／／Ｄ１６７０ば０．６４であった。Example 4 After soaking 4.102 of the wet chitosan beads prepared in Example 3 in dioxane and replacing the solvent, dioxane 2o
rnl and added 0.0% monochloroacetic anhydride to the dispersion.
907 was added and reacted for 66 hours. After the reaction, the precipitate was washed with methanol, washed repeatedly with water, and then replaced with methanol and then with benzene, followed by freeze-drying. The dry weight of the obtained reaction product was 0.1711, the degree of chloroacetylation was 1.43, the chlorine content was 12.7%, and the absorbance ratio was D1750.
//D1670 was 0.64.
実施例５
キトサン（アミン基の値５．９２ミリ当量１５’）４．
０１をｌθ％酢酸水溶液２００ｍ／！に溶かし、２％キ
トサン溶液を調製した。Example 5 Chitosan (value of amine groups 5.92 meq 15')4.
01 in lθ% acetic acid aqueous solution 200m/! to prepare a 2% chitosan solution.
このキトサン溶液５．Ｏｒにスパン６００２％ベンゼン
溶液１５ｍ１を加え、エマルジョン化させた。This chitosan solution 5. 15 ml of Span 6002% benzene solution was added to Or to form an emulsion.
このエマルジョン溶液を激しくかきまぜながら２．５係
水酸化ナトリウム水溶液２００ｍＪ中に流し込み、３０
分間かきまぜ続けてキトサンを凝固させた。This emulsion solution was poured into 200 mJ of a 2.5% sodium hydroxide aqueous solution while stirring vigorously.
Stirring was continued for a minute to solidify the chitosan.
析出した沈殿物を集めてメタノールで洗ってから、中性
になるまで水洗を繰返した。水洗を終ったキトサンビー
ズは、吸着水をメタノールで置換し、さらにベンゼン置
換を行ってから、これをベンゼン２ｏｍｌ中に分散させ
た。この分散液にアルコールを添加し、無水モノクロル
酢酸を加えて反応させ、得られた反応生成物の重量、り
ｐルアセチル化度、塩素含量及び吸光度比Ｄ１７．。／
Ｄ１６７０を検べた。アルコールの種類及び添加量を変
えて同様に反応させ、その結果を反応系の条件とともに
下掲第１表に示す。なお、アルコール類を添加せず、無
水モノクロル酢酸の使用量を大巾に変えた場合の結果も
表中にまとめて示した。The precipitate was collected, washed with methanol, and then washed with water repeatedly until it became neutral. After washing the chitosan beads with water, the adsorbed water was replaced with methanol, and the beads were further replaced with benzene, and then dispersed in 2 oml of benzene. Alcohol is added to this dispersion liquid, monochloroacetic anhydride is added and reacted, and the weight of the reaction product obtained, the degree of acetylation, the chlorine content, and the absorbance ratio D17. . /
I was able to test for D1670. The reaction was carried out in the same manner by changing the type and amount of alcohol added, and the results are shown in Table 1 below along with the conditions of the reaction system. Note that the results obtained when no alcohol was added and the amount of monochloroacetic anhydride used was varied widely are also summarized in the table.
比較のために、本発明方法とは異なり２％キトサン溶液
５．０５’に２％スパン６ｏのベンゼン溶液１５ｍ１加
えて乳化し、これに５％水酸化ナトリウム水溶液を７
、０ ｍｌ加えて、凝固析出したキトサンを含む反応混
合物に直接無水モノクロル酢酸１．７６１をベンゼン５
．ｏｍｌに溶かした溶液を加えて４時間かきまぜた後、
１日間装置してから、沈殿物を分離、洗浄処理を行い、
乾燥して０．０５５７の固形物を得たが、赤外線吸収ス
ペクトルはキトサンに近いパターンを示した。捷た、同
様の方法で無水アクリル酸のベンゼン溶液を作用させた
後、沈殿物の分離を試みたが、生成物は水媒体中で著し
く膨潤しており、キトサンのＮ−アシル化はほとんど起
っていないことが分った。For comparison, unlike the method of the present invention, 15 ml of a 2% span 6o benzene solution was added to 5.05' of a 2% chitosan solution to emulsify it, and 7 ml of a 5% aqueous sodium hydroxide solution was added to this.
, 0 ml was added, and 1.761 ml of monochloroacetic anhydride was added directly to the reaction mixture containing the coagulated and precipitated chitosan with 5 ml of benzene.
．． After adding the solution dissolved in oml and stirring for 4 hours,
After leaving the device for one day, the precipitate was separated and washed,
After drying, a solid with a particle size of 0.0557 was obtained, and its infrared absorption spectrum showed a pattern similar to that of chitosan. An attempt was made to separate the precipitate after applying a benzene solution of acrylic anhydride using the same method, but the product swelled significantly in the aqueous medium and almost no N-acylation of chitosan occurred. I found out that it wasn't.
