화학적으로 개질된 콜타르 핏치로부터 마이크로 비드의 제조

양갑승; 김찬; 안계혁

Polymer(Korea), Vol.20, No.4, 691-700, July, 1996

Export Citation

화학적으로 개질된 콜타르 핏치로부터 마이크로 비드의 제조

Preparation of Microbead from Coal Tar Pitch with Chemical Modification

양갑승, 김찬, 안계혁

초록

본 연구에서는 THF (tetrahydrofuran) 가용 콜타르 핏치와 여기에 화학적으로 개질하여 분자량을 조절한 핏치를 혼합, 열처리하여 마이크로 비드를 제조하였다. 핏치의 화학적 개질로는 30wt.%의 파라벤조퀴논을 150℃와 250℃에서 각각 1시간 반응시켜 얻었으며, 반응은 FT-lR을 사용하여 확인하였다. 마이크로 비드는 THF 가용분과 개질된 핏치를 각각 중량비 3/7, 5/5,7/3으로 혼합하여 420℃에서 시간을 달리하여 열처리한 다음 생성된 비드를 피리딘을 이용하여 추출하는 방법을 사용하였다. 피리딘 불용분의 함량은 개질된 핏치의 함량이 증가할수록 증가하였다. 이방성 함량은 편광현미경을 사용하여 측정하였으며, 반응시간이 짧은 30분에는 함량에 관계없이 모두 등방성상을 나타냈으나, 피리딘 불용분의 주사 전자 현미경 분석 결과 함량이 5/5인 경우는 직경 10μm 내외의 등방성 마이크로 비드가 생성되었다. 반응시간이 증가할수록 마이크로 비드외에 불용분의 함량이 증가하였으며, 생성된 비드가 점차 성장, 합체되는 것을 확인하였다. 탄화후 X-선 회절과 편광현미경을 사용하여 분석하였으며, 분자량이 큰 개질된 핏치의 함량이 증가할수록 분자내 유동성을 저하시켜 L_c002의 감소와 모자이크 texture를 갖는 것을 확인하였다.

In this study, microbeads were prepared by heat treatment of the mixtures of two kinds of pitches which have different molecular weights. They were THF (tetrahydrofuran) soluble coal-tar pitch (CP) and that of chemically modified (MCP) with 30 wt.% benzoquinone for lhour at 150℃, 250℃. The compositions of CP/MCP chosen were 3/7, 5/5, 7/3 wt.% ratio. The microbeads were separated by solvent extraction with pyridine. The concentration of the pyridine insoluble increased with an increase in MCP con-centration. All the samples in 30 minutes showed isotropic under polarized light microscope, however, the microbeads were observed in the 5/5 (CP/MCP ) sample with isotropic property under SEM. With an increase in heat treatment time, following behaviors were observed : an increase in fraction of pyridine insoluble, growth in bead size, coalescence of the beads, ultimate transformation to bulk mesophase. Microstructure and optical textures of carbonized products were characterized by using X-ray diffractometer and polarized light microscope. With an increase in concentration of MCP, the stack height (L_Lc002 value) reduced, which represents that the molecules of high w suppressed the mobility of molecules resulting mosaic texture.

Keywords:microbead;modified coal tar pitch;pyridine insoluble;β-resin;mosaic texture

[References]

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[1] Japan Patent, 05,325,947 (1993)

[2] Honda H, Yamada Y, Oi S, Fukuda K, Tanso, 7, 3 (1973)

[3] Yamasa Y, Imamura T, Kakiyama H, Honda H, Oi S, Fukuda K, Carbon, 12, 307 (1974)

[4] Japan Patent, 50,60595 (1973)

[5] Repsol Petroles, S.A. EP 585,193 (1993)

[6] Kodama M, Fujiura T, Esumi K, Meguro K, Honda H, Carbon, 26, 595 (1988)

[7] Honda H, Fujiura T, Ikawa E, Esumi K, Meguro K, Honda H, Carbon, 29, 43 (1991)

[8] Brooks GD, Talyor GH, Carbon, 3, 185 (1965)

[9] Mochida I, Maeda K, Takeshita K, Carbon, 15, 17 (1977)

[10] Huttinger KJ, Carbon'72, Arbeitskreis Kohlenstoff der Deutschen Keramischen Gesellschaft E., Barden-Baden, p. 5 (1972)

[11] Kovac CA, Lewis IC