KR100328335B1 - Method of preparing quaternary ammonium group N-substituted water soluble chitosan derivatives - Google Patents
Method of preparing quaternary ammonium group N-substituted water soluble chitosan derivatives Download PDFInfo
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- KR100328335B1 KR100328335B1 KR1019990052023A KR19990052023A KR100328335B1 KR 100328335 B1 KR100328335 B1 KR 100328335B1 KR 1019990052023 A KR1019990052023 A KR 1019990052023A KR 19990052023 A KR19990052023 A KR 19990052023A KR 100328335 B1 KR100328335 B1 KR 100328335B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
Abstract
유기용매/물의 혼합용매계에서 키토산에 양이온성 치환기를 도입하여 양이온성 키토산 유도체를 제조하는 방법에 관한 것이다. 본 발명은 글리시딜 트리알킬 암모늄염, 글리시딜 아릴염 등을 유기용매/물의 혼합용매계에서 키토산과 현탁상태로 반응시키는 것을 특징으로 한 양이온성 4차 암모늄기가 N-치환된 키토산 유도체 의 제조에 관한 것이다. 따라서 치환도가 높고 반응 생성물의 회수가 쉽기 때문에 제조 방법이 효율적이고 경제적으로 제조할 수 있어서 공업적 생산이 용이하다.The present invention relates to a method for preparing a cationic chitosan derivative by introducing a cationic substituent to chitosan in an organic solvent / water mixed solvent system. The present invention is to prepare a cationic quaternary ammonium group N-substituted chitosan derivative, characterized in that the glycidyl trialkyl ammonium salt, glycidyl aryl salt and the like react with chitosan in a suspended state in a mixed solvent system of organic solvent / water It is about. Therefore, since the degree of substitution is high and the recovery of the reaction product is easy, the production method can be efficiently and economically produced, and industrial production is easy.
본 발명에서 제조한 양이온성 키토산 유도체는 화장품, 농업용, 섬유 처리제, 이온교환수지, 정정기 대전 방지제, 응집제, 접착제, 잉크 등에 사용할 수 있다.The cationic chitosan derivatives prepared in the present invention can be used in cosmetics, agriculture, textile treatment agents, ion exchange resins, corrective antistatic agents, flocculants, adhesives, inks and the like.
Description
본 발명은 양이온성 키토산을 제조하는 방법으로서 4차 암모늄기가 N-치환된 수용성 키토산 유도체 제조 방법에 관한 것이다.The present invention relates to a method for producing a cationic chitosan, a method for producing a water-soluble chitosan derivative in which the quaternary ammonium group is N-substituted.
키틴은 무고다당으로서 안정한 결정성 구조를 가지고 있기 때문에 유용한 산업적 재료임에도 불구하고 용해성이 없어서 유용하게 이용하지 못하였다. 또한 키틴을 탈아세틸화하여 제조된 키토산은 약산에 용해시켜 항균제, 탈취제, 건강보조식품, 식품첨가제 등으로 사용하고 있으나, 산성 용액에만 용해되기 때문에 사용범위가 제한되어 있다. 따라서 물, 수용매에 용이하게 용해될 수 있고 항균성 등의 기능이 강화된 키토산 유도체를 개발함으로써 산업적 유용성이 확대 될 것이다.Chitin is an innocent polysaccharide and has a stable crystalline structure. However, although it is a useful industrial material, chitin has not been useful because it is insoluble. In addition, chitosan prepared by deacetylating chitin is used in antimicrobial agents, deodorants, health supplements, food additives, etc. by dissolving in weak acid, but the range of use is limited because it is dissolved only in acidic solutions. Therefore, industrial usefulness will be expanded by developing chitosan derivatives which can be easily dissolved in water and aqueous solvents and have enhanced functions such as antibacterial properties.
