KR20020090783A - Manufacturing method chitosan derivatives - Google Patents

Manufacturing method chitosan derivatives Download PDF

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KR20020090783A
KR20020090783A KR1020010029800A KR20010029800A KR20020090783A KR 20020090783 A KR20020090783 A KR 20020090783A KR 1020010029800 A KR1020010029800 A KR 1020010029800A KR 20010029800 A KR20010029800 A KR 20010029800A KR 20020090783 A KR20020090783 A KR 20020090783A
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chitosan
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KR100407790B1 (en
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김성수
전병찬
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주식회사 이제
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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

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Abstract

PURPOSE: A method for preparing a water-soluble chitosan derivative is provided, to improve the manufacturing process for increasing the production yield by employing a specific starting reaction solution. CONSTITUTION: The method comprises the steps of adding a aqueous NaOH solution to chitosan to prepare a starting reaction solution of pH 10 or more; heating the solution at 90 deg.C; adding a reaction material to the solution and stirring it to react the mixture; cooling the solution to a room temperature; and filtering, washing with an organic solvent and drying it. The starting reaction solution is prepared by mixing chitosan and an organic acid with stirring to adjust the pH to be 3-4; dropping 1,500-2,500 parts by weight of isopropanol to the mixture based on 100 parts by weight of chitosan; and adding an aqueous NaOH solution to the solution to adjust the pH to be 10 or more. Preferably the organic acid is formic acid, lactic acid or acetic acid. N,O-carboxymethyl chitosan, N-hydropropyl chitosan and N-hydrobutyl chitosan are obtained from the reaction material of monochloroacetic acid, propylene oxide and butylene oxide, respectively.

Description

키토산 유도체의 제조방법{Manufacturing method chitosan derivatives}Manufacturing method chitosan derivatives

본 발명은 각종 화장품 원료로 많이 사용되고 있는 수용성 키토산 유도체의 제조방법에 관한 것으로, 보다 상세하게는 기존 키토산 유도체의 제조방법에 비하여 수율이 월등하게 높은 키토산 유도체의 제조방법에 관한 것이다.The present invention relates to a method for producing a water-soluble chitosan derivative that is widely used as a raw material for various cosmetics, and more particularly, to a method for producing a chitosan derivative having a higher yield than a conventional method for producing chitosan derivatives.

일반적으로 키틴은 셀룰로우스를 구성하는 기본 단당류인 글루코피라노우스 (glucopyranose) 2번 탄소의 수산기(-OH) 대신에 N-아세틸기(-N-acetyl)가 결합한 N-아세틸글루코피라노우스(N-acetylglucopyranose)가 연속적으로 β-1,4 결합된 구조를 가지며, 상기 키틴을 강알칼리로 처리하여 탈아세틸화(deacetylation)시키면 아세틸기가 아민기로 바뀐 키토산을 얻을 수 있다.In general, chitin is N-acetylglucopyranose, in which N-acetyl group (-N-acetyl) is bonded instead of hydroxyl group (-OH) of glucopyranose No. 2 carbon, which is a basic monosaccharide of cellulose. (N-acetylglucopyranose) has a β-1,4 bonded structure continuously, and deacetylation by treating the chitin with strong alkali can yield chitosan whose acetyl group is changed to an amine group.

상기 키토산은 고분자 물질이므로 수불용성을 나타내며, 따라서 그 용도가 극히 제한적일 수밖에 없다는 단점이 있다. 따라서 키토산이 가지는 물성을 그대로 확보함과 동시에 수용성을 갖는 키토산 유도체에 관한 많은 기술이 공지되어 있다.Since the chitosan is a high molecular material, it exhibits water insolubility, and thus has a disadvantage in that its use is extremely limited. Therefore, many technologies are known regarding chitosan derivatives having water solubility as well as securing physical properties of chitosan.

상기 수용성 키토산의 경우 키토산이 가지는 여러 물성을 보완함과 동시에 넓은 pH 범위(pH3 내지 pH10)에서 사용될 수 있으며, 특히 흡착성, 지속성, 보습성, 피막형성능력 및 증점성이 우수하여 샴푸 샴푸, 린스, 트리트먼트, 헤어셋 로션 등의 두발용 화장품을 비롯하여 크림, 유액 팩, 파운데이션, 비누, 치약 등의 수성 첨가제로 널리 사용되고 있다. 또한, 항균성이 우수하여 입안 세균에 의한 치아의 플라그 생성과 충치를 예방해 주는 치석제거제로도 사용되고 있다.The water-soluble chitosan can be used in a wide pH range (pH3 to pH10) at the same time as complementing the various physical properties of chitosan, in particular, sorbent shampoo, rinse, It is widely used as an aqueous additive such as creams, latex packs, foundations, soaps, toothpastes, as well as hair cosmetics such as treatments and hairset lotions. In addition, it is also used as a tartar remover to prevent plaque formation and tooth decay of teeth by bacteria in the mouth due to excellent antibacterial properties.

