JPH032203A - Production of low molecular weight chitosan - Google Patents
Production of low molecular weight chitosanInfo
- Publication number
- JPH032203A JPH032203A JP13717289A JP13717289A JPH032203A JP H032203 A JPH032203 A JP H032203A JP 13717289 A JP13717289 A JP 13717289A JP 13717289 A JP13717289 A JP 13717289A JP H032203 A JPH032203 A JP H032203A
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- molecular weight
- acid
- molecular
- low
- 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 63
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 abstract description 20
- 125000003277 amino group Chemical group 0.000 abstract description 12
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 abstract description 7
- 229930182470 glycoside Natural products 0.000 abstract description 5
- 238000004040 coloring Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 abstract description 2
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 abstract description 2
- 229940048102 triphosphoric acid Drugs 0.000 abstract description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 abstract 1
- 229940005657 pyrophosphoric acid Drugs 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 229920002101 Chitin Polymers 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000000850 deacetylating effect Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000238557 Decapoda Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- FZHXIRIBWMQPQF-UHFFFAOYSA-N Glc-NH2 Natural products O=CC(N)C(O)C(O)C(O)CO FZHXIRIBWMQPQF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- FZHXIRIBWMQPQF-SLPGGIOYSA-N aldehydo-D-glucosamine Chemical compound O=C[C@H](N)[C@@H](O)[C@H](O)[C@H](O)CO FZHXIRIBWMQPQF-SLPGGIOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229960002442 glucosamine Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000003563 glycoside group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003385 ring cleavage reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
本発明はキチンを脱アセチル化して得られる高分子量の
キトサンから任意の分子量、あるいは狭い分子量分布を
有する低分子化キトサンを製造する方法に関するもので
ある。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing low-molecular-weight chitosan having a desired molecular weight or narrow molecular weight distribution from high-molecular-weight chitosan obtained by deacetylating chitin. It is.
キトサンは２−アミノ−２−デオキシ−Ｄ−グルコース
がβ−１，４結合にてグリコサイド結合した塩基性多糖
である。通常キトサンはカニ・エビ等の甲殻や菌類の細
胞壁等に含まれるキチンを脱アセチル化することにより
得られる。Chitosan is a basic polysaccharide in which 2-amino-2-deoxy-D-glucose is glycoside-linked through β-1,4 bonds. Chitosan is usually obtained by deacetylating chitin contained in the shells of crabs, shrimps, etc., and the cell walls of fungi.
キトサンには反応性に富む遊離アミノ基があり、これを
誘導体化することにより各種用途への利用が考えられて
いる
しかしながらキトサンが希酸にしか溶けないこと、及び
その溶液の粘度が高いこと等の理由により用途が限定さ
れてしまっている。そこでキトサンの低分子化が種々検
討されている。Chitosan has a highly reactive free amino group, and derivatization of this group can be used for various purposes.However, chitosan only dissolves in dilute acids, and the viscosity of its solution is high. Due to these reasons, its uses are limited. Therefore, various methods of reducing the molecular weight of chitosan are being investigated.
従来より低分子化キトサンを得る方法として、キチンを
高濃度のアルカリで処理することにより脱アセチル化と
同時にグリコサイド結合を切断させる方法や、キチンを
希塩酸等の希酸で処理してグリコサイド結合を切断した
のち脱アセチル化してキトサンを得る方法が知られてい
る。Conventional methods for obtaining low-molecular-weight chitosan include treating chitin with a highly concentrated alkali to deacetylate and simultaneously break the glycoside bonds, and treating chitin with a dilute acid such as dilute hydrochloric acid to break the glycoside bonds. A method is known in which chitosan is obtained by cutting and then deacetylating.
しかしこれらの方法は過酷な条件を長時間必要とし、任
意の分子量のものが得られないばかりでなく、副反応に
よってキトサンのアミノ基含量の低下がみられるという
問題点があった。However, these methods require harsh conditions for a long period of time, and have problems in that not only are chitosan unable to obtain a desired molecular weight, but also the amino group content of chitosan is reduced due to side reactions.
これらの問題点を解消するために特公昭５６３３４０１
号や特開昭６１−４０３０３号ではキトサンを過酸化水
素や過ホウ酸ソーダで処理する方法が提案されている。In order to solve these problems,
No. 61-40303 proposes a method of treating chitosan with hydrogen peroxide or sodium perborate.