본 발명의 목적은 산업적으로 유용하고 수용매에 용해될 수 있을 뿐만 아니라, 섬유처리제, 화장품 등에 사용하였을 때의 유화성, 기포력, 정정기 방지성, 항균성, 염색성 등의 기능이 강화된 4차 암모늄기가 N-치환된 키토산 유도체(화학식 1)의 제조 방법을 제공하는데 있다.An object of the present invention is a quaternary ammonium group which is industrially useful and can be dissolved in a solvent, and also has enhanced functions such as emulsification, foaming, anti-correction, antibacterial, and dyeing properties when used in textile treatment agents and cosmetics. Is to provide a method for preparing an N-substituted chitosan derivative (Formula 1).
종래에 4차 암모늄기가 N-치환된 키토산 유도체의 제조 방법은 염산 수용액에 용해시킨 후 가성소다 용액을 가하여 침전시켜 물이 함유된 키토산을 만들고 이 물함유 키토산을 가압 반응기에 넣어 에틸렌 옥사이드 또는 프로필렌 옥사이드를 첨가하고, 여기에 글리시딜 트리알킬 암모늄염을 가하여 반응시켰다. 이 반응용액을 과량의 아세톤에 침전시키든가 투석하여 순수한 4차 암모늄기가 N-치환된 키토산 유도체을 제조하였다.(US 4,772,689) 또한 염산 수용액에 용해시킨 다음 가성소다로 재참전하는 과정을 생략하고 물/알코올 혼합용매에서 상기의 방법과 동일한 방법으로 4차 암모늄기가 N-치환된 키토산 유도체를 제조하기도 하였다.(US 4,976,952) 그러나 상기의 방법들은 전저리 과정이 복잡하고 가압 반응기등에서 제조해야 하는 등 제조조건이 어렵고, 제조하였을 때 용매에 용해되어 있는 상태기 때문에 정제및 회수 과정에서 과량의 아세톤 등 유기용매를 사용해야하는 등 후처리과정이 복잡하고 환경 문제를 일으킬 수 있는 단점이 있다.Conventionally, a method for preparing a chitosan derivative having an N-substituted quaternary ammonium group is dissolved in an aqueous hydrochloric acid solution and then precipitated by adding a caustic soda solution to make chitosan containing water, and the water-containing chitosan is placed in a pressurized reactor to give ethylene oxide or propylene oxide. Was added, and glycidyl trialkyl ammonium salt was added thereto to react. The reaction solution was precipitated in excess acetone or dialyzed to prepare chitosan derivatives having N-substituted pure quaternary ammonium groups. (US 4,772,689) Also, the process of dissolving in aqueous hydrochloric acid solution and then rejoining with caustic soda was omitted. In the alcohol mixed solvent, chitosan derivatives having N-substituted quaternary ammonium groups were prepared by the same method as described above. (US 4,976,952) However, the above methods are complicated by pretreatment and must be prepared in a pressurized reactor. This is difficult, and since it is dissolved in a solvent when manufactured, there is a disadvantage that the post-treatment process may be complicated and cause environmental problems such as using an excess of an organic solvent such as acetone in the purification and recovery process.
본 발명에서는 상기에서 지적한 문제를 해결하여 전처리 과정이 필요없고 제조 조건이 일반적이면서 제조방법이 간편하고 치환도가 높은 4차 암모늄기가 N-치환된 수용성 키토산 유도체(화학식 1)의 제조 방법을 제공하는데 있다.The present invention solves the above-mentioned problems and provides a method for preparing a water-soluble chitosan derivative (Formula 1) in which a quaternary ammonium group is N-substituted, having no pretreatment process, a general manufacturing condition, a simple manufacturing method, and a high degree of substitution. have.