まだ、本発明の方法で析出させたキトサンの代りにキチ
ンのけん化によって得られるキトサンの粉末（粒度８０
〜１５０メツシユ、コロイド滴定によるアミン基の値５
．９２ミリ当量／７）０．０３６７をベンゼン中に分散
し、無水モノクロル酢酸１，６０ｉを２４時間作用する
と、生成物の得量は０．０４０１であった。このものの
クロルアセチル化度が０．７１、塩素含量が８．５％、
吸光度比Ｄ１７５０／Ｄ１６７ｏは０．８２であった。However, instead of chitosan precipitated by the method of the present invention, chitosan powder obtained by saponification of chitin (particle size 80
~150 mesh, value of amine group by colloid titration 5
．． 92 meq/7) 0.0367 was dispersed in benzene and treated with 1,60 i of monochloroacetic anhydride for 24 hours, yielding 0.0401 of the product. The degree of chloroacetylation of this product is 0.71, the chlorine content is 8.5%,
The absorbance ratio D1750/D167o was 0.82.
したがって、この反応生成物は、本発明方法による反応
物と異なり、局部的にクロルアセチル化されたも−ので
あることが分った。Therefore, it was found that this reaction product was locally chloroacetylated, unlike the reaction product obtained by the method of the present invention.
実施例６
ｉ施例５の方法で調製したキトサンビーズをジメチルア
セトアミドに浸して溶剤置換したのち、ジメチルアセト
アミド２０ｒｎｌ中に分散させ、無水アクリル酸１．１
１を加え、４８時間攪拌反応させた。生成物の得量は定
量的であり、アクリロイル基の置換度は１．３０、吸光
度比Ｄ１□２８／Ｄ工、６．は０．６７であった。Example 6 i Chitosan beads prepared by the method of Example 5 were immersed in dimethylacetamide to replace the solvent, then dispersed in 20 rnl of dimethylacetamide, and mixed with 1.1 ml of acrylic anhydride.
1 was added thereto, and the mixture was stirred and reacted for 48 hours. The yield of the product was quantitative, the degree of substitution of the acryloyl group was 1.30, the absorbance ratio was D1□28/D, 6. was 0.67.
実施例７
キトサン４．０１を１０％酢酸水溶液２００ｍ／！に溶
かした溶液をガラス板上に塗布し、乾燥後、０．５係水
酸化ナトリウム水溶液中に浸してキトサン皮膜を凝固さ
せた。凝固した皮膜をガラス板から剥離し、水洗、次い
でメタノール浸せき及びベンゼン浸せきを行った。この
ようにして洗浄、ならびに溶剤置換したフィルム（厚さ
１９〜２４μｍ）をベンゼン２０ｍ１中に浮遊させて、
その中に無水モノクロル酢酸１．６ｙ−を加えて反応を
行うと、１６７０ ｃｍ ”と１５４５ｉ１にそれぞれ
アミドＩ、アミド■の強い吸収を示し、１７５０ｃｒｉ
１’にエステル結合のカルボニルの吸収を示すフィルム
が得られた。比較として、本発明の方法によらないで調
製されたキトサンフィルムを乾燥後、ベンゼン中に浸せ
きして１．６１の無水モノクロル酢酸を３８時間作用さ
せた場合は、１６７０ 、 ”、１５４５．’に弱い吸
収を示し、１７５０ｉ’に微弱な吸収のあるフィルムが
得られたのみであって、アシル化は極めて起りにくいこ
とが明らかである。Example 7 Chitosan 4.01 in 10% acetic acid aqueous solution 200m/! A solution dissolved in the above was applied onto a glass plate, and after drying, the chitosan film was coagulated by immersing it in a 0.5% aqueous sodium hydroxide solution. The coagulated film was peeled off from the glass plate, washed with water, and then immersed in methanol and benzene. The film (thickness 19-24 μm) washed and solvent-substituted in this way was suspended in 20 ml of benzene,
When 1.6y- of monochloroacetic anhydride was added to the reaction mixture, strong absorption of amide I and amide II was observed at 1670 cm'' and 1545i1, respectively, and 1750 cr
A film was obtained that showed absorption of the carbonyl of the ester bond at 1'. For comparison, when a chitosan film prepared without the method of the present invention was dried and then immersed in benzene and treated with 1.61 monochloroacetic anhydride for 38 hours, the results were 1670, 1545. A film showing only weak absorption and a weak absorption at 1750i' was obtained, and it is clear that acylation is extremely unlikely to occur.