これらの方法ではアミノ基に影響を与えずに無着色の低
分子化キトサンが得られるが、この方法によって得られ
るキトサンの分子量は小さくても１００００以上に限定
されてしまい、低分子化は充分とはいえない。With these methods, uncolored, low-molecular-weight chitosan can be obtained without affecting the amino groups, but the molecular weight of the chitosan obtained by this method is limited to at least 10,000, and low-molecularization is insufficient. No, no.
特開昭６１−２１１０２号ではキトサンを塩酸加水分解
することにより中性の水に可溶な低分子化合物を得てい
るが、この方法にも、切断が進み過ぎて大部分がモノマ
ーのグルコサミンとなり、それより重合度の大きなもの
の収率が低いこと、反応のコントロールが困難なこと、
更に酸の除去に多大な労力を必要とすること等の問題点
がある。In JP-A No. 61-21102, a neutral water-soluble low-molecular compound was obtained by hydrolyzing chitosan with hydrochloric acid, but even with this method, the cleavage progressed too much and most of it became monomer glucosamine. , the yield is low for products with a higher degree of polymerization, and the reaction is difficult to control.
Furthermore, there are other problems such as the need for a great deal of effort to remove the acid.
又、特開昭６２−１８４００２号では亜硝酸塩を用いて
中性の水に可溶な低分子化合物を得ているが、亜硝酸塩
によって環開裂反応に伴うアミノ基含量の低下が生じる
ことが報告されている〔「キチン・キトサンの開発と応
用」、４頁〜７頁。In addition, in JP-A-62-184002, a neutral water-soluble low-molecular compound was obtained using nitrite, but it was reported that nitrite caused a decrease in the amino group content due to ring cleavage reaction. [“Development and Application of Chitin and Chitosan”, pp. 4-7.
１９８７年、工業技術会〕。1987, Industrial Technology Society].
更に、特開昭６３−６３７０１号ではアスコルビン酸を
用いたキトサンの分解を行っているが、この方法も反応
時間が長いことや生成物の分子量がかなり大きいこと等
の欠点を有している。Furthermore, in JP-A-63-63701, chitosan is decomposed using ascorbic acid, but this method also has drawbacks such as a long reaction time and a considerably large molecular weight of the product.
本発明はキトサンから任意の分子量を持つ低分子化キト
サンを効率よく製造し、しかも後処理の容易な方法を提
供することを目的とする。An object of the present invention is to provide a method for efficiently producing low-molecular-weight chitosan having a desired molecular weight from chitosan and for easy post-treatment.
本発明者らはキトサンを原料として任意の分子量を有す
る低分子化キトサンを得る方法について鋭意研究を重ね
た結果、高分子量キトサンをリン酸にて処理することに
より従来の方法に比べてより簡便に所望の低分子化キト
サンを製造できることを見出し本発明を完成するに至っ
た。The present inventors have conducted intensive research on a method for obtaining low-molecular-weight chitosan with a desired molecular weight using chitosan as a raw material. As a result, we have found that by treating high-molecular-weight chitosan with phosphoric acid, it is easier than the conventional method. The present invention was completed by discovering that it is possible to produce the desired low-molecular-weight chitosan.
すなわち本発明は、キトサンをリン酸水溶液中で処理す
ることにより低分子量のキトサンを得ることを特徴とす
る低分子化キトサンの製造方法を提供するものである。That is, the present invention provides a method for producing low-molecular-weight chitosan, which is characterized by obtaining low-molecular-weight chitosan by treating chitosan in an aqueous phosphoric acid solution.
本発明においては、原料のキトサンとしてはキチンを脱
アセチル化して得られるキトサンあるいは市販のキトサ
ンのいずれも使用可能である。ちなみに、キチンからキ
トサンを得る場合には、キチンを４０〜５０％のアルカ
リ液に浸漬し、１１５〜１３０″Ｃで５時間処理して脱
アセチル化を行った後、アルカリ液を除去し、次いで水
洗後乾燥すればフレーク状のキトサンを得ることができ
、これを粉砕すれば粉末状のキトサンを得ることができ
る。In the present invention, as the raw material chitosan, either chitosan obtained by deacetylating chitin or commercially available chitosan can be used. By the way, when obtaining chitosan from chitin, chitin is immersed in a 40-50% alkaline solution, treated at 115-130"C for 5 hours to perform deacetylation, and then the alkaline solution is removed, and then By washing with water and drying, flaky chitosan can be obtained, and by crushing this, powdered chitosan can be obtained.