본 발명은 물과 적어도 한가지 이상의 유기용매와의 혼합용매에서 현탁상태로 반응시키는 것을 특징으로하는 4차 암모늄기가 N-치환된 수용성 키토산 유도체(화학식 1)를 제조하는 방법에 관한 것이다. 더욱 상세히 설명하면 유기용매/물 혼합계에 키토산을 분산시키고 4차 암모늄 할로하이드린과 4차 암모늄 에폭사이드 등의 에테르 시약을 반응시켜 4차 암모늄기가 N-치환된 수용성 키토산 유도체(화학식 1)의 제조 방법에 관한 것이다. 상기의 방법으로 제조한 4차 암모늄기가 N-치환된 수용성 키토산 유도체는 화장품, 섬유제품, 의약품, 식품, 응집제, 항균제, 염색제, 이온교환수지, 정정기 방지제, 접착제, 잉크 등에 다양하게 사용할 수 있다.The present invention relates to a method for preparing a water-soluble chitosan derivative having a N-substituted quaternary ammonium group, which is reacted in suspension in a mixed solvent of water and at least one organic solvent. In more detail, chitosan is dispersed in an organic solvent / water mixture, and an ether reagent such as quaternary ammonium halohydrin and quaternary ammonium epoxide is reacted to obtain a water-soluble chitosan derivative having N-substituted quaternary ammonium group (Formula 1). It relates to a manufacturing method. The quaternary ammonium group N-substituted water-soluble chitosan derivatives prepared by the above method can be used in a variety of cosmetics, textile products, pharmaceuticals, foods, flocculants, antibacterial agents, dyes, ion exchange resins, anti-correction agents, adhesives, inks and the like.
본 발명은 물/유기용매의 혼합용액에 키토산을 분산시키고 이 현탁액에 글리시딜 트리알킬 암모늄염, 글리시딜 아릴염 등의 에테르 시약을 상온에서 첨가한 다음 이를 25 내지 80℃에서 반응시키는 것과 물/유기용매의 혼합용액에 키토산을 분산시키고 4차 할로하이드린과 4차 에폭사이드 등의 에테르시약을 현탁상태로 반응시켜 제조하는 것을 특징으로 하는 4차 암모늄기가 N-치환된 수용성 키토산 유도체(화학식 1)의 제조 방법에 관한 것이다.In the present invention, chitosan is dispersed in a mixed solution of water / organic solvent, and ether reagents such as glycidyl trialkyl ammonium salt and glycidyl aryl salt are added to the suspension at room temperature, followed by reaction at 25 to 80 ° C. and water A water-soluble chitosan derivative having an N-substituted quaternary ammonium group, which is prepared by dispersing chitosan in a mixed solution of an organic solvent and reacting an ether reagent such as quaternary halohydrin and quaternary epoxide in a suspended state. It relates to the manufacturing method of 1).
이를 더욱 상세히 설명하면 유기용매와 물의 비율이 중량비로 95/5 내지 50/50인 혼합 용매에 키토산을 용매에 대하여 10 내지 50 중량부를 가하고 여기에 글리시딜 트리알킬 암모늄염, 글리시딜 아릴염 등의 4차 암모늄 에폭사이드 에테르화 시약을 키토산의 글루코오스아민 당량의 0.5 내지 15배몰을 첨가하여 반응온도을 25 내지 80℃에서 2시간 내지 16시간 반응시켜 에테르화 한다. 또는 키토산을 분산시키는 단계는 상기의 방법과 동일하게 현탁시키고 여기에 3-클로로-2-하이드록시 프로필 트리알킬 암모늄 염(3-chloro-2-hydroxy propyl trialkyl ammonium salt), 3-클로로-2-하이드록시 프로필 아릴 암모늄 염(3-chloro-2-hydroxy propyl aryl ammonium salt), 3-클로로 프로필 트리알킬 암모늄 염(3-chloropropyl trialkyl ammo Nium salt) 또는 3-클로로 프로필 아릴 암모늄 염(3-chloropropyl aryl ammonium salt)의 4차 암모늄 할로하이드린 에테르 시약을 가한 다음 알칼리를 고상 또는 수용액상으로 에테르 시약과 동몰 내지는 2배 몰을 가하여 에테르화시키는 단계로 이루어진다. 에테르 시약과 알칼리의 첨가는 40℃이하에서 이루어지는 것이 바람직하며 알칼리는 수용액상으로 첨가하는 것이 바람직하다. 알칼리를 첨가한 후 반응온도와 시간은 상기의 방법과 동일하게 시행한다.To explain this in more detail, 10 to 50 parts by weight of chitosan is added to the mixed solvent in which the ratio of the organic solvent and water is 95/5 to 50/50 by weight, and glycidyl trialkyl ammonium salt, glycidyl aryl salt, and the like are added thereto. The quaternary ammonium epoxide etherification reagent of was added in an amount of 0.5 to 15 times the molar equivalent of the glucoseamine equivalent of chitosan, followed by etherification by reacting the reaction temperature at 25 to 80 ° C. for 2 to 16 hours. Alternatively, the step of dispersing the chitosan may be suspended in the same manner as the above method, and 3-chloro-2-hydroxy propyl trialkyl ammonium salt, 3-chloro-2- 3-chloro-2-hydroxy propyl aryl ammonium salt, 3-chloropropyl trialkyl ammo Nium salt or 3-chloropropyl aryl ammonium salt A quaternary ammonium halohydrin ether reagent of ammonium salt) is added, followed by etherification of the alkali by adding an equimolar or double molar moiety with the ether reagent in solid or aqueous solution. The addition of the ether reagent and the alkali is preferably performed at 40 ° C. or lower, and the alkali is preferably added in the form of an aqueous solution. After addition of alkali, the reaction temperature and time are carried out in the same manner as above.
본 발명에 사용된 키토산의 예로는 새우껍질, 게껍질 등을 가성소다로 가열하고 염산 등으로 처리하여 얻은 키틴을 탈아세틸화하여 얻어지는 α-키토산 또는 갑오징어 뼈 등을 을 가성소다 및 염산으로 처리하여 제조한 β-키토산을 사용할 수 있다. 본 발명에 사용한 키토산은 탈아세틸화도 50-100%이고 중합도 200-30000정도를 사용하면 적당하다. 또한 키도산은 시판품을 사용해도 무방하다.As an example of chitosan used in the present invention, α-chitosan or cuttlefish bone obtained by deacetylating chitin obtained by heating shrimp shells and crab shells with caustic soda and treating with hydrochloric acid or the like is treated with caustic soda and hydrochloric acid. Can be used. The chitosan used for this invention is 50-100% of deacetylation degree, and it is suitable to use about 200-30000 degree of polymerization. In addition, you can use commercially available products.
본 발명에서 사용한 에테르화 시약의 예로는 4차 암모늄염으로써 4차 할로하이드린(화학식 2)과 4차 에폭사이드(화학식 3)이다.Examples of etherification reagents used in the present invention are quaternary halohydrin (Formula 2) and quaternary epoxide (Formula 3) as quaternary ammonium salts.
여기서 Z는 할로겐 원소로서 염소(Cl), 브롬(Br), 요오도(I)이며 X는 염소(Cl), 브롬(Br), 요오도(I), 설페이트(SO3), 설폰산(SO3H), 니트레이트( NO3), 포스페이트(PO4), 아세테이트(CH3COO) 등이며 R1, R2, R3는 알킬, 아릴, 알킬, 알킬아릴, 시클로알킬, 알콕시알킬, 알콕시아릴 등이며 구체적인 예로는 메틸, 에틸, 프로필, 부틸, 피리딘, α-메틸피리딘, 3,5-디메틸피리딘 등이다.Where Z is a halogen element, chlorine (Cl), bromine (Br), iodo (I) and X is chlorine (Cl), bromine (Br), iodo (I), sulfate (SO 3 ), sulfonic acid (SO 3 H), nitrate (NO 3 ), phosphate (PO 4 ), acetate (CH 3 COO) and the like, and R 1, R 2, R 3 are alkyl, aryl, alkyl, alkylaryl, cycloalkyl, alkoxyalkyl, alkoxyaryl and the like. Specific examples are methyl, ethyl, propyl, butyl, pyridine, α-methylpyridine, 3,5-dimethylpyridine and the like.
