Cellulose/NMMO 용액에서의 Cellulose 결정화 거동

박성하; 정연호; 이화섭; 강호종

Polymer(Korea), Vol.22, No.5, 779-785, September, 1998

Export Citation

Cellulose/NMMO 용액에서의 Cellulose 결정화 거동

Crystallization Behavior of Cellulose in Cellulose/NMMO Solutions

박성하, 정연호, 이화섭, 강호종

초록

셀룰로오스 섬유제조의 용액으로 사용되는 셀룰로오스/N-methylmorpholine Noxide(NMMO) 용액에 있어서 셀룰로오스의 분자량 및 농도, NMMO의 함수율, 그리고 산화방지제가 셀룰로오스 결정화거동에 미치는 영향에 대하여 살펴보았다. 셀룰로오스/NMMO 용액의 결정화는 NMMO 결정 형성에 따른 transcrystallization에 의하여 발현됨을 확인하였다. 셀룰로오스의 분자량이 크고, 농도가 높은 용액의 경우 상대적으로 NMMO의 결정형성에 제한을 받고 따라서 같은 조건에서 저분자량 및 저농도 용액에 비하여 셀룰로오스의 결정화 속도는 감소함을 알 수 있었다. 또한 NMMO에 포함하고 있는 수분의 증가는 NMMO 자체의 결정화를 방해하여 셀룰로오스의 결정화 속도를 감소시키는 요인으로 작용함을 알 수 있었다. 사용된 산화방지제는 셀룰로오스 결정화 지연제의 역할을 함을 아울러 확인할 수 있었다.

Crystallization of cellulose/NMMO (N-methylmorpholin N-oxide) solutions has been investigated to understand the effects of molecular weight, dope concentration, water content in NMMO and anti-oxidant on the crystallization kinetic of cellulose. From the dynamic crystallization kinetic results, it was verified that crystallization of cellulose in the cellulose/NMMO solution was mainly due to the transcrystallization from the crystallization of NMMO solvent. Consequently, the crystallization rate in the dopes with a higher molecular weight and a higher solution concentration was slower than the dope with a lower molecular weight and lower concentration due to the less formation of NMMO crystallite. The water in NMMO causes the difficulty in the crystallization of NMMO. As a result, the dopes with a higher water content show slow crystallization. It was also found that anti-oxidants for cellulose/NMMO dope acted as the crystallization retarder for cellulose.

Keywords:N-methylmorpholine N-oxide;cellulose;transcrystallization;isothermal crystallization;cellulose fiber

[References]

Cole D, Jones A, Lenzinger Berichte, 69, 73 (1990)
Davies S, Textile Horizons, Feb., 62 (1989)
Chun SW, Lee WS, Jo SM, Kim JD, J. Korean Fiber Soc., 29(6), 44 (1992)
Cross CF, Beran EJ, Beadle C, Br. Patent, 8700 (1892)
Kim DB, Lee WS, Kang HJ, Polymer, to submitted
Kim DB, Lee WS, Kang HJ, Polym.(Korea), in accepted
Smith P, Pennings AJ, Polymer, 15, 413 (1974)
Smith P, Pennings AJ, J. Mater. Sci., 11, 1450 (1976)
Wittmann JC, John Manley R, J. Polym. Sci. B: Polym. Phys., 15, 1089 (1977)
Chanzy H, Peguy A, J. Polym. Sci. C: Polym. Lett., 17, 219 (1979)
Chanzy H, Carbohydrate Polym., 2, 229 (1984)
Nishio Y, Hirose N, Takahashi T, Polym. J., 21, 347 (1989)
Nishio Y, "Wood Processing and Utilization," J.F. Kennedy, G.O. Phillips, and P.A. Williams eds., pt. 4, ch. 32, Ellis Horwood, Chichester (1989)
Lee WS, Jo SM, Kang HJ, Kim DB, Park JS, U.S. Patent, 5,584,919 (1996)
Chanzy H, Nawrot S, Peguy A, Smith P, J. Polym. Sci. C: Polym. Lett., 20, 1909 (1982)

[Referenced By]

[1] Cole D, Jones A, Lenzinger Berichte, 69, 73 (1990)

[2] Davies S, Textile Horizons, Feb., 62 (1989)

[3] Chun SW, Lee WS, Jo SM, Kim JD, J. Korean Fiber Soc., 29(6), 44 (1992)

[4] Cross CF, Beran EJ, Beadle C, Br. Patent, 8700 (1892)

[5] Kim DB, Lee WS, Kang HJ, Polymer, to submitted

[6] Kim DB, Lee WS, Kang HJ, Polym.(Korea), in accepted

[7] Smith P, Pennings AJ, Polymer, 15, 413 (1974)

[8] Smith P, Pennings AJ, J. Mater. Sci., 11, 1450 (1976)

[9] Wittmann JC, John Manley R, J. Polym. Sci. B: Polym. Phys., 15, 1089 (1977)

[10] Chanzy H, Peguy A, J. Polym. Sci. C: Polym. Lett., 17, 219 (1979)

[11] Chanzy H, Carbohydrate Polym., 2, 229 (1984)

[12] Nishio Y, Hirose N, Takahashi T, Polym. J., 21, 347 (1989)

[13] Nishio Y, "Wood Processing and Utilization," J.F. Kennedy, G.O. Phillips, and P.A. Williams eds., pt. 4, ch. 32, Ellis Horwood, Chichester (1989)

[14] Lee WS, Jo SM, Kang HJ, Kim DB, Park JS, U.S. Patent, 5,584,919 (1996)

[15] Chanzy H, Nawrot S, Peguy A, Smith P, J. Polym. Sci. C: Polym. Lett., 20, 1909 (1982)