本発明に使用されるリン酸としては、メタリン酸、ビロ
リン酸、オルトリン酸、三リン酸、四リン酸、及びこれ
らリン酸の塩を含有するリン酸類等が挙げられる。これ
らのリン酸は適当な濃度の水溶液として用いられる。Examples of the phosphoric acid used in the present invention include metaphosphoric acid, birophosphoric acid, orthophosphoric acid, triphosphoric acid, tetraphosphoric acid, and phosphoric acids containing salts of these phosphoric acids. These phosphoric acids are used as aqueous solutions of appropriate concentrations.
上記リン酸の濃度、反応温度、及び反応時間等を種々設
定することにより任意の分子量、例えば５００〜５００
００、好ましくは８００〜２０００という低分子量を有
する低分子化キトサンを得ることができる。By variously setting the concentration, reaction temperature, reaction time, etc. of the above-mentioned phosphoric acid, it is possible to obtain an arbitrary molecular weight, for example, from 500 to 500.
Low molecular weight chitosan having a low molecular weight of 0.00, preferably 800 to 2000 can be obtained.
本発明の実施方法を以下に具体的に示す。A method for implementing the present invention will be specifically shown below.
原料キトサンに対し重量比で０．５〜１Ｏ００のリン酸
水溶液（濃度１０％〜９０％、好ましくは４０％〜８５
％）を添加する０反応系は懸濁状となるため反応混合物
を攪拌せしめ、反応温度３０°Ｃ〜１００°Ｃ１好まし
くは５０″Ｃ〜９０°Ｃにて０．５時間〜４８時間、好
ましくは２時間〜２４時間反応させる。反応終了後、リ
ン酸を中和するために等価量のアルカリ性物質の水溶液
あるいは水への分散溶液を加える。アルカリ性物質とし
てはアルカリ金属あるいはアルカリ土類金属の水酸化物
が挙げられるが、後処理におけるリン酸塩の除去の容易
さを考えると水酸化カルシウムが好適である。A phosphoric acid aqueous solution (concentration 10% to 90%, preferably 40% to 85% by weight relative to the raw material chitosan)
%) is added to form a suspension, the reaction mixture is stirred, and the reaction temperature is 30°C to 100°C, preferably 50"C to 90°C, for 0.5 to 48 hours, preferably is reacted for 2 to 24 hours. After the reaction is complete, an equivalent amount of an aqueous solution or a dispersion of an alkaline substance in water is added to neutralize the phosphoric acid. As an alkaline substance, an aqueous solution of an alkali metal or an alkaline earth metal is added. Examples include oxides, but calcium hydroxide is preferred in view of ease of removing phosphate in post-treatment.
アルカリ性物質は５％〜５０％、好ましくは１０％〜２
５％の水への分散溶液として用いることができる。The alkaline substance is 5% to 50%, preferably 10% to 2
It can be used as a dispersion solution in 5% water.
中和処理後、遠心分離等の分離処理を施し、上澄液に更
にアセトン、メタノール、エタノール、イソプロピルア
ルコール等のケトン類あるいは低級アルコール類の有機
溶媒を添加することにより、沈澱物として目的とする低
分子化キトサンを得ることができる。After neutralization, a separation process such as centrifugation is performed, and an organic solvent such as ketones or lower alcohols such as acetone, methanol, ethanol, and isopropyl alcohol is added to the supernatant to obtain the desired precipitate. Low molecular weight chitosan can be obtained.
これらの操作により着色の少ない低分子化キトサンを効
率よく得ることができる。By these operations, low-molecular-weight chitosan with little coloring can be efficiently obtained.
本発明によれば、キトサンの分解に使用した過剰のリン
酸を前記アルカリ性物質との塩、例えばカルシウム塩と
して沈澱分離せしめることにより、低分子化キトサンを
含む反応系中より容易に分離することができる。これは
反応工程の簡便化あるいは低分子化キトサンの品質を高
める上でも本発明の方法が従来の方法に比べて数段効果
的であることを示すものである。According to the present invention, the excess phosphoric acid used to decompose chitosan is precipitated and separated as a salt with the alkaline substance, for example, a calcium salt, so that it can be easily separated from the reaction system containing low-molecular-weight chitosan. can. This shows that the method of the present invention is much more effective than conventional methods in terms of simplifying the reaction process and improving the quality of low-molecular-weight chitosan.