본 발명에서 사용한 유기용매의 예로는 1-4개의 탄소를 갖는 지방족 알코올(메탄올, 에탄올, 프로판올, 이소프로판올, 부탄올, 이소부탄올, 에틸렌글리콜, 프로필렌글리콜 등), 글리콜모노알킬에테르(에틸렌글리콜 모노메틸에테르, 에틸렌글리콜모노에틸에테르 등), 방향족 탄화수소 화합물(벤젠, 톨루엔, 크실렌, 에틸벤젠 등), 디알킬케톤(아세톤, 디에틸케톤, 에틸메틸케톤, 디- N-프로필케톤, 메틸프로필케톤 등), 그리고 이들의 혼합물을 들 수 있다.Examples of the organic solvent used in the present invention include aliphatic alcohols having 1-4 carbons (methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, etc.), glycol monoalkyl ethers (ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, etc.), aromatic hydrocarbon compounds (benzene, toluene, xylene, ethylbenzene, etc.), dialkyl ketones (acetone, diethyl ketone, ethyl methyl ketone, di-N-propyl ketone, methyl propyl ketone, etc.) And mixtures thereof.
본 발명에서 사용한 알칼리의 예는 수산화나트륨, 수산화칼륨 등을 들 수 있다.Examples of the alkali used in the present invention include sodium hydroxide and potassium hydroxide.
상기의 방법으로 제조한 4차 암모늄기가 N-치환된 키토산 유도체는 화장품,섬유제품, 의약품, 식품, 응집제, 항균제, 염색제,이온교환수지, 정정기 방지제, 접착제, 잉크 등에 다양하게 사용할 수 있으며 제조방법이 효율적이고 경제적이어서 공업적 생산이 가능하다.The quaternary ammonium group N-substituted chitosan derivatives prepared by the above method can be used in cosmetics, textile products, medicines, foods, flocculants, antibacterial agents, dyes, ion exchange resins, anti-correction agents, adhesives, inks, etc. It is efficient and economical, allowing industrial production.
더욱 상세하게 예를 들면 다음의 실시 예와 같다.For example, it is the same as the following example.
실시예 1Example 1
키토산 50g을 물 50㎖와 300㎖의 아세톤 혼합용액에 분산시켜 30분간 30 내지 40℃에서 패윤시킨 후 60% 글리시딜 트리메틸 암모늄 크로라이이드 78.5g을 서서히 가한 후 가성소다를 약간 첨가하여 60℃에서 6시간 반응시켰다. 이 반응 혼합물을 여과하고 80% 아세톤 수용액으로 3회 세척 후 풍건하여 건조하였다. 얻어진 4차 암모늄기가 N-치환된 키토산 유도체는 치환도가 88%, 수율이 98%이었으며, 0.5 중량%로 용해시켰을 때 불용분이 0.1%이었다.50 g of chitosan was dispersed in a mixture of 50 ml of water and 300 ml of acetone. The reaction was carried out for 6 hours. The reaction mixture was filtered, washed three times with an aqueous 80% acetone solution, air-dried and dried. The obtained chitosan derivatives having N-substituted quaternary ammonium groups had a substitution degree of 88% and a yield of 98%, and when dissolved at 0.5% by weight, the insoluble content was 0.1%.
실시예 2Example 2
본 실시예에서는 60% 글리시딜 트리메틸 암모늄 클로라이이드를 157g 사용한것 외에는 실시예 1과 동일한 방법으로 실시하였다.제조된 4차 암모늄기가 N-치환된 키토산 유도체는 치환도가 97%, 수율이 95%이었으며 0.5 중량%로 용해시켰을 때 불용분이 0%이었다.In this example, except that 157 g of 60% glycidyl trimethyl ammonium chloride was used in the same manner as in Example 1. The prepared chitosan derivative having N-substituted quaternary ammonium group had 97% substitution and yield. 95% and insoluble content was 0% when dissolved at 0.5% by weight.
