KR100225789B1 - Fluorescent dye intermediate using chitosan oligomer and method for preparing thereof - Google Patents

Fluorescent dye intermediate using chitosan oligomer and method for preparing thereof Download PDF

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KR100225789B1
KR100225789B1 KR1019970038378A KR19970038378A KR100225789B1 KR 100225789 B1 KR100225789 B1 KR 100225789B1 KR 1019970038378 A KR1019970038378 A KR 1019970038378A KR 19970038378 A KR19970038378 A KR 19970038378A KR 100225789 B1 KR100225789 B1 KR 100225789B1
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chitosan
oligomer
chitosan oligomer
dye intermediate
fluorescent dye
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KR19990015967A (en
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김종석
안종일
임완빈
박찬구
최하영
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주덕영
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0017—Influencing the physical properties by treatment with an acid, H2SO4

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Abstract

본 발명은 키토산(Chitosan) 올리고머를 이용한 형광염료 중간체 및 그 제조방법에 관한 것으로, 키토산 폴리머를 과산화수소 1-5% 용액에 넣고 pH를 10.5 내지 12.5로 유지하면서 50 내지 100℃에서 반응시켜서 키토산 올리고머를 만든 후, 시아누릭 클로라이드(cyanuric chloride)를 가하여 0 내지 10℃, pH 7내지 9의 조건을 반응시켜 키토산 올리고머 -시아누릭 클로라이드 결합체(CO-CY)를 형성시키고, 이 결합체에 4,4'-디아미노스틸벤-2,2'-디설포닉 산(DAS)을 가하고 반응시켜 키토산 올리고머-시아누릭 클로라이드-4,4'-디아미노스틸벤-2,2'-디설포닉 산(CO-CY-DAS) 결합체를 형성시키는 것을 특징으로 하며, 본 발명에 의하여 키토산 폴리머로부터 항균성 및 방취성이 우수한 펜타머 또는 헥사머의 함량이 높은 올리고머를 얻어서 염료 중간체에 결합시킬 수 있다.The present invention relates to a fluorescent dye intermediate using a chitosan oligomer and a method for preparing the same. The chitosan oligomer is prepared by reacting a chitosan polymer in a 1-5% hydrogen peroxide solution at 50 to 100 ° C. while maintaining a pH of 10.5 to 12.5. After the preparation, cyanuric chloride is added to react the conditions at 0 to 10 ° C. and pH 7 to 9 to form a chitosan oligomer-cyanuric chloride conjugate (CO-CY), which forms 4,4′-. Chitosan oligomer-cyanuric chloride-4,4'-diaminostilben-2,2'-disulfonic acid (CO-CY- It is characterized in that to form a DAS) conjugate, by the present invention can be obtained from chitosan polymer to obtain an oligomer having a high content of pentamers or hexamers excellent in antibacterial and deodorizing properties can be bonded to the dye intermediate.

Description

키토산 올리고머를 이용한 형광염료 중간체 및 그 제조방법Fluorescent dye intermediate using chitosan oligomer and preparation method thereof

본 발명은 키토산(Chitosan) 올리고머를 이용한 형광염료 중간체 및 그 제조방법에 관한 것이다.The present invention relates to a fluorescent dye intermediate using a chitosan oligomer and a method for producing the same.

천연물인 게껍질로부터 얻어 낸 키토산 올리고머를 가수분해하여 얻은 올리고머 중 펜타머(pentamer), 헥사머(hexamer)는 항균성 및 항암성이 뛰어 난 물질로 밝혀 졌으며(Suzuki K, Mikami T, Okawa Y, Tokoro A, Suzuki S and Suzuki M. Carbohydr Res 1986; 151: 403), 현재 이를 이용한 여러 종류의 항생제, 항균제, 항암제의 실용화에 관한 연구가 세계적으로 활발하게 이루어 지고 있다.Among the oligomers obtained by hydrolyzing chitosan oligomers obtained from natural crab shells, pentamers and hexamers were found to have excellent antibacterial and anticancer properties (Suzuki K, Mikami T, Okawa Y, Tokoro). A, Suzuki S and Suzuki M. Carbohydr Res 1986; 151: 403). Currently, researches on the practical use of various antibiotics, antibacterial agents and anticancer agents have been actively conducted worldwide.