상기와 같이 다양한 용도로 사용되는 키토산 유도체의 일반식을 하기 화학식 1에 나타내었다.The general formula of the chitosan derivative used for various purposes as described above is shown in the following formula (1).

상기 화학식 1에서 n은 1이상의 정수를 나타내며, R1은 H, OH, COOH 또는 CH2COOH기 이며, R2는 H, COCH3, CH2COOH, CHOHCH2CH3또는 CH2CHOHCH2CH2CH3기이다.In Formula 1 n represents an integer of 1 or more, R 1 is H, OH, COOH or CH 2 COOH group, R 2 is H, COCH 3 , CH 2 COOH, CHOHCH 2 CH 3 or CH 2 CHOHCH 2 CH 2 CH 3 group.

이중에서도 널리 사용되는 키토산 유도체로는 상기 화학식 1에서 R1과 R2가 모두 CH2COOH기인 하기 화학식 2의 N,O-카르복시메틸 키토산(N,O-carboxymethyl chitosan; 이하 NOCC라 함)과; R1이 OH 이고 R2가 CHOHCH2CH3인 하기 화학식 3의 N-하이드로프로필 키토산(N-hydropropryl chitosan; 이하 NHPC라 함); 및 R1이 OH 이고 R2가 CH2CHOHCH2CH2CH3인 하기 화학식 4의 N-하이드로부틸 키토산(N-hydrobutylchitosan; 이하 NHBC라 함)이 있다.Among them, chitosan derivatives widely used include N, O-carboxymethyl chitosan (N, O-carboxymethyl chitosan; hereinafter referred to as NOCC) of Formula 2, wherein R 1 and R 2 are both CH 2 COOH groups in Formula 1; N-hydropropyl chitosan (N-hydropropryl chitosan; hereafter referred to as NHPC) in which R 1 is OH and R 2 is CHOHCH 2 CH 3 ; And N-hydrobutylchitosan (hereinafter referred to as NHBC) of Formula 4 wherein R 1 is OH and R 2 is CH 2 CHOHCH 2 CH 2 CH 3 .

상기 화학식 2에서 n은 1이상의 정수를 나타낸다.In Formula 2, n represents an integer of 1 or more.

상기 화학식 3에서 n은 1이상의 정수를 나타낸다.In Formula 3, n represents an integer of 1 or more.

상기 화학식 4에서 n은 1이상의 정수를 나타낸다.In Formula 4, n represents an integer of 1 or more.

특히 상기 NOCC, NHPC 및 NHBC는 모두 수용성을 가지고 있으며, 특성 또한 유사한 것으로 알려져 있다. 또한 그 제조방법도 유사하며, 제조방법상의 차이점은 각각 R1과 R2에 붙어 있는 작용기가 상이하므로 반응물질에 차이점이 있다.In particular, the NOCC, NHPC and NHBC are all water-soluble, it is known that the properties are similar. In addition, the manufacturing method is similar, and the difference in the manufacturing method is different in the reactants because the functional groups attached to R1 and R2 respectively.

상기 수용성 키토산 유도체의 제조방법을 NOCC의 제조방법을 통해 보다 상세하게 설명하면 다음과 같다.The production method of the water-soluble chitosan derivative will be described in more detail through the production method of NOCC.

키토산에 NaOH 수용액을 첨가 교반하여 출발 반응용액을 제조한 다음, 이 반응물을 90℃로 가열하고 모노클로로아세트산나트륨을 가하고 교반한 후, 여기에 NaOH 수용액을 첨가하여 pH 10 내지 10.5로 유지시킨 후 반응물을 24시간 동안 90℃에서 교반하고, 이를 상온으로 냉각시킨 다음 아세트산 수용액을 사용하여 pH를 8.5로 중화시키고, 중화된 반응물을 증류수에 대해 투석하고 동결 건조시키면 NOCC를 얻을 수 있다.NaOH aqueous solution was added to the chitosan, followed by stirring to prepare a starting reaction solution. The reaction was heated to 90 ° C., sodium monochloroacetate was added and stirred, and then the aqueous NaOH solution was added thereto and maintained at pH 10 to 10.5. The solution was stirred at 90 ° C. for 24 hours, cooled to room temperature, neutralized to pH 8.5 using aqueous acetic acid solution, and the neutralized reaction was dialyzed against distilled water and lyophilized to obtain NOCC.

그러나 상기한 방법으로 키토산 유도체를 제조할 경우 키토산이 NaOH 수용액에서 팽윤이 제대로 이루어지지 않아 미반응 출발물질(키토산)이 많이 남아 수득율이 현저하게 낮고, 또한 키토산 유도체가 겔상태로 얻어지는 단점이 있다.However, when the chitosan derivative is prepared by the above-described method, the chitosan does not swell properly in an aqueous NaOH solution, so that many unreacted starting materials (chitosan) remain, so that the yield is remarkably low, and the chitosan derivative is obtained in a gel state.