添付図面は、上記方法で得られた各フィルムの赤外線吸
収スペクトルで、ａは本発明の方法によらない無水モノ
クロル酢酸処理キトサンフィルムのものであり、対比の
ために非処理キトサンフィルムの吸収スペクトルを点線
で示しだ。ｂは本発明の方法で得られたクロルアセチル
化キトサンフィルムの吸収スペクトルである。両スペク
トルから明らかなように、ａはもとのキトサンフィルム
とほとんど吸収傾向を有するのに対し、ｂは３つのクロ
ルアセチル化に基づくシャープなピークが存在する。The attached drawings show the infrared absorption spectra of each film obtained by the above method, where a shows the infrared absorption spectrum of the chitosan film treated with monochloroacetic anhydride, which is not performed by the method of the present invention, and the absorption spectrum of the untreated chitosan film is shown for comparison. It is shown by the dotted line. b is an absorption spectrum of the chloroacetylated chitosan film obtained by the method of the present invention. As is clear from both spectra, a has almost the same absorption tendency as the original chitosan film, whereas b has three sharp peaks based on chloroacetylation.
実施例８
実施例７の方法でキトサン溶液から作成したキトサンフ
ィルムをベンゼン１００ｍ１中に浮遊させて、これに無
水アクリル酸を０．５５ｊｉ’加えて４２時間反応すせ
た。反応後ベンゼンで洗い、メタノールに１０分間浸せ
きしてから水洗を繰返し行ったのち、乾燥した。生成物
は強じん、透明なフィルムであ ゛す、１６６２ ｃｒ
ｉ１’と１５５０滅１に強いアミド基の吸収が、また１
７２ｓ函’にエステル基の吸収が認められた。Example 8 A chitosan film prepared from a chitosan solution according to the method of Example 7 was suspended in 100 ml of benzene, and 0.55 ji' of acrylic anhydride was added thereto and allowed to react for 42 hours. After the reaction, it was washed with benzene, immersed in methanol for 10 minutes, washed with water repeatedly, and then dried. The product is a tough, transparent film, 1662 cr.
i1' and 1550 have a strong absorption of amide group, but also 1
Absorption of ester groups was observed in the 72s box.
無水アクリル酸の代りに無水メタクリル酸を用い、同じ
方法で処理して、同様に強じんかつ透明なフィルムが得
られた。そのフィルムは、１６６０ｚ’と１５５０ ｃ
ｉｍ ’に強いアミド基の吸収を示し、１７５０ ｃｍ
’附近めエステル結合に基因する吸収は極めて微弱で
あった。A similarly tough and transparent film was obtained using methacrylic anhydride instead of acrylic anhydride and treated in the same manner. The film is 1660z' and 1550c
It shows strong absorption of amide group at im', 1750 cm
'The absorption due to the ester bond was extremely weak.
図ｉｄ、キトサンフィルム及びその無水モノクロ酢酸処
理フィルムの赤外線吸収スペクトルで、ａは本発明外の
方法によるもの、ｂは本発明の方法によるもの及び点線
は非処理キトサンフィルムのものである。
特許出願人 工業技術院長 石板誠−指定代理人
大阪工業技術試験所長
内藤−男Figure id is an infrared absorption spectrum of a chitosan film and its monochloroacetic anhydride-treated film, where a is obtained by a method other than the present invention, b is obtained by a method of the present invention, and the dotted line is that of an untreated chitosan film. Patent applicant Makoto Ishiita, Director of the Agency of Industrial Science and Technology - Designated Agent
Osaka Industrial Technology Testing Institute Director Osaka Naito
Claims (1)
接触させて粉粒状、繊維状又はフィルム状に凝固させ、
この凝−物を不活性溶剤に分散させてアシル化剤と反応
させることを特徴トするＮ−アシル化キトサンの製造方
法０２ アシル化剤が無水酢酸、無水モノクロル酢酸、
無水アクリル酸及び無水メタアクリル酸から選択される
１種又は２種以上のものである特許請求の範囲第１項記
載の製造方法。 ３ 不活性溶剤が非プロトン性のアミド系化合物、芳香
族炭化水素化合物、脂肪族塩素化合物及び脂肪族エーテ
ル化合物から選択される１種又は２種以上のものである
特許請求の範囲第１項記載の製造方法。 ４ 非プロトン性のアミド系化合物がジメチルホルムア
ミド、ジメチルアセトアミド又はＮ〜メチルピロリドン
である特許請求の範囲第３項記載の製造方法。 ５ 不活性溶剤がアルコール類を含有する混合溶剤であ
る特許請求の範囲第３項又は第４項記載の製造方法。[Claims] 1. Chitosan is dissolved in an acid, and this solution is brought into contact with an alkaline solution to coagulate it into a powder, fibrous or film form,
Method 02 for producing N-acylated chitosan characterized by dispersing this coagulated material in an inert solvent and reacting it with an acylating agent 02 The acylating agent is acetic anhydride, monochloroacetic anhydride,