以下実施例を挙げて本発明を更に詳細に説明するが、本
発明はこれらの実施例に限定されるものではない。EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.
尚、各実施例における分子量及びその分布の測定は高速
液体クロマトグラフィー（ポンプ：日本分光ＢＩＰ−１
；検出器： ５ＨＯＤＥＸ ＲＩＳＥ−３１；カラム：
ＡＳＡＨＩＰＡに）によって測定した。又、アミノ基
含量はポリビニル硫酸カリウム溶液を用いたコロイド滴
定法により測定した。The molecular weight and its distribution in each example were measured using high performance liquid chromatography (pump: JASCO BIP-1).
;Detector: 5HODEX RISE-31;Column:
ASAHIPA). Moreover, the amino group content was measured by a colloid titration method using a polyvinyl potassium sulfate solution.
実施例１
キトサン（平均分子量５ｏｏｏｏ、アミノ基含量８．１
％）２０ｇを６０％オルトリン酸水溶液１１０ｇに懸濁
し、攪拌しなから７０°Ｃで４時間反応を行った。これ
に等価量の水酸化カルシウムを含む３００威のスラリー
を添加し、中和を行い、次いで遠心分離（８０００ｒｐ
ｍ、 １５ ｍ１ｎ）により上澄液を得た。Example 1 Chitosan (average molecular weight 5oooo, amino group content 8.1
%) was suspended in 110 g of a 60% aqueous orthophosphoric acid solution, and the reaction was carried out at 70°C for 4 hours without stirring. A slurry of 300 mm containing an equivalent amount of calcium hydroxide was added to this to neutralize it, and then centrifuged (8000 rpm).
A supernatant liquid was obtained using 15 m1n).
この上澄液からアセトン沈澱により低分子化キトサンを
分取し、常法に従って淡黄色の粉末状キトサンを得た（
収率２０．２％）。得られた低分子化キトサンの平均分
子量は１３００であり、アミノ基含量は６．８％であっ
た。Low-molecular-weight chitosan was separated from this supernatant by acetone precipitation, and light yellow powdered chitosan was obtained using a conventional method (
yield 20.2%). The average molecular weight of the obtained low-molecular-weight chitosan was 1300, and the amino group content was 6.8%.
実施例２
実施例１で用いたキトサン２０ｇを４０％オルトリン酸
水溶液１１０ｇに懸濁し、攪拌しなから９０°Ｃで４時
間反応を行った。これ以後の操作は実施例１に準じて低
分子化キトサンを製造を行い、淡黄色の粉末状キトサン
を得た（収率１１．６％）。Example 2 20 g of chitosan used in Example 1 was suspended in 110 g of a 40% orthophosphoric acid aqueous solution, and a reaction was carried out at 90°C for 4 hours without stirring. The subsequent operations were performed to produce low-molecular-weight chitosan in accordance with Example 1, and pale yellow powdered chitosan was obtained (yield: 11.6%).
得られた低分子化キトサンの平均分子量は９８０であり
、アミノ基含量は７．５％であった。The average molecular weight of the obtained low-molecular-weight chitosan was 980, and the amino group content was 7.5%.
実施例３
キトサン（平均分子量２５００００．アミノ基含量８．
２％）２０ｇを６０％オルトリン酸水溶液１１０ｇに懸
濁し、攪拌しながら７０°Ｃで８時間反応を行った。こ
れ以後の操作は実施例１に準じて低分子化キトサンを製
造を行い、白色の粉末状キトサンを得た（収率１９．１
％）、得られた低分子化キトサンの平均分子量は１４０
０であり、アミノ基含量は７．３％であった。Example 3 Chitosan (average molecular weight 250,000. Amino group content 8.
2%) was suspended in 110 g of a 60% orthophosphoric acid aqueous solution, and the reaction was carried out at 70°C for 8 hours with stirring. The subsequent operations were carried out to produce low-molecular chitosan according to Example 1, and white powdered chitosan was obtained (yield: 19.1
%), the average molecular weight of the obtained low-molecular chitosan was 140
0, and the amino group content was 7.3%.