따라서 본 발명자는 상기한 방법을 개선하여 높은 수율로 키토산 유도체를 얻을 수 있는 키토산 유도체의 제조방법을 연구한 끝에 본 발명을 완성하기에 이르렀다.Therefore, the present inventors have completed the present invention after studying the preparation method of the chitosan derivative which can obtain the chitosan derivative with high yield by improving the above-described method.

이에 본 발명은 종래 키토산 유도체의 제조방법을 개선하여 보다 높은 수율로 키토산 유도체를 제조할 수 있도록 한 키토산 유도체의 제조방법을 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a method for preparing a chitosan derivative, which is capable of producing a chitosan derivative with a higher yield by improving a conventional method for producing a chitosan derivative.

상기한 목적을 달성하기 위하여 본 발명은 키토산에 NaOH 수용액을 첨가하여 pH10 이상인 출발 반응용액을 제조한 다음, 이 반응물을 90℃로 가열하고 여기에반응물질을 가하고 교반하여 반응시킨 다음, 이를 상온으로 냉각시켜 여과하고 유기용매로 세척하여 건조시키는 키토산 유도체의 제조방법에 있어서,In order to achieve the above object, the present invention prepares a starting reaction solution having a pH of 10 or more by adding NaOH aqueous solution to chitosan, and then heating the reactant at 90 ° C., adding a reactant thereto, and stirring and reacting the same to room temperature. In the manufacturing method of the chitosan derivative which is cooled, filtered, washed with an organic solvent and dried,

상기 출발 반응용액이 키토산을 유기산 또는 무기산과 혼합하여 교반하면서 pH3 내지 4로 조절한 다음, 여기에 이소프로판올(isopropanol)을 키토산 100중량부에 대하여 1500중량부 내지 2500중량부 천천히 첨가(dropping)하고 NaOH 수용액을 첨가하여 pH10 이상으로 하여 제조됨을 특징으로 하는 키토산 유도체의 제조방법을 제공함으로서 달성할 수 있다.The starting reaction solution was adjusted to pH 3 to 4 by mixing chitosan with an organic acid or an inorganic acid while stirring, and then isopropanol was slowly added to 1500 parts by weight to 2500 parts by weight based on 100 parts by weight of chitosan, followed by NaOH. It can achieve by providing the manufacturing method of the chitosan derivative characterized by manufacturing by adding aqueous solution to pH10 or more.

이하 본 발명을 보다 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail.

본 발명에서는 키토산 유도체를 제조하기 위하여 키토산을 유기산 또는 무기산과 혼합하여 교반하면서 pH3 내지 4로 조절한 다음, 여기에 이소프로판올을 키토산 100중량부에 대하여 1500중량부 내지 2500중량부 천천히 첨가(dropping)하고 NaOH 수용액을 첨가하여 pH10 이상인 출발 반응액을 제조한 다음, 이 반응액을 90℃로 가열하고 여기에 반응물질을 가하고 교반하여 반응시킨 다음 이를 상온으로 냉각시켜 여과하고 유기용매로 세척하여 건조시켜 제조하게 된다.In the present invention, in order to prepare a chitosan derivative, the chitosan is mixed with an organic acid or an inorganic acid and adjusted to pH 3 to 4 while stirring, and then isopropanol is slowly added to 1500 to 2500 parts by weight based on 100 parts by weight of chitosan. NaOH aqueous solution was added to prepare a starting reaction solution having a pH of 10 or more.Then, the reaction solution was heated to 90 ° C, reacted with stirring and reacted, cooled to room temperature, filtered, washed with an organic solvent and dried. Done.

먼저 키토산을 유기산 또는 무기산과 혼합하여 교반하면서 pH3 내지 4로 조절하게 되는데, 이는 상기 키토산이 유기산 또는 무기산에 잘 용해되기 때문에 이와 같은 조작을 통하여 일단 키토산을 겔상태로 용해시키게 된다.First, the chitosan is mixed with an organic acid or an inorganic acid and adjusted to pH 3 to 4 while stirring. Since the chitosan is well dissolved in an organic acid or an inorganic acid, the chitosan is dissolved in a gel state through such an operation.

이때 상기 유기산으로 사용 가능한 산에는 포름산(formic acid), 락틱산(lactic acid) 또는 아세트산(acetic acid) 등이 있으며, 무기산으로 사용 가능한 것에는 염산(HCl)이 있다.The acid usable as the organic acid may include formic acid, lactic acid or acetic acid, and the like may be hydrochloric acid (HCl).

상기와 같은 유기산 또는 무기산을 사용할 경우 pH3 내지 4로 조절하게 되는데 이는 키토산의 용해를 고려한 것으로 특히 유기산일 경우에는 pH가 3미만일 경우에도 키토산이 잘 용해되지만 무기산의 경우에는 pH 3미만일 경우 키토산이 다시 결정상태로 되기 때문에 pH를 상기 범위 내로 조절하는 것이 바람직하다.When using the organic or inorganic acid as described above is adjusted to pH 3 to 4, which takes into account the dissolution of chitosan, especially in the case of organic acid chitosan is well dissolved even if the pH is less than 3, but in the case of inorganic acid is less than pH 3 chitosan again It is preferable to adjust pH within the said range because it will become a crystalline state.

본 발명에서는 상기 키토산을 용해시키기 위해 95% 아세트산을 첨가하여 pH를 3 내지 4로 조절한 다음 교반하여 겔상태를 갖도록 하였다.In the present invention, to dissolve the chitosan was added to 95% acetic acid to adjust the pH to 3 to 4 and then stirred to have a gel state.

상기와 같이 키토산에 아세트산을 첨가한 다음, 여기에 이소프로판올을 키토산 100중량부에 대하여 1500중량부 내지 2500중량부 천천히 첨가(dropping)하고 NaOH 수용액을 첨가하여 pH10 이상인 출발 반응액을 제조하게 된다.After adding acetic acid to chitosan as described above, isopropanol is slowly added to 1500 parts by weight to 2500 parts by weight based on 100 parts by weight of chitosan, and an aqueous NaOH solution is added to prepare a starting reaction solution having a pH of 10 or more.

이때 이소프로판올은 키토산이 산에 의해 팽윤시 교반을 원활하게 함과 동시에 팽윤을 보조하는 역할을 하는 것으로 그 첨가량이 키토산 100중량부에 대하여 1500중량부 미만으로 첨가될 경우 키토산이 충분히 팽윤되지 않아 교반이 용이하지 않은 문제점이 발생하게 되고, 그 첨가량이 2500중량부를 초과할 필요는 없으나 그 첨가량이 2500중량부를 초과할 경우 오히려 반응시간을 지연시키고 제조단가를 상승시키는 문제점이 있으므로 상기 범위내에서 이소프로판올을 첨가하는 것이 바람직하다. 이때 이소프로판올을 천천히 첨가하게 되면 겔상태의 키토산이 약간 풀어진 고체상태를 나타낸다.At this time, isopropanol facilitates agitation when chitosan swells with acid and assists swelling. If the amount is less than 1500 parts by weight based on 100 parts by weight of chitosan, the chitosan is not sufficiently swollen. It is not easy to cause problems, and the addition amount does not need to exceed 2500 parts by weight, but when the addition amount exceeds 2500 parts by weight, there is a problem of delaying the reaction time and increasing the manufacturing cost, thus adding isopropanol within the above range. It is desirable to. At this time, when isopropanol is slowly added, the gel chitosan is slightly released.

이와 같이 이소프로판올을 첨가한 후 NaOH 수용액을 사용하여 용액내의 pH를 10이상이 되도록 하여 출발 반응액을 제조하게 된다. 본 발명에서는 40% NaOH 수용액을 사용하였으며, 상기 NaOH 수용액을 첨가하게 되면 젤 상태가 풀어진 고체상태로 교반이 이루어지게 된다. 이때 NaOH 수용액은 천천히 첨가하여야 고체가 엉키지 않고 교반이 이루어질 수 있으므로 주의한다.In this way, after adding isopropanol, a starting reaction solution is prepared by using a NaOH aqueous solution to bring the pH in the solution to 10 or more. In the present invention, 40% NaOH aqueous solution was used, and when the NaOH aqueous solution was added, stirring was performed in a solid state in which the gel was released. At this time, the NaOH aqueous solution should be added slowly so that the solid may not be tangled and stirring may be performed.

상기와 같이 출발 반응액을 제조한 다음, 통상의 방법을 통하여 상기 반응액을 90℃로 가열하고 여기에 반응물질을 가하고 교반하여 반응시킨 다음 이를 상온으로 냉각시켜 여과하고 유기용매로 세척하여 건조시키면 본 발명에 의한 키토산 유도체를 높은 수율을 얻을 수 있게 된다. 이때 상기 반응시간이 5시간 미만일 경우 충분한 반응이 일어나지 않아 수율이 저하되는 단점이 있으므로 5시간 이상 반응시키는 것이 좋다.After the starting reaction solution is prepared as described above, the reaction solution is heated to 90 ° C. through a conventional method, and reacted by adding the reactant thereto, stirring the mixture, cooling it to room temperature, filtering it, washing with an organic solvent, and drying it. It is possible to obtain a high yield of the chitosan derivative according to the present invention. In this case, if the reaction time is less than 5 hours, there is a disadvantage in that the yield is lowered because a sufficient reaction does not occur.

이때 상기 유기용매로는 아세톤, 에탄올 또는 에틸아세테이트 등과 같은 유기용매를 사용할 수 있으며, 본 발명에서는 메탄올을 이용하여 세척하였다.In this case, an organic solvent such as acetone, ethanol or ethyl acetate may be used as the organic solvent. In the present invention, the organic solvent was washed with methanol.

상기와 같이 본 발명에서는 키토산을 이용하여 키토산 유도체를 제조하는 과정에서 종래 알칼리 수용액에 키토산을 팽윤시킨 다음 반응을 진행한 것과는 달리 키토산을 유기산 또는 무기산에 용해시켜 이를 다시 알칼리 수용액으로 팽윤시킨 것이 특징이다. 이와 같이 키토산이 충분히 팽윤될 수 있도록 함으로서 미반응 출발물질이 적어 최종 제조된 키토산 유도체가 높은 수율로 얻어질 수 있는 것이다.As described above, the present invention is characterized in that, in the process of preparing a chitosan derivative using chitosan, the chitosan is swelled in an aqueous alkali solution and then reacted with the chitosan. . By allowing chitosan to be sufficiently swollen as described above, there is less unreacted starting material, and thus the final manufactured chitosan derivative can be obtained in high yield.

상기에서 최종적으로 원하는 키토산 유도체를 얻기 위해서는 반응물질을 변화시키면 되는데, 일예로 반응물질로 모노클로로아세트산을 첨가할 경우 NOCC를 제조할 수 있으며, 프로필렌 옥사이드를 첨가할 경우 NHPC를, 부틸렌 옥사이드를 제조할 경우 NHBC를 제조할 수 있게 된다.In order to finally obtain the desired chitosan derivative, the reactant may be changed. For example, when monochloroacetic acid is added as a reactant, NOCC may be prepared, and NHPC and butylene oxide may be prepared when propylene oxide is added. In this case, NHBC can be produced.

이때 상기 반응물질의 첨가량은 통상적으로 첨가되는 범위 내에서 첨가될 수있으며, 본 발명에서는 NOCC를 제조하기 위해 키토산 100중량부에 대하여 200중량부 내지 300중량부의 모토클로로아세트산을 첨가하였으며, NHPC를 제조하기 위해 키토산 100중량부에 대하여 80중량부 내지 150중량부의 프로필렌 옥사이드를 첨가하였으며, NHBC를 제조하기 위해 키토산 100중량부에 대하여 120중량부 내지 180중량부의 부틸렌 옥사이드를 첨가하였다.In this case, the amount of the reactant may be added within a range generally added. In the present invention, 200 parts by weight to 300 parts by weight of motochloroacetic acid was added to 100 parts by weight of chitosan to prepare NOCC, and NHPC was prepared. 80 parts by weight to 150 parts by weight of propylene oxide was added to 100 parts by weight of chitosan, and 120 parts by weight to 180 parts by weight of butylene oxide was added to 100 parts by weight of chitosan to prepare NHBC.

이하 본 발명을 하기한 실시예를 통하여 보다 상세하게 설명하기로 하나 이는 본 발명의 이해를 돕기 위하여 제시된 것일 뿐 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, which are presented to aid the understanding of the present invention, but the present invention is not limited thereto.

<실시예 1 내지 5><Examples 1 to 5>

키토산 10g에 95% 아세트산을 첨가하여 pH를 3으로 조절한 다음, 여기에 이소프로판올을 하기 표 1에 나타낸 량만큼 천천히 첨가(dropping)한 후 40% NaOH 수용액을 첨가하여 pH10이 되도록 하여 키토산을 팽윤시켰다. 상기 팽윤시킨 반응물을 90℃로 가열하고 여기에 반응물질로 모노클로로아세트산 25g을 가하고 7시간 동안 교반한 다음 이를 상온으로 냉각시켜 여과하고 메탄올로 세척하여 건조시켜 NOCC를 제조하였다. 이때 그 수득율을 하기 표 1에 함께 나타내었다.The pH was adjusted to 3 by adding 95% acetic acid to 10 g of chitosan, and then isopropanol was slowly added to the amount shown in Table 1, followed by 40% aqueous NaOH solution to bring the pH to 10 to swell the chitosan. . The swollen reactant was heated to 90 ° C., 25 g of monochloroacetic acid was added thereto as a reactant, stirred for 7 hours, cooled to room temperature, filtered, washed with methanol, and dried to prepare NOCC. The yield is shown together in Table 1 below.

<실시예 6 내지 13><Examples 6 to 13>

키토산 10g에 95% 아세트산을 첨가하여 pH를 3으로 조절한 다음, 여기에 이소프로판올 180g을 천천히 첨가(dropping)한 후 40% NaOH 수용액을 첨가하여 pH10이 되도록 하여 키토산을 팽윤시켰다. 상기 팽윤시킨 반응물을 90℃로 가열하고 여기에 반응물질로 모노클로로아세트산을 하기 표 1에 나타낸 량만큼 가하고 반응시간을 하기 표 1과 같이 변화시키면서 교반한 다음 이를 상온으로 냉각시켜 여과하고 메탄올로 세척하여 건조시켜 NOCC를 제조하였다. 이때 그 수득율을 하기 표 1에 함께 나타내었다.The pH was adjusted to 3 by adding 95% acetic acid to 10 g of chitosan, and 180 g of isopropanol was slowly added thereto, followed by 40% aqueous NaOH solution to make pH 10, thereby swelling the chitosan. The swelled reactant was heated to 90 ° C. and monochloroacetic acid was added thereto as a reactant, and the reaction time was changed while changing the reaction time as shown in Table 1, which was then cooled to room temperature, filtered and washed with methanol. Dry to prepare NOCC. The yield is shown together in Table 1 below.

