고분자 음전해질 및 양전해질의 염 농도에 따른 용액 속에서의 형태변화

양재영; 손대원; 김남정; Jaeyoung Yang; Deawon Sohn; Nam-Jeong Kim

Polymer(Korea), Vol.23, No.5, 708-716, September, 1999

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고분자 음전해질 및 양전해질의 염 농도에 따른 용액 속에서의 형태변화

Conformations of Anionic and Cationic Polyelectrolytes in Various Salt Concentration Solutions

양재영, 손대원^†, 김남정¹

한양대학교 화학과
¹삼육대학교 화학과

Jaeyoung Yang, Deawon Sohn^†, and Nam-Jeong Kim¹

Department of Chemistry, Hanyang University, Haengdang Dong 17, Seungdong Ku, Seoul, Korea
¹Department of Chemistry, Sahmyook University, 223 Kongneung 2-Dong, Nohwon Ku, Seoul, Korea

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초록

H₂O/NaCl용액 속에서 두 개의 다른 고분자 전해질, polystyene sulfonate (PSS, Mw=500 k, 70 k)와 polyallyamine (PAA, Mw=70 k)의 염 농도 변화에 따른 형태 변화를 점도계, 동적 광산란, 주사 전자 현미경을 이용하여 관찰하였다. 용액 속에서 고분자 전해질의 성질은 반대 이온 세기. 고분자 전해질의 펼친 길이와 고분자 전해질의 종류에 따라 영향을 받는다. 서로 반대 전하를 띤 PSS, PAA의 점성도는 염의 농도가 높을수록 감소하고 염의 농도가 감소함에 따라 모두 증가했다. 또 광산란 실험에서 염 농도를 0.0 M에서 0.5 M까지 증가시킴에 따라 PSS와 PAADML 수화 반경은 점점 작게 되고 낮은 염 농도에서 이들의 상관 함수는 두 개의 확산 계수를 나타내는 이중 지수 함수를 나타내었다. 또한 고분자 전해질 용액에서 염에 대한 영향성을 시각화하기 위해 시료를 동결 건조 후 주사 전자 현미경을 사용하여 그 형상을 관찰했다. 염의 첨가가 없는 용액에서 PSS와 PAA의 형상은 매끈한 표면을 나타내었다. 반면 염의 농도가 증가함에 따라 작은 많은 낱알들이 PSS와 PAA의 미끈한 표면과 공존하는데, 이것을 통해 PSS와 PAA용액의 광산란 실험에서 확산 계수가 두 개로 나타나는 원인 설명하였다.

The conformational change of two different polyelectrolytes, polystyrene sulfonate(PSS) and polyallylamine(PAA), in H₂O/NaCl was investigated as a function of the ionic strength using viscometer, light scattering (LS), and scanning electron microscope(SEM). The behavior of polyelectrolyte depended on the ionic strength of the solution, the contour length of the polymer, and the type of polyion. The viscosity of the high ionic strength sample was lower at all polymer concentrations and increased by decreasing the salt concentration. When we increased the salt concentration from 0.0 M to 0.5 M, the hydrodynamic radius decreased, and the correlation functions of the light scattering showed double ponential in the low salt condition. To visualize the conformational change of the polyelectrolyte at different salt conditions, SEM was used after freeze-drying the sample. In the salt free solution the images of PCS and PAA showed a smooth surface. The polyelectrolyte, however, generate many small aggregated grains by increasing the salt concentration. Based on these experiments, we propose a model of conformational change due to the electrostatic interaction at various ionic strengths.

Keywords:polyelectrolyte;polystryrene sulfonate;polyallylamine;salt effect;light scattering;O-E transition

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[1] Belloni L, Drifford M, J. Phys. Lett., 46, 1183 (1985)

[2] Stevens MJ, Plimpton SJ, Eur. Phys. J. B, 2, 341 (1998)

[3] Anderson CF, Record MT, Annu. Rev. Phys. Chem., 33, 191 (1982)

[4] Noyola MM, Rendon AV, Phys. Rev., A, 32, 3596 (1985)

[5] Odijk T, Macromolecules, 12, 688 (1979)

[6] Drifford M, Dalbiez L, Chattopadhya AK, J. Colloid Interface Sci., 105, 587 (1985)

[7] Ise N, Okubo T, Yamamoto K, Matsuoka H, Kawai H, Fujimura M, J. Chem. Phys., 78, 541 (1983)

[8] Ware B, Adv. Colloid Interface Sci., 4, 1 (1974)

[9] Hodgson DF, Amis EJ, J. Chem. Phys., 91, 2635 (1989)

[10] Levij M, de Bleiser J, Leyte M, Chem. Phys. Lett., 83, 183 (1981)

[11] Matsuoka H, Ise N, Okubo T, Kunugi S, Tomilama H, Yoshikawa Y, J. Chem. Phys., 83, 378 (1985)

[12] Ise N, Okubo T, Kunugi S, Matsuoka H, Yamamoto K, Ishii Y, J. Chem. Phys., 81, 3294 (1984)

[13] Dautzenberg H, Karibyants N, Macromol. Chem. Phys., 200, 118 (1999)

[14] Lin SC, Shurr JM, Biopolymer, 17, 425 (1978)

[15] Drifford M, Dalbiez JP, Biopolymer, 24, 1501 (1985)

[16] Drifford M, Dalbiez JP, J. Phys. Lett., 46, L311 (1985)

[17] Schmitz KS, Mei L, Gauntt J, J. Chem. Phys., 78, 5059 (1983)

[18] Wissenburg P, Odijk T, Cirkel P, Mandel M, Macromolecules, 28(7), 2315 (1995)

[19] Sedlak M, Amis EJ, J. Chem. Phys., 96, 826 (1992)

[20] Schmitz K, "An Introduction to Dynamic Light Scattering by Macromolecules," Academic Press Inc., San Diego, CA, U.S.A. (1990)

[21] Li X, Reed WF, J. Chem. Phys., 94, 4568 (1991)

[22] Sedlak M, Macromolecules, 28(3), 793 (1995)

[23] Drifford M, Dalbiez JP, Delsanti M, Belloni L, Ber. Bunsenges. Phys. Chem., 100, 829 (1996)

[24] Borochov N, Eisenberg H, Macromolecules, 27(6), 1440 (1994)