위와같은 연구의 결과로 최근에는 키토산을 섬유에 배합 또는 침적방법 등으로 적용시켜 항균성 및 방취성을 부여한 기술이 개발된 바 있다. 그러나 이 기술은 섬유에 부여된 키토산 성분의 내세탁성의 결여로 인하여 항균성이 지속되지 아니하는 문제점이 있다.As a result of the above research, a technique has been recently developed in which chitosan is applied to the fiber by blending or depositing to give antibacterial and deodorizing properties. However, this technique has a problem that the antimicrobial activity does not persist due to the lack of washing resistance of the chitosan component imparted to the fiber.

본 발명은 상기한 바와 같은 문제점을 해결하기 위한 것으로, 키토산을 섬유에 적용시키되 항균 및 항공팡이 효과가 지속적으로 유지되도록 하는 것을 목적으로 한다. 본 발명의 또 다른 목적은 키토산 함유 염료 중간체를 제공하는 것이다.The present invention is to solve the problems described above, it is an object to apply chitosan to the fiber, but to maintain the antibacterial and airborne effect continuously. Another object of the present invention is to provide a chitosan-containing dye intermediate.

본 발명자는 상기 목적을 달성하기 위하여 연구한 결과, 키토산 올리고머를 과산화수소를 포함한 염기성 수용액에서 가수분해하여 펜타며, 헥사머 상태의 키토산 올리고머(이하, CO로 칭함)를 얻은 다음, 이 것과 형광증백염료의 중간체인 4,4'-diaminostilbene-2,2'-disulfonic acid (이하, DAS로 칭함)를 염기성 수용액에서 cyanuric chloride(이하, CY로 칭함)로 연결하게 되면 키토산 함유 염료 중간체가 얻어 짐을 밝혀 내게 되었다.The present inventors have studied to achieve the above object, and as a result, the chitosan oligomer is hydrolyzed in a basic aqueous solution containing hydrogen peroxide to obtain a hexamer chitosan oligomer (hereinafter referred to as CO). Linking the intermediate 4,4'-diaminostilbene-2,2'-disulfonic acid (hereinafter referred to as DAS) to cyanuric chloride (hereinafter referred to as CY) in an aqueous solution yields a chitosan-containing dye intermediate. It became.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

키토산 올리고머의 저분자화에는 산, 염기 가수분해 또는 효소를 이용한 가수분해를 들 수 있는데, 산 가수분해 조건에서는 염산의 농도와 가열온도에 따라 모노머로부터 헵타머까지 얻을 수 있으나, 목적하는 펜타머와 헥사머를 주된 생성물로 얻기는 어렵다. 또한 효소인 chitosanase를 이용하여 가수분해를 할 경우에도 얻어지는 주된 생성물이 다이머와 트리머로서, 목적하는 펜타머와 헥사머를 주된 생성물로 얻기가 어렵다.The low molecular weight of chitosan oligomers may include acid, base hydrolysis or hydrolysis using enzymes. Under acid hydrolysis conditions, from the monomer to the heptamer, depending on the concentration of hydrochloric acid and the heating temperature, the desired pentamers and hexa It is difficult to obtain mer as the main product. In addition, even in the case of hydrolysis using the enzyme chitosanase, the main products obtained are dimers and trimers, and it is difficult to obtain desired pentamers and hexamers as main products.

본 발명에서는 과산화수소를 첨가한 염기성 가수분해를 이용하여 펜타머와 헥사머의 함량이 높은 키토산 올리고머를 얻는다(반응식 1 참조). 염기성 용액 중에서 첨가된 과산화수소의 도움으로 키토산 올리고머의 연결구조가 깨어져서 올리고머로 가수분해되며, 용액의 pH가 10.5 내지 12.5, 과산화수소의 농도가 1 내지 5중량% 일 때 펜타머와 헥사머의 생성확율이 높다.In the present invention, chitosan oligomers having a high content of pentamers and hexamers are obtained by using basic hydrolysis with hydrogen peroxide (see Scheme 1). With the help of hydrogen peroxide added in the basic solution, the linkage structure of the chitosan oligomer is broken and hydrolyzed to the oligomer. high.

얻어진 올리고머를 물에 녹인 후 CY를 가한 후 pH를 9.0 내지 10.0 정도로 유지하면서 반응을 진행시켜 CO-CY를 얻은 다음(반응식 II 참조), 여기에 DAS를 가하여 반응을 진행시키게 되면 CO-CY-DAS를 얻을 수 있다(반응식 III 참조).After dissolving the oligomer in water, CY was added and the reaction was carried out while maintaining the pH of about 9.0 to 10.0 to obtain CO-CY (see Scheme II), and then DAS was added thereto to proceed with the reaction. Can be obtained (see Scheme III).

Figure kpo00001
Figure kpo00001

Figure kpo00002
Figure kpo00002

Figure kpo00003
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본 발명의 실시예는 다음과 같다.Embodiments of the present invention are as follows.

[실시예 1]Example 1

키토산 올리고머(CO)의 제조Preparation of Chitosan Oligomers (CO)

키토산 폴리머 10g을 과산화수소 3% 용액 100ml에 넣고 10% NaOH 수용액을 가하여 pH를 11.5로 유지하면서 70℃에서 12시간 동안 반응시킨 후 용해되지 않은 것은 여과하고 용해된 것을 모아서 회전증발기로 물을 제거한 다음, 메탄올을 넣고 가열한 후 에테르로 침전을 얻어 건조시켜서 펜타머와 헥사머의 함량이 75%인 키토산 올리고머 5g을 얻었다.10 g of chitosan polymer was added to 100 ml of a 3% solution of hydrogen peroxide, and then reacted at 70 ° C. for 12 hours while maintaining a pH of 11.5 by adding a 10% aqueous NaOH solution. Methanol was added thereto, heated, and then precipitated with ether, followed by drying to obtain 5 g of chitosan oligomer having a pentamer and hexamer content of 75%.

얻어진 키토산 올리고머의 분자량 측정은 Waters 150C GPC(column: Ultrahydrogel 250, eluent: H2O, flow rate: 0.8ml/min, injection volume: 50μl)를 사용하여 측정하였으며 스켄다드는 폴리에틸렌 글리콜을 사용하였다.The molecular weight of the chitosan oligomer obtained was measured using Waters 150C GPC (column: Ultrahydrogel 250, eluent: H 2 O, flow rate: 0.8ml / min, injection volume: 50μl) and the scandard was polyethylene glycol.

[실시예 2]Example 2

CO-CY의 제조Manufacture of CO-CY

실시예 1을 통하여 얻은 키토산 올리고머(CO) 5g 을 300ml의 물에 녹인 후 4℃로 유지하면서 100ml의 1,4-dioxane에 CY 2g을 녹인 용액을 40분간 서서히 적하시킨다음, 10% Na2CO3를 가하여 pH를 8.0 내지 9.0으로 유지하면서 다시 4℃에서 2시간 동안 반응시켜 CO-CY를 제조하였다.After dissolving 5 g of chitosan oligomer (CO) obtained in Example 1 in 300 ml of water and maintaining the solution at 4 ° C., a solution of 2 g of CY dissolved in 100 ml of 1,4-dioxane was slowly added dropwise for 40 minutes, followed by 10% Na 2 CO. 3 was added thereto, and the mixture was reacted at 4 ° C. for 2 hours while maintaining the pH at 8.0 to 9.0 to prepare CO-CY.

[실시예 3]Example 3

CO-CY-DAS의 제조Manufacture of CO-CY-DAS

실시예 2를 통하여 얻은 CO-CY를 서서히 40℃로 승온한 후, DAS 1g을 10% Na2CO3에 녹여 서서히 적사시킨 후 pH를 8.0 내지 9.0으로 유지시키면서 2시간 동안 반응을 진행시켰다. 반응 후 물을 제거한 다음 20% 이소프로필알콜로 2번 세척한 후 건조시켜서 CO-CY-DAS를 얻었다.After slowly raising the CO-CY obtained in Example 2 to 40 ° C, 1 g of DAS was dissolved in 10% Na 2 CO 3 and slowly dropwise added, followed by reaction for 2 hours while maintaining the pH at 8.0 to 9.0. After the reaction, water was removed, washed twice with 20% isopropyl alcohol, and dried to obtain CO-CY-DAS.

얻어진 CO-CY-DAS의 구조 확인을 위하여 Gemini 200 NMR 스펙트로미터를 사용하여1H-NMR, 스펙트럼 분석으로 확인하였다. 키토산 올리고머의 단량체인 glucosamine(GA)과 CY 및 DAS와의 반응에서 DAS의 aromitic proton peak의 위치가 약 7 - 8 ppm에서 7.5 - 8.5 ppm으로 쉬프트(shift)되었고, glucosamine(GA)의 anomeric proton peak의 위치도 4.7, 5.2 ppm에서 5.2, 6.1 ppm으로 쉬프트됨으로 CO-CY-DAS가 합성되었음을 알 수 있었다. 또한 CO-CY-DAS의 반응에서도 DAS의 aromatic proton peak의 위치가 7.4 - 8.4 ppm으로 쉬프트됨으로 CO-CY-DAS가 합성되었음을 확인할 수 있었다.In order to confirm the structure of the obtained CO-CY-DAS, it was confirmed by 1 H-NMR and spectral analysis using a Gemini 200 NMR spectrometer. The position of the aromitic proton peak of DAS shifted from about 7-8 ppm to 7.5-8.5 ppm in the reaction between glucosamine (GA), a monomer of chitosan oligomer, and 7.5-8.5 ppm of glucosamine (GA), and the anomeric proton peak of glucosamine (GA). It was found that CO-CY-DAS was synthesized by shifting the position from 4.7 and 5.2 ppm to 5.2 and 6.1 ppm. In addition, it was confirmed that CO-CY-DAS was synthesized by shifting the position of aromatic proton peak of DAS to 7.4-8.4 ppm in the reaction of CO-CY-DAS.

이상의 실시예를 통하여 알 수 있는 바와 같이 본 발명에 의하여 키토산 올리고머로부터 항균성 및 방취성이 우수한 펜타머 또는 헥사머의 함량이 높은 올리고머를 얻어서 염료 중간체에 결합시킬 수 있다.As can be seen from the above examples, oligomers having a high content of pentamers or hexamers having excellent antibacterial and deodorizing properties can be obtained from chitosan oligomers and bound to dye intermediates.

펜타머 또는 헥사머의 함량이 높은 키토산 올리고머가 결합된 염료는 섬유에 적용되었을 때 지속적인 항균, 방취성을 발휘하게 된다.Dyes combined with high pentamers or hexamer chitosan oligomers exhibit continuous antimicrobial and deodorization properties when applied to fibers.

Claims (3)

키토산 올리고머를 과산화수소 1-5% 용액에 넣고 pH를 10.5 내지 12.5로 유지하면서 50 내지 100℃에서 반응시켜서 키토산 올리고머를 만든 후, 시아누릭 클로라이드(cyanuric chloride)를 가하여 0 내지 10℃, pH 7 내지 9의 조건에서 반응시켜 키토산 올리고머 - 시아누릭 클로라이드 결합체(CO-CY)를 형성시키고, 이 결합체에 4,4'-디아미노스틸벤-2,2'-디설포닉 산(DAS)을 가하고 반응시켜 키토산 올리고머-시아누릭 클로라이드-4,4'-디아미노스틸벤-2,2'-디설포닉 산(COCY-DAS) 결합체를 형성시키는 것을 특징으로 하는 키토산 올리고머를 이용한 형광염료 중간체의 제조방법.The chitosan oligomer was placed in a 1-5% hydrogen peroxide solution and reacted at 50 to 100 ° C. while maintaining a pH of 10.5 to 12.5 to form a chitosan oligomer, followed by adding cyanuric chloride to 0 to 10 ° C., pH 7 to 9 Reaction under conditions of chitosan oligomer-cyanuric chloride conjugate (CO-CY) to form, 4,4'- diaminostilben-2,2'- disulfonic acid (DAS) is added to the conjugate and reacted with chitosan A method for producing a fluorescent dye intermediate using a chitosan oligomer, characterized by forming an oligomer-cyanuric chloride-4,4'-diaminostilben-2,2'-disulfonic acid (COCY-DAS) conjugate. 제1항에 있어서, 키토산 올리고머는 펜타머와 헥사머의 함량이 70%이상인 것을 특징으로 하는 키토산 올리고머를 이용한 형광염료 중간체의 제조방법.The method of claim 1, wherein the chitosan oligomer is a method for producing a fluorescent dye intermediate using chitosan oligomer, characterized in that the content of pentamers and hexamers more than 70%. 아래 구조식을 가지는 것을 특징으로 하는 키토산 올리고머를 이요한 형광염료 중간체Fluorescent dye intermediate using chitosan oligomer, characterized by having the following structural formula
Figure kpo00004
Figure kpo00004
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CN107955085A (en) * 2017-11-06 2018-04-24 华侨大学 A kind of preparation method of O- chloros Triazine chitosan quaternary ammonium salt

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CN104140473A (en) * 2014-06-10 2014-11-12 盐城市印染有限公司 Chitosan s-triazine sulfonate derivative as well as preparation method and application of silicon hybridization solution thereof

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