<실시예 14 내지 21><Examples 14 to 21>

키토산 10g에 95% 아세트산을 첨가하여 pH를 3으로 조절한 다음, 여기에 이소프로판올 180g을 천천히 첨가(dropping)한 후 40% NaOH 수용액을 첨가하여 pH10이 되도록 하여 키토산을 팽윤시켰다. 상기 팽윤시킨 반응물을 90℃로 가열하고 여기에 반응물질로 프로필렌 옥사이드를 하기 표 1에 나타낸 량만큼 가하고 반응시간을 하기 표 1과 같이 변화시키면서 교반한 다음 이를 상온으로 냉각시켜 여과하고 메탄올로 세척하여 건조시켜 NHPC를 제조하였다. 이때 그 수득율을 하기 표 1에 함께 나타내었다.The pH was adjusted to 3 by adding 95% acetic acid to 10 g of chitosan, and 180 g of isopropanol was slowly added thereto, followed by 40% aqueous NaOH solution to make pH 10, thereby swelling the chitosan. The swelled reactant was heated to 90 ° C., and propylene oxide was added thereto as the reactant, and the reaction time was changed while changing the reaction time as shown in Table 1, which was then cooled to room temperature, filtered, and washed with methanol. Drying made NHPC. The yield is shown together in Table 1 below.

<실시예 22 내지 29><Examples 22 to 29>

키토산 10g에 95% 아세트산을 첨가하여 pH를 3으로 조절한 다음, 여기에 이소프로판올 180g을 천천히 첨가(dropping)한 후 40% NaOH 수용액을 첨가하여 pH10이 되도록 하여 키토산을 팽윤시켰다. 상기 팽윤시킨 반응물을 90℃로 가열하고 여기에 반응물질로 부틸렌 옥사이드를 하기 표 1에 나타낸 량만큼 가하고 반응시간을 하기 표 1과 같이 변화시키면서 교반한 다음 이를 상온으로 냉각시켜 여과하고 메탄올로 세척하여 건조시켜 NHBC를 제조하였다. 이때 그 수득율을 하기 표 1에 함께 나타내었다.The pH was adjusted to 3 by adding 95% acetic acid to 10 g of chitosan, and 180 g of isopropanol was slowly added thereto, followed by 40% aqueous NaOH solution to make pH 10, thereby swelling the chitosan. The swelled reactant was heated to 90 ° C., and butylene oxide was added thereto as the reactant, and the reaction time was changed while changing the reaction time as shown in Table 1, which was then cooled to room temperature, filtered and washed with methanol. And dried to prepare NHBC. The yield is shown together in Table 1 below.

<비교예 1>Comparative Example 1

25g의 키토산을 200g의 5중량%수성 NaOH중에 슬러리화하고 이 슬러리를 1시간 동안 교반한다음, 이 반응물을 90℃로 가열하고 58.2g의 나트륨 클로로 아세테이트를 고체로서 4분획으로 10분 간격으로 가하고, 이 반응액의 pH를 4중량 %의 수성 NaOH을 첨가하여 10내지 10.5로 유지시킨 후 반응물을 24시간 동안 90℃에서 교반하였다. 이 반응 혼합물을 25℃로 냉각시키고 50중량 %아세트산 수용액을 사용하여 pH를 8.5로 중화시킨 다음, 이를 증류수에 대해 투석하고 동결 건조시켜 NOCC 키토산 유도체를 11.9g (36%)을 수득하였다.25 g of chitosan was slurried in 200 g of 5% by weight aqueous NaOH and the slurry was stirred for 1 hour, then the reaction was heated to 90 ° C. and 58.2 g of sodium chloro acetate as a solid were added in 4 portions at 10 minute intervals. The pH of the reaction solution was maintained at 10 to 10.5 by adding 4% by weight of aqueous NaOH, and the reaction was stirred at 90 ° C. for 24 hours. The reaction mixture was cooled to 25 ° C. and neutralized to a pH of 8.5 using a 50 wt% aqueous acetic acid solution, then dialyzed against distilled water and lyophilized to give 11.9 g (36%) of the NOCC chitosan derivative.