실시예 3Example 3
본 실시예에서는 키토산 50g을 300㎖의 아세톤에 분산시키고 60% 3-클로로-2-하이드록시 플로필 트리메틸 암모늄 클로라이드(3-chloro-2-hydroxypropyl trimethyl ammonium chloride) 97g을 가한 다음 60% NaOH용액 20㎖를 서서히 가하여 반응시킨 것을 제외하고는 실시예 1과 동일한 방법으로 실시하였다. 제조된 4차 암모늄기가 N-치환된 키토산 유도체는 치환도가 85%, 수율이 97%이었으며 0.5 중량%로 용해시켰을 때 불용분이 0.5%이었다.In this example, 50 g of chitosan was dispersed in 300 ml of acetone, and 97 g of 60% 3-chloro-2-hydroxy flofil trimethyl ammonium chloride was added, followed by 60% NaOH solution 20 The reaction was carried out in the same manner as in Example 1, except that the reaction was slowly added by ml. The prepared quaternary ammonium group N-substituted chitosan derivatives had a substitution degree of 85%, a yield of 97%, and an insoluble content of 0.5% when dissolved at 0.5% by weight.
실시예 4Example 4
본 실시예에서는 키토산 50g을 300㎖의 아세톤에 분산시키고 60% 3-클로로 프로필 트리메틸 암모늄 클로라이드(3-chloropropyl trimethyl ammonium chloride) 90g을 가한 다음 60% NaOH용액 20㎖를 서서히 가하여 반응시킨 것을 제외하고는 실시예 1과 동일한 방법으로 실시하였다. 제조된 4차 암모늄기가 N-치환된 수용성 키토산 유도체는 치환도가 76%, 수율이 97%이었으며 0.5 중량%로 용해시켰을 때 불용분이 5%이었다.In this example, 50 g of chitosan was dispersed in 300 ml of acetone, 90 g of 60% 3-chloropropyl trimethyl ammonium chloride was added, and then 20 ml of 60% NaOH solution was added slowly to react. It carried out by the same method as Example 1. The prepared water-soluble chitosan derivatives having N-substituted quaternary ammonium groups had a substitution degree of 76%, a yield of 97%, and an insoluble content of 5% when dissolved at 0.5% by weight.
실시예 5Example 5
본 실시예에서는 유기용매를 이소프로필알콜을 사용한 것 외에는 실시예 1과 동일한 방법으로 실시하였다. 제조된 4차 암모늄기가 N-치환된 수용성 키토산 유도체의 치환도가 94%, 수율이 95%이었으며 0.5 중량%로 용해시켰을 때 불용분이 0.1%이었다.In this example, the organic solvent was used in the same manner as in Example 1 except that isopropyl alcohol was used. The degree of substitution of the prepared quaternary ammonium group N-substituted water-soluble chitosan derivative was 94%, yield 95%, and insoluble content was 0.1% when dissolved at 0.5% by weight.
본 발명의 4차 암모늄기가 N-치환된 키토산 유도체는 4급 염의 치환도가 높고 반응생성물의 회수가 쉽기 때문에 제조방법이 효율적이고 경제적으로 제조할 수 있어서 공업적 생산이 용이하다.Since the quaternary ammonium group N-substituted chitosan derivative of the present invention has a high degree of substitution of quaternary salts and easy recovery of reaction products, the production method can be manufactured efficiently and economically, and thus industrial production is easy.
또한 본 발명에서 제조한 양이온성 키토산 유도체는 기포성, 코팅성, 정전기방지성, 항균성 등의 기능을 가지고 중성에서 수용성이기 때문에 화장품, 농업용, 섬유 처리제, 이온교환수지, 정정기 방지제, 응지제, 접착제, 잉크, 식품 첨가제, 의약부 외품, 의료용, 농업용 소재 등에 광범위하게 사용할 수 있다.In addition, the cationic chitosan derivative prepared in the present invention has the functions of foaming, coating, antistatic, antimicrobial, etc., and is neutral in water so that it can be used in cosmetics, agriculture, textile treatment, ion exchange resin, anti-correction agent, coagulant, adhesive, It can be widely used for ink, food additives, quasi-drugs, medical and agricultural materials.
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