폴리(비닐 알코올)/키토산 블렌드와 블렌드 수화젤의 열특성

박준서; 박장우; 김병호; Jun Seo Park; Jang Woo Park; Byung Ho Kim

Polymer(Korea), Vol.29, No.2, 183-189, March, 2005

Export Citation

폴리(비닐 알코올)/키토산 블렌드와 블렌드 수화젤의 열특성

Thermomechanical Characteristics of Poly(vinyl alcohol)/Chitosan Films and Its Blend Hydrogels

박준서^†, 박장우¹, 김병호¹

한경대학교 화학공학과 계면공학연구소
¹한경대학교 식품생물공학과

Jun Seo Park^†, Jang Woo Park¹, and Byung Ho Kim¹

Department of Chemical Engineering and Center for Applied Interfacial Technology, Hankyong National University, 67 Sukjung-dong, Ansung-si, Gyeonggi 456-749, Korea
¹Department of Food and Biotechnology, Hankyong National University, 67 Sukjung-dong, Ansung-si, Gyeonggi 456-749, Korea

E-mail:

초록

폴리(비닐 알코올)/키토산 블렌드와 블렌드 수화젤 필름을 용액캐스팅 방법으로 제조하였다. 블렌드와 블렌드 수화젤의 상용성에 대해서 전 조성 비율에 걸쳐서 DSC, TGA 및 DMA를 이용하여 조사를 하였다. DSC 분석에 따르면 키토산의 비율이 증가하면 블렌드내에서 폴리(비닐 알코올)의 용융점 감소와 결정화온도의 저하가 관측되었다. TGA 분석 결과, 키토산은 폴리(비닐 알코올) 보다 열적으로 더 안정하며, 블렌드내에서의 폴리(비닐 알코올)의 열안정성은 단독 폴리(비닐 알코올)의 열안정성과 비교하여 더 안정하였는데 이것은 블렌드의 구성고분자 사이에 상호작용이 존재함을 가리킨다. DMA 분석으로 키토산과 폴리(비닐 알코올)의 유리전이온도(Tg)를 측정하였는데, 각각 160과 90 ℃에서 나타났으며, 블렌드의 Tg는 블렌드에서 키토산의 함량에 따라서 변화하였다. 블렌드의 열적 및 점탄성의 분석결과는 키토산과 폴리(비닐 알코올) 사이에 상용성이 있음을 나타내고 있다. 고분자내에 수분과 화학가교는 친수성 고분자의 열적 및 물리적 특성에 크게 영향을 미치는데, 폴리(비닐 알코올)/키토산 블렌드의 상용성에 약간의 영향을 미쳤다.

Films of poly(vinyl alcohol)(PVA)/chitosan blends and its blend hydrogels were prepared by the solution casting method. The state of miscibility of the blends and blend hydrogels were examined over the entire composition range by differential scanning carorimetry (DSC), thermogravimetry (TGA), and dynamic mechanical analysis (DMA). DSC analysis shows the depression of melting point of PVA in the blends and the decrease of crystallization temperature of PVA in the blends were observed with increasing chitosan content in the blends. TGA analysis indicates that chitosan was thermally more stable than PVA and the thermal stability of PVA in the blends was higher than that of pure PVA, due to some interactions between two component polymers in the blend. The glass transition temperature (Tg) of the chitosan and of PVA, measured by DMA, were at 160 and 90 ℃, respectively. The Tg of the blends was changed with the content of chitosan in the blends. The results of thermal and viscoelastic analysis indicate some miscibility between component polymers in the blend exists. Moisture and cross linking in the blend and blend hydrogel, which strongly change thermal and physical properties of hydrophilic polymers, affected the miscibility of chitosan and PVA to a small extent.

Keywords:PVA;chitosan;hydrogel;miscibility;crosslinking

[References]