The manufacturing method according to claim 1, wherein the material is one or more selected from acrylic anhydride and methacrylic anhydride. 3. Claim 1, wherein the inert solvent is one or more selected from aprotic amide compounds, aromatic hydrocarbon compounds, aliphatic chlorine compounds, and aliphatic ether compounds. manufacturing method. 4. The manufacturing method according to claim 3, wherein the aprotic amide compound is dimethylformamide, dimethylacetamide, or N-methylpyrrolidone. 5. The manufacturing method according to claim 3 or 4, wherein the inert solvent is a mixed solvent containing alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12759781A JPS5930163B2 (en) | 1981-08-13 | 1981-08-13 | Method for producing N-acylated chitosan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12759781A JPS5930163B2 (en) | 1981-08-13 | 1981-08-13 | Method for producing N-acylated chitosan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5829801A true JPS5829801A (en) | 1983-02-22 |
| JPS5930163B2 JPS5930163B2 (en) | 1984-07-25 |
Family
ID=14964014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12759781A Expired JPS5930163B2 (en) | 1981-08-13 | 1981-08-13 | Method for producing N-acylated chitosan |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5930163B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60215003A (en) * | 1984-04-10 | 1985-10-28 | Unitika Ltd | Chitosan molding and its production |
| JPS6462302A (en) * | 1987-09-01 | 1989-03-08 | Nippon Suisan Kaisha Ltd | Water-soluble chitosan salt and production thereof |
| US4833237A (en) * | 1984-07-31 | 1989-05-23 | Fuji Spinning Co., Ltd. | Process for producing granular porous chitosan |
| EP0628655A1 (en) * | 1993-06-11 | 1994-12-14 | Ciba-Geigy Ag | Bleaching aids |
| JP2002308901A (en) * | 2001-04-12 | 2002-10-23 | Kao Corp | Method for manufacturing compound having sugar skeleton |
| CZ301899B6 (en) * | 2009-03-17 | 2010-07-21 | Contipro C, A.S. | Process for preparing derivatives of hyaluronic acid using O-acyl-O?-alkylcarbonate in the presence of substituted pyridine |
| CZ302856B6 (en) * | 2006-09-27 | 2011-12-14 | Cpn Spol. S R. O. | Process for preparing polysaccharide derivatives |
| CN102863553A (en) * | 2012-04-01 | 2013-01-09 | 金陵科技学院 | Chitosan derivative with cross-linking polymerization and containing drug ligand |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62299934A (en) * | 1986-06-20 | 1987-12-26 | Konica Corp | Wiping up device for dirt on optical system mirror in copying machine |
-
1981
- 1981-08-13 JP JP12759781A patent/JPS5930163B2/en not_active Expired
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60215003A (en) * | 1984-04-10 | 1985-10-28 | Unitika Ltd | Chitosan molding and its production |
| JPH0578578B2 (en) * | 1984-04-10 | 1993-10-29 | Unitika Ltd | |
| US4833237A (en) * | 1984-07-31 | 1989-05-23 | Fuji Spinning Co., Ltd. | Process for producing granular porous chitosan |
| JPS6462302A (en) * | 1987-09-01 | 1989-03-08 | Nippon Suisan Kaisha Ltd | Water-soluble chitosan salt and production thereof |
| JPH0232281B2 (en) * | 1987-09-01 | 1990-07-19 | Nippon Suisan Kaisha Ltd | |
| EP0628655A1 (en) * | 1993-06-11 | 1994-12-14 | Ciba-Geigy Ag | Bleaching aids |
| JP2002308901A (en) * | 2001-04-12 | 2002-10-23 | Kao Corp | Method for manufacturing compound having sugar skeleton |
| CZ302856B6 (en) * | 2006-09-27 | 2011-12-14 | Cpn Spol. S R. O. | Process for preparing polysaccharide derivatives |
| CZ301899B6 (en) * | 2009-03-17 | 2010-07-21 | Contipro C, A.S. | Process for preparing derivatives of hyaluronic acid using O-acyl-O?-alkylcarbonate in the presence of substituted pyridine |
| CN102863553A (en) * | 2012-04-01 | 2013-01-09 | 金陵科技学院 | Chitosan derivative with cross-linking polymerization and containing drug ligand |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5930163B2 (en) | 1984-07-25 |
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