키토산과 폴리에틸렌글리콜 모노메타크릴레이트의 그라프트중합과 약물(Vitamin B₁₂)방출에 관한 연구

Studies on the Graft Polymerization of Polyethyleneglycol Monomethacrylate onto Chitosan and Drug(Vitamin B₁₂) Permeation Behavior

생체적합성이 좋은 천연고분자인 chitosan에 수용성의 비닐계 단량체인 polyethyleneglycol monomethacrylate series를 그라프트중합시켜 그 반응조건과 물성을 검토하였다. 그라프트중합은 ethylene oxide 부가몰수에 따라 PE-90, PE-200, PE-350의 세 가지 단량체에 ceric ammonium nitrate(CAN)를 개시제로 사용하였으며, 중합에서 개시제의 농도, 단량체의 농도, 반응온도, 반응시간이 총전환율, 그라프트율, 그라프트효율에 미치는 영향을 조사하여 최적조건을 규명하였다. 반응은 개시제농도 $4{\sim}5{\times}10^{-3}M$, 단량체농도 0.5~0.6M, 반응시간 2~3시간, 반응온도 $40^{\circ}C$에서 최고의 그라프트율과 총전환율을 나타냈다. 합성한 공중합체의 열적 성질, 용해성 및 점성도를 검토한 결과 고농도의 개시제를 사용하면 그라프트 중합체는 chitosan의 특성을 급격히 감소시켰다. 고유점성도의 경우, chitosan-g-PE-90이 2.81dl/g, chitosan-g-PE-200이 3.01dl/g, chitosan-g-PE-350이 4.93d1/g으로 증가하는 경향이 나타났다. 공중합체를 막으로 성형하여 그라프트율과 polyethyleneglycol monomethacrylates의 ethylene oxide 부가몰수에 따른 공중합체의 기계적 물성과 함수율을 측정하였다. 가교화 공중합체막은 150분 이내에 함수율이 평형에 이르렀다. 공중합체의 물성은 그라프트율과 ethylene oxide 부가몰수의 영향을 받았으며 chitosan의 기계적 물성과 함수율이 공중합체에서 증가되었음을 확인하였으며 그라프트율이 증가함에 따라 vitamin $B_{12}$의 투과량도 증가하였다.

Chitosan is known to be a good biocompatible natural polymer. Polyethyleneglycol monomethacrylates(PEGM) were grafted onto chitosan and their reaction conditions and properties of the graft polymers obtained were estimated. Using ceric ammonium nitrate(CAN) as the initiator, the optimum condition for graft polymerization was determined amount of the initiator and monomer concentrations and reaction time. Grafting yields such as total conversion, the percentage of grafting and the efficiency of grafting were calculated and examined the optimum reaction condition for high grafting yields. The percentage of grafting and total conversion were maximum at condition that the concentration of initiator was $4{\sim}5{\times}10^{-3}M$, the concentration of monomer was 0.5~0.6M, the reaction time was 2~3 hours and the reaction temperature was about $40^{\circ}C$. Thermal characteristics, solubility for chitosan solvents and inherent viscosity of synthesized graft copolymers were investigated. In high initiator concentration, characteristics of chitosan were greatly diminshed. In case of inherent viscosities, chitosan-g-PE-90 was 2.81 dl/g, chitosan-g-PE-200, 3.01dl/g and chitosan-g-PE-350, 4.93dl/g. And a tendency of viscosity increase depending on the length of ethylene oxide residue was confirmed. Degree of swelling, tensile strength, elongation of membrane prepared from graft copolymers were determined. Properties of graft copolymers were affected by percentage of grafting and length of ethylene oxides residue in polyethylene glycol monomethacrylates. Tensile strength, elongation and degree of swelling of graft copolymers were remarkably improved than chitosan. As percentage of grafting increased, the amount of drug permeation was also increased.