구분division 이소프로판올Isopropanol 모노클로로아세트산Monochloroacetic acid 프로필렌 옥사이드Propylene oxide 부틸렌 옥사이드Butylene oxide 반응시간Reaction time 수율(%)yield(%) 실시예 1Example 1 100100 2525 -- -- 77 9090 실시예 2Example 2 150150 2525 -- -- 77 9494 실시예 3Example 3 200200 2525 -- -- 77 9494 실시예 4Example 4 250250 2525 -- -- 77 9595 실시예 5Example 5 300300 2525 -- -- 77 8484 실시예 6Example 6 180180 1515 -- -- 55 8585 실시예 7Example 7 180180 2020 -- -- 55 9595 실시예 8Example 8 180180 2525 -- -- 55 9797 실시예 9Example 9 180180 3030 -- -- 55 9797 실시예 10Example 10 180180 2525 -- -- 33 8787 실시예 11Example 11 180180 2525 -- -- 55 9595 실시예 12Example 12 180180 2525 -- -- 77 9797 실시예 13Example 13 180180 2525 -- -- 99 92.492.4 실시예 14Example 14 180180 -- 66 -- 55 8282 실시예 15Example 15 180180 -- 1010 -- 55 9696 실시예 16Example 16 180180 -- 1515 -- 55 9696 실시예 17Example 17 180180 -- 2020 -- 55 9393 실시예 18Example 18 180180 -- 1010 -- 33 8585 실시예 19Example 19 180180 -- 1010 -- 55 9696 실시예 20Example 20 180180 -- 1010 -- 77 9797 실시예 21Example 21 180180 -- 1010 -- 99 94.494.4 실시예 22Example 22 180180 -- -- 77 77 8383 실시예 23Example 23 180180 -- -- 1010 77 9090 실시예 24Example 24 180180 -- -- 1515 77 9696 실시예 25Example 25 180180 -- -- 2020 77 9595 실시예 26Example 26 180180 -- -- 1010 33 8585 실시예 27Example 27 180180 -- -- 1010 55 9292 실시예 28Example 28 180180 -- -- 1010 77 9797 실시예 29Example 29 180180 -- -- 1010 99 95.495.4 비교예 1Comparative Example 1 -- -- -- -- -- 3636

상기 표 1에서 보는 바와 같이 이소프로판올의 첨가량을 변화시키면서 실시한 실시예 1 내지 5에 있어서, 그 첨가량에 관계 없이 모두 수율이 높은 것을 알 수 있으나, 실험실 실시예 1의 경우 교반이 안되는 문제점이 있었으며, 실시예 5의 경우 그 첨가량이 많아 반응속도가 지연되어 동일시간 하에서는 수율이 저하되는 것을 알 수 있으나 반응시간을 높여줄 경우 높은 수율로 얻을 수 있다.As shown in Table 1, in Examples 1 to 5 carried out while changing the addition amount of isopropanol, it can be seen that the yield is high regardless of the addition amount, but in the case of laboratory Example 1 there was a problem that can not be stirred, In the case of Example 5, the addition rate is large, the reaction rate is delayed, it can be seen that the yield is lowered under the same time, but when the reaction time is increased, a high yield can be obtained.

또 반응물질을 모노클로로 아세트산, 프로필렌 옥사이드 및 부틸렌 옥사이드로 바꾸면서 그 첨가량을 변화시키면서 실시한 실시예 6 내지 29에 있어서, 본 발명의 바람직한 첨가예의 경우 수율이 높으며, 특히 반응시간이 5시간 이상일 경우 수율이 매우 높음을 알 수 있다.In addition, in Examples 6 to 29 carried out while changing the amount of the reactants while changing the reaction material to monochloro acetic acid, propylene oxide and butylene oxide, the yield is high in the case of the preferred addition example of the present invention, especially when the reaction time is 5 hours or more You can see this is very high.

특히, 본 발명에 의한 HIEC 제조방법의 경우 수율이 90%이상으로 종래의 NOCC제조방법에 비하여 매우 높게 나타남을 알 수 있다.In particular, the HIEC manufacturing method according to the present invention can be seen that the yield is very high compared to the conventional NOCC manufacturing method of 90% or more.

상기 실시예 8에서 제조한 키토산 유도체(NOCC), 상기 실시예 16에서 제조한 키토산 유도체(NHPC) 및 상기 실시예 24에서 제조한 키토산 유도체(NHBC)의 IR(KBr) 및13C NMR(D2O) 데이터를 하기 표 2에 나타내었으며, 상기 표 2에서 보는 바와 같이 각각의 구조물을 확인할 수 있다.IR (KBr) and 13 C NMR (D 2 ) of the chitosan derivative (NOCC) prepared in Example 8, the chitosan derivative (NHPC) prepared in Example 16, and the chitosan derivative (NHBC) prepared in Example 24 O) The data is shown in Table 2 below, and each structure can be identified as shown in Table 2 above.

구분division IRIR NMRNMR 실시예 8Example 8 1635cm-1ν(C=O)1530cm-1ν(N-H)1635 cm-1ν (C = O) 1530 cm-1ν (N-H) δ176.4(COOH), δ174.9(C=O), δ101.8(C-1-NCM)δ98.2(C-1) δ77.6(C-4), δ75.4(C-5)δ71.9(C-3) δ61.2(C-6) δ56.3(C-2)δ 176.4 (COOH), δ 174.9 (C = O), δ 101.8 (C-1-NCM) δ 98.2 (C-1) δ 77.6 (C-4), δ 75.4 (C-5 ) δ71.9 (C-3) δ61.2 (C-6) δ56.3 (C-2) 실시예 16Example 16 -- δ98.2(C-1), δ76.4(C-4), δ74.3(C-5)δ73.9(C-3), δ59.2(C-6), δ54.3(C-2)δ50.2(C-C-OH)δ98.2 (C-1), δ76.4 (C-4), δ74.3 (C-5) δ73.9 (C-3), δ59.2 (C-6), δ54.3 (C- 2) δ 50.2 (CC-OH) 실시예 24Example 24 -- δ98.7(C-1), δ78.4(C-4), δ73.4(C-5)δ68.9(C-3), δ61.2(C-6), δ56.5(C-2)δ51.2(C-C-OH) δ20.6(CH3)δ98.7 (C-1), δ78.4 (C-4), δ73.4 (C-5) δ68.9 (C-3), δ61.2 (C-6), δ56.5 (C- 2) δ 51.2 (CC-OH) δ 20.6 (CH 3 )

상기에서 설명한 바와 같이 본 발명은 종래 키토산 유도체의 제조방법을 개선하여 보다 높은 수율로 키토산 유도체를 제조할 수 있도록 한 키토산 유도체의 제조방법을 제공하는 유용한 발명이다.As described above, the present invention is a useful invention that provides a method for preparing a chitosan derivative, which is capable of producing a chitosan derivative in a higher yield by improving a conventional method for producing a chitosan derivative.

Claims (5)

키토산에 NaOH 수용액을 첨가하여 pH10 이상인 출발 반응용액을 제조한 다음, 이 반응물을 90℃로 가열하고 여기에 반응물질을 가하고 교반하여 반응시킨 다음 이를 상온으로 냉각시켜 여과하고 메탄올로 세척하여 건조시키는 키토산 유도체의 제조방법에 있어서,NaOH aqueous solution was added to the chitosan to prepare a starting reaction solution having a pH of 10 or more, and the reactant was heated to 90 ° C., and the reactant was added thereto, stirred and reacted. The mixture was cooled to room temperature, filtered, washed with methanol, and dried. In the preparation method of the derivative, 상기 출발 반응용액이 키토산을 유기산과 혼합하여 교반하면서 pH3 내지 4로 조절한 다음, 여기에 이소프로판올을 키토산 100중량부에 대하여 1500중량부 내지 2500중량부 천천히 첨가(dropping)하고 NaOH 수용액을 첨가하여 pH10 이상으로 하여 제조됨을 특징으로 하는 키토산 유도체의 제조방법.The starting reaction solution was adjusted to pH 3 to 4 by mixing chitosan with an organic acid while stirring, and then slowly adding isopropanol to 1500 parts by weight to 2500 parts by weight based on 100 parts by weight of chitosan, and then adding an aqueous NaOH solution to pH10. Method for producing a chitosan derivative, characterized in that prepared as above. 청구항 1에 있어서, 유기산으로 95% 아세트산을 사용함을 특징으로 하는 키토산 유도체의 제조방법.The method for producing a chitosan derivative according to claim 1, wherein 95% acetic acid is used as the organic acid. 청구항 1 또는 청구항 2에 있어서, 상기 반응물질로 키토산 100중량부에 대하여 200중량부 내지 300중량부의 모토클로로아세트산을 첨가하여 N,O-카르복시메틸 키토산(N,O-carboxymethyl chitosan)을 제조함을 특징으로 하는 키토산 유도체의 제조방법.The N, O-carboxymethyl chitosan is prepared by adding 200 to 300 parts by weight of motochloroacetic acid with respect to 100 parts by weight of chitosan. Method for producing chitosan derivatives 청구항 1 또는 청구항 2에 있어서, 상기 반응물질로 키토산 100중량부에 대하여 80중량부 내지 150중량부의 프로필렌 옥사이드를 첨가하여 N-하이드로프로필 키토산(N-hydropropryl chitosan)을 제조함을 특징으로 하는 키토산 유도체의 제조방법.The chitosan derivative according to claim 1 or 2, wherein N-hydropropryl chitosan is prepared by adding 80 parts by weight to 150 parts by weight of propylene oxide based on 100 parts by weight of chitosan as the reactant. Manufacturing method. 청구항 1 또는 청구항 2에 있어서, 상기 반응물질로 키토산 100중량부에 대하여 120중량부 내지 180중량부의 부틸렌 옥사이드를 첨가하여 N-하이드로부틸 키토산(N-hydrobutyl chitosan)을 제조함을 특징으로 하는 키토산 유도체의 제조방법.The chitosan according to claim 1 or 2, wherein 120 parts by weight to 180 parts by weight of butylene oxide is added to 100 parts by weight of chitosan as the reactant to prepare N-hydrobutyl chitosan. Process for the preparation of derivatives.
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