Muzzarelli RAA, Chitin, Pergamon Press, Oxford (1977)
Rathke TD, Hudson SM, J. Macrmol. Sci. Part C: Rev. Macromol. Chem. Phys., 34, 375 (1994)
Zikakis JP, Ed., Chitin, Chitosan and Related Enzymes, Academic Press, Orlando, Florida (1984)
Roberts GAF, Taylor KE, Makromol. Chem., 190, 951 (1989)
Arguelles-Monal W, Goycoolea FM, Peniche C, Higuera-Ciapara I, Polymer Gels and Networks, 6, 429 (1998)
Finch CA, Poly(vinyl alcohol), 2nd edition, New York, Wiley (1992)
Hassan CM, Peppas NA, J. Appl. Polym. Sci., 76(14), 2075 (2000)
Nijenhui K, Adv. Polym. Sci., 130, 1 (1997)
Shafee EE, Naguib HF, Polymer, 44(5), 1647 (2003)
Caro JR, PaikSung CS, Merrill EW, J. Appl. Polym. Sci., 20, 3241 (1976)
Korsmeyer RW, Peppas NA, J. Membr. Sci., 9, 211 (1981)
Folkes MJ, Hope PS, in Polymer Blends and Alloys, Chapman and Hall, London/New York, pp 430-440 (1985)
Dufresne A, Cavaille JY, Dupeyre D, Garcia-Ramirez M, Romero J, Polymer, 40(7), 1657 (1999)
Ratto JA, Chen CC, Blumstein RB, J. Appl. Polym. Sci., 59(9), 1451 (1996)
Qurashi MT, Blair HS, Allen SJ, J. Appl. Polym. Sci., 46, 255 (1992)
Park JS, Shin KH, J. Korea Soc. Packaging Sci. Tech., 8, 18 (2002)
Blair HS, Guthrie J, Law T, Turkington P, J. Appl. Polym. Sci., 33, 641 (1987)
Kim JH, KIm JY, Lee YM, Kim KY, J. Appl. Polym. Sci., 45, 1711 (1992)
Sakurai K, Maegawa T, Takahashi T, Polymer, 41(19), 7051 (2000)
Ikejima T, Yagi K, Inoue Y, Macromol. Chem. Phys., 200, 413 (1999)
Nishi T, Wang TT, Macromolecules, 8, 909 (1975)
Arvanitoyannis I, Kolokuris I, Nakayama A, Yamamoto N, Aiba S, Carbohydr. Polym., 34, 9 (1997)
Kaymin IF, Ozolinya GA, Plisko YA, Polym. Sci. U.S.S.R., 22, 171 (1980)
Pizzoli M, Ceccorulli G, Scandola M, Carbohydr. Res., 222, 205 (1991)
Kim SS, Kim SJ, Moon YD, Lee YM, Polymer, 35(15), 3212 (1994)
Aoi K, Takasu A, Tsuchiya M, Okada M, Macromol. Chem. Phys., 199, 2805 (1998)
Montes H, Mazeau K, Cavaille JY, Macromolecules, 30(22), 6977 (1997)
Shafee EE, Naguib HF, Polymer, 44(5), 1647 (2003)
Sato H, Tsuge S, Ohtani H, Aoi K, Takasu A, Okada M, Macromolecules, 30(14), 4030 (1997)

[Referenced By]

[1] Muzzarelli RAA, Chitin, Pergamon Press, Oxford (1977)

[2] Rathke TD, Hudson SM, J. Macrmol. Sci. Part C: Rev. Macromol. Chem. Phys., 34, 375 (1994)

[3] Zikakis JP, Ed., Chitin, Chitosan and Related Enzymes, Academic Press, Orlando, Florida (1984)

[4] Roberts GAF, Taylor KE, Makromol. Chem., 190, 951 (1989)

[5] Arguelles-Monal W, Goycoolea FM, Peniche C, Higuera-Ciapara I, Polymer Gels and Networks, 6, 429 (1998)

[6] Finch CA, Poly(vinyl alcohol), 2nd edition, New York, Wiley (1992)

[7] Hassan CM, Peppas NA, J. Appl. Polym. Sci., 76(14), 2075 (2000)

[8] Nijenhui K, Adv. Polym. Sci., 130, 1 (1997)

[9] Shafee EE, Naguib HF, Polymer, 44(5), 1647 (2003)

[10] Caro JR, PaikSung CS, Merrill EW, J. Appl. Polym. Sci., 20, 3241 (1976)

[11] Korsmeyer RW, Peppas NA, J. Membr. Sci., 9, 211 (1981)

[12] Folkes MJ, Hope PS, in Polymer Blends and Alloys, Chapman and Hall, London/New York, pp 430-440 (1985)

[13] Dufresne A, Cavaille JY, Dupeyre D, Garcia-Ramirez M, Romero J, Polymer, 40(7), 1657 (1999)

[14] Ratto JA, Chen CC, Blumstein RB, J. Appl. Polym. Sci., 59(9), 1451 (1996)

[15] Qurashi MT, Blair HS, Allen SJ, J. Appl. Polym. Sci., 46, 255 (1992)

[16] Park JS, Shin KH, J. Korea Soc. Packaging Sci. Tech., 8, 18 (2002)

[17] Blair HS, Guthrie J, Law T, Turkington P, J. Appl. Polym. Sci., 33, 641 (1987)

[18] Kim JH, KIm JY, Lee YM, Kim KY, J. Appl. Polym. Sci., 45, 1711 (1992)

[19] Sakurai K, Maegawa T, Takahashi T, Polymer, 41(19), 7051 (2000)

[20] Ikejima T, Yagi K, Inoue Y, Macromol. Chem. Phys., 200, 413 (1999)

[21] Nishi T, Wang TT, Macromolecules, 8, 909 (1975)

[22] Arvanitoyannis I, Kolokuris I, Nakayama A, Yamamoto N, Aiba S, Carbohydr. Polym., 34, 9 (1997)

[23] Kaymin IF, Ozolinya GA, Plisko YA, Polym. Sci. U.S.S.R., 22, 171 (1980)

[24] Pizzoli M, Ceccorulli G, Scandola M, Carbohydr. Res., 222, 205 (1991)

[25] Kim SS, Kim SJ, Moon YD, Lee YM, Polymer, 35(15), 3212 (1994)

[26] Aoi K, Takasu A, Tsuchiya M, Okada M, Macromol. Chem. Phys., 199, 2805 (1998)

[27] Montes H, Mazeau K, Cavaille JY, Macromolecules, 30(22), 6977 (1997)

[28] Shafee EE, Naguib HF, Polymer, 44(5), 1647 (2003)

[29] Sato H, Tsuge S, Ohtani H, Aoi K, Takasu A, Okada M, Macromolecules, 30(14), 4030 (1997)