本発明の製造方法によりリン酸水溶液中でキトサンを処
理すると、キトサンのアミノ基含量に影響をおよぼさず
選択的にグリコサイド結合のみを切断し、又リン酸水溶
液の濃度、反応の温度及び時間を種々設定することによ
り任意の分子量を有する着色の少ない低分子化キトサン
を得ることができる。When chitosan is treated in an aqueous phosphoric acid solution according to the production method of the present invention, only the glycoside bonds are selectively cleaved without affecting the amino group content of chitosan, and the concentration of the phosphoric acid aqueous solution, reaction temperature and By setting various times, it is possible to obtain low-molecular-weight chitosan with a desired molecular weight and little coloring.
又、従来の方法で塩酸等を用いた場合に多大な労力を必
要としていた過剰の酸の除去操作も本発明によれば、過
剰のリン酸は水不溶性の塩として容易にしかも完全に除
去することができるので操作上の効率を高めることがで
きる。Furthermore, according to the present invention, excess phosphoric acid can be easily and completely removed as a water-insoluble salt, which required a great deal of labor when using hydrochloric acid or the like in the conventional method. This makes it possible to improve operational efficiency.
Claims (1)
分子量のキトサンを得ることを特徴とする低分子化キト
サンの製造方法。 ２ 処理液にアルカリ性物質を加えて過剰のリン酸を水
に不溶性の塩として沈澱分離する請求項１記載の低分子
化キトサンの製造方法。[Scope of Claims] 1. A method for producing low-molecular-weight chitosan, which comprises obtaining low-molecular-weight chitosan by treating chitosan in an aqueous phosphoric acid solution. 2. The method for producing low-molecular-weight chitosan according to claim 1, wherein an alkaline substance is added to the treatment liquid to precipitate excess phosphoric acid as a water-insoluble salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13717289A JP2721546B2 (en) | 1989-05-30 | 1989-05-30 | Method for producing low molecular weight chitosan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13717289A JP2721546B2 (en) | 1989-05-30 | 1989-05-30 | Method for producing low molecular weight chitosan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH032203A true JPH032203A (en) | 1991-01-08 |
| JP2721546B2 JP2721546B2 (en) | 1998-03-04 |
Family
ID=15192499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13717289A Expired - Fee Related JP2721546B2 (en) | 1989-05-30 | 1989-05-30 | Method for producing low molecular weight chitosan |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2721546B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705634A (en) * | 1995-03-02 | 1998-01-06 | Perimmune Holdings, Inc. | High yield preparation of dimeric to decameric chitin oligomers |
-
1989
- 1989-05-30 JP JP13717289A patent/JP2721546B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705634A (en) * | 1995-03-02 | 1998-01-06 | Perimmune Holdings, Inc. | High yield preparation of dimeric to decameric chitin oligomers |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2721546B2 (en) | 1998-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4195175A (en) | Process for the manufacture of chitosan | |
| JPH0558002B2 (en) | ||
| JPH0220292A (en) | Production of depolymerized chitosan | |
| WO1991000298A1 (en) | Method for continuous manufacture of microcrystalline chitosan | |
| CN106243245B (en) | A kind of preparation method of chitosan | |
| Roberts et al. | Preparation of chitin and chitosan | |
| JPH032203A (en) | Production of low molecular weight chitosan | |
| EP0440717A1 (en) | Method for producing chitosan | |
| JP5256509B2 (en) | Method for producing N-acetylglucosamine and use thereof | |
| JP2002177000A (en) | Method for manufacturing chitin olygosaccharide | |
| JPH0931104A (en) | Production of low-molecular chitosan and chitooligosaccharide | |
| JPS62184002A (en) | Production of low-molecular weight water-soluble chitosan | |
| JP2521764B2 (en) | Method for producing low molecular weight chitosan | |
| JPS63120701A (en) | Production of chitosan of low molecular weight | |
| JPH1072502A (en) | Production of water-soluble, partially acetylated chitosan solution | |
| JPH0633321B2 (en) | Method for producing water-soluble chitosan | |
| CN104497170A (en) | Method for preparing chitin oligosaccharide via homogeneous phase | |
| JP3055965B2 (en) | Enzymatic degradation method of chitin-containing material | |
| JPH0725803B2 (en) | Method for producing water-soluble low molecular weight chitosan | |
| JPS6317901A (en) | Purification of chitosan | |
| JPH0133482B2 (en) | ||
| RU2065447C1 (en) | Method of chitosan preparing | |
| US2416176A (en) | Process for the treatment of plant flesh and the recovery of pectic products therefrom | |
| JP2758475B2 (en) | Chitosan oligomer and method for producing the same | |
| JPH0564595A (en) | Enzymatic decomposition of chitin-containing material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |