1231816 A7 Β7 - -------------- 五、發明說明（) — 幾丁胺醣爲一種天然高分子化合物，其化學式如1231816 A7 Β7--------------- 5. Description of the invention () — Chitosamine is a natural polymer compound with a chemical formula such as
OH NH2OH NH2
分子鏈上含有胺基（amino group)及乙酿胺基（acetyl_ amido group)二種構造單无，脱乙酿度（degree of de-acetylation)爲幾丁胺醣的重要规格春數，影響其物後與 化性。 幾丁胺醣具有胺基，可以溶解於酸之水溶液中，然而 在中性及鹼性狀態下，幾丁胺醣並不溶於水或其他的溶劑 中，因此幾丁胺醣用於製造衍生物時，經常是以不均勻相 進行化學反應，亦即直接以幾丁胺醣固體在反應液中攪拌 進行，必須依靠反應物之分子滲入幾丁胺醣固殖中才能夠 與官能基發生作用。 十 Λ 然而幾丁胺醣爲高分子化合物，並且具備氫氧基、胺 基、乙醯$基，形成強烈的分子間氫鍵，造成高结晶度的 物理结構，一般化學反應只能夠在高分子的非結晶區發生 ，因此如何提高反應率，一直是幾丁胺醣衍生物製程期待 解決的間顏。以溶液形式進行均勻相反應爲最佳途徑，然 而由於受限於反應條件，經常是無法獲得。因此，在保留 冢紙认尺度〗十家把專（（、阳）Μ規格（210X297公釐） 1231816 A7 B7 V| 十 .火 乂:J )i Λ ϋ 印 今.: 7λ、發明説明（） 固態形體的條件下，破壞結晶區，增加反應物參人幾丁按 膽的全區域，是提高反應率的解決方法。 幾丁胺醣高分子上的胺基（NIL)與酸结合可形成帶 正電的基困（NH5+)，而溶解於水中，如果遇見帶負電的 大分子，如腠離子界面活性劑，立即形成錯合物（c〇rap^ ex)，通常這些錯合物不溶於水，並且安定性良好。 本發明利用幾丁胺醣溶解於酸的過程緩慢，而形成錯 II的過程非常迅速之原理，令幾丁胺醣高分子浸泡於包含 飨離子界面活性劑之酸液中，當幾丁胺醣遇見酸之後，形 成NH/之解離，陰離界面活性劑滲入分子内與NH/結合， 由於界面活性劑油基鏈之間的凝聚作用形成撖胞結構，加 速破壞幾丁胺醣之结晶區，並製造孔隙，使分子容易滲透 進入。 利用本發明之方法，適合幾丁胺醣進行「不均勻反應 」之前處理，可以视需要以飨離子界面活性劑之酸液處理 幾丁胺醣固體後，保留錯合物型態進行衍生物反應。或經 過驗浸及水洗除去幾丁胺醣上的險離子界面活性劑，而以 純幾丁胺之非結晶結構進行衍生物反應。 本紙队尺度這W十K國家樣率（CNS ) Λ4規格（210X 297公釐） (誚先閱讀背面之注意事項π本頁 •裳· 、1Τ 1231816 A7 B7 五、發明说明（） 程序： 幾丁胺醣固體 險離子界面活性劑酸液處理 完全非结晶結構 圖式之簡單説明： ' ιΐ 部 中 .火 λ (丨: 第一蔺爲處理前之幾丁胺醣之结構示意圖 第二圖爲處理後之幾丁胺醣之完全非结晶結構示意圖 圖始説明： 1、 结晶區 2、 非结晶區 本紙张尺度逍州个囤國家桴卑（C’NS ) Α4規格（210Χ 297公釐） 1231816五、發明说明（) 3、歡抱 A7 B7 4、界面活性劑分子 實例一： 對於10 0 g之幾丁按踏（脱乙殖率爲7〇％)進行 脱乙醯率衍生物之製作，先秤取200 g之十二燒基磺酸 钠及300g濃度30%之乙酸溶於1〇升水中配製成處 理液，在常溫狀態下，將上列幾丁胺醣浸泡於處理液中3 小時，幾丁胺醣產生膨脹，過濾除去多餘水份後，將處理 過的幾丁胺賭，以5升濃度爲40%之氫氧化钠溶液’在 1 0 Ot：溫度反應2小時，得到脱乙醯率爲94%之幾丁 胺醣。 實例二： 對於50g脱乙醯率爲8 5%之幾丁胺醣進行羧曱基 衍生物（carboxymethyl derivatives )之製作。幾丁胺 O 11 V|> 消 Μ 膽先以除離子界面活性剩之酸液浸泡4小時，溶波之組成 爲3%之十六烷基硫酸钠、1%之哽脂酸钠、1%之鹽酸 溶於水中。將處理後之幾丁胺醣過濾，除去多餘水份，再 浸泡於1务濃度4 0%之氫氧化钠溶液中，攪拌2小時以 後，在溶液中徐徐加入50 g之一氣乙酸，加料期間爲1 小時，再將溫度上升至5 ου，繼續攪拌6小時，得到取 代率爲0.9之Ν.0—叛甲基衍生物（Ν. 0 - car boxy methyl chitosan) 0 ITk张尺度述州不國國家掠率（CNS )八4規格（210X 297公釐） 1231816 A7 B7 五、發明説明（） 實例三： 對於2 0 g脱乙醯率爲8 5%之幾丁胺醣進行酯化反 應；先對幾丁胺醣進行預處理，浸泡在1升濃度爲0.5% 之十二烷基硫酸钠與1%甲酸之水溶液中，攪拌2小時以 後，取出過濾，將處理後之幾丁胺醣錯合物加入30 0m 1 冰醋酸中，進行攪拌，在室溫下滴入醋酸酐與過氣酸之混 合液，（過氣酸/醋酸酐組成爲7ml/250inl)， ，反應8小時以後得到取代率爲0 · 8之幾丁胺醣乙酸脂 (〇 - acetyl chitosan ester )，其脱乙酿率仍維持於8 5%。 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消f合作社印製 本紙張尺度適;彳]中國國家標绛（CNS ) Λ4規格（210X297公釐）The molecular chain contains two kinds of structures: amino group and acetyl_ amido group. The degree of de-acetylation is an important specification of chitosamine, which affects its number. After physical and chemical properties. Chitosanose has an amine group and can be dissolved in an aqueous acid solution. However, in neutral and alkaline states, chitosanose is not soluble in water or other solvents, so chitosanose is used to make derivatives. In this case, the chemical reaction is often carried out in a heterogeneous phase, that is, the chitosan solid is directly stirred in the reaction solution, and the molecular of the reactant must be penetrated into the chitosan solidification to interact with the functional group. Ten Λ However, chitosamine is a polymer compound, and has hydroxyl, amine, and acetamidine groups, forming strong intermolecular hydrogen bonds, resulting in a physical structure with high crystallinity. Generally, chemical reactions can only occur in polymers. The occurrence of non-crystalline regions, so how to improve the reaction rate has always been the look of the chitosan derivative process. A homogeneous reaction in the form of a solution is the best approach, but it is often not available due to the limited reaction conditions. Therefore, in retaining the grave paper recognition standards, ten professional ((, yang) M specifications (210X297 mm) 1231816 A7 B7 V | X. Fire 乂: J) i Λ 印 Imprint today: 7λ, description of the invention () Under the condition of solid form, the crystallization area is destroyed, and the whole area of the reaction product, including chitin and gall bladder, is a solution to improve the reaction rate. The amine group (NIL) on the chitosan polymer combines with the acid to form a positively charged radical (NH5 +), which is dissolved in water. If it encounters a negatively charged macromolecule, such as a sulfonium surfactant, it will form immediately Complexes (copar ^ ex), usually these complexes are insoluble in water and have good stability. The invention utilizes the principle that the process of dissolving chitosan in acid is slow, and the process of forming wrong II is very fast. The chitosan polymer is immersed in an acid solution containing a sulfonium surfactant, and when the chitosan is dissolved, After meeting the acid, dissociation of NH / is formed, and the anionic surfactant penetrates into the molecule and combines with NH /. Due to the cohesion between the oil-based chains of the surfactant, a cell structure is formed, which accelerates the destruction of the crystalline region of chitosanose. And create pores to make molecules easily penetrate into. The method of the present invention is suitable for pretreatment of "heterogeneous reaction" of chitosanose. If necessary, the chitosan solid can be treated with an acid solution of a phosphonium ion surfactant, and the complex reaction can be retained for derivative reaction. . Or, the dangerous ionic surfactant on the chitosanose can be removed by dipping and washing with water, and the derivative reaction can be performed with the non-crystalline structure of pure chitosan. The size of this paper is the W10K national sample rate (CNS) Λ4 specification (210X 297mm) (诮 Please read the notes on the back side first page · Shang · 1T 1231816 A7 B7 V. Description of the invention () Procedure: Chitin A brief description of the complete non-crystalline structure of the amine sugar solid ionic surfactant acid solution treatment: 'ιΐ 部. 火 λ (丨: The first 蔺 is a schematic diagram of the structure of chitosan before treatment The second picture is the treatment The following figure shows the complete amorphous structure of chitosanose: 1. Crystallized area 2. Amorphous area This paper is standard Paper size in Xiaozhou (C'NS) Α4 size (210 × 297 mm) 1231816 2. Description of the invention (3) Hugging A7 B7 4. Example of surfactant molecule 1: For 100 g of chitin, press the step (deacetylation rate of 70%) to make the deacetylation rate derivative, first Weigh 200 g of sodium dodecyl sulfonate and 300 g of 30% acetic acid in 10 liters of water to prepare a treatment solution. Under normal temperature conditions, soak the above chitosan sugar in the treatment solution for 3 hours. , Chitosamine swells, after filtering to remove excess water, the treated Chitamine was reacted with 5 liters of a 40% sodium hydroxide solution at 10 Ot: temperature for 2 hours to obtain a chitosanose with a deacetylation rate of 94%. Example 2: For 50 g of deacetylated Preparation of carboxymethyl derivatives with chitosamine at a rate of 8 5%. Chitinamine O 11 V | > Elimination of gallbladder was first immersed in the acid solution remaining at the deionization interface for 4 hours, dissolved The composition of the wave is 3% sodium hexadecyl sulfate, 1% sodium gallate, 1% hydrochloric acid dissolved in water. The treated chitosan is filtered to remove excess water, and then immersed in 1 serving In a 40% sodium hydroxide solution, after stirring for 2 hours, 50 g of a gaseous acetic acid was slowly added to the solution, the feeding period was 1 hour, the temperature was increased to 5 ου, and the stirring was continued for 6 hours to obtain the substitution rate. Ν.0 of 0.9—Carboxy methyl chitosan 0 ITk Zhang scale State and country predation rate (CNS) 8 4 specifications (210X 297 mm) 1231816 A7 B7 V. Invention Explanation () Example 3: Esterification reaction of chitosan sugar with a deacetylation rate of 8 5% at 20 g; chitin Pretreatment, soak in 1 liter of 0.5% sodium dodecyl sulfate and 1% formic acid in water, stir for 2 hours, remove and filter, add the treated chitosan complex to 300 0m 1 In glacial acetic acid, stir, dropwise add a mixture of acetic anhydride and peroxyacid at room temperature (peroxyacid / acetic anhydride composition is 7ml / 250inl). After 8 hours of reaction, the substitution rate will be 0 · 8. Chitosan acetate (〇-acetyl chitosan ester), its deacetylation rate is still maintained at 8 5%. (Please read the precautions on the back before filling this page) Printed by Bei Gong Xiao Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs This paper is of suitable size; 彳] China National Standard 绛 (CNS) Λ4 size (210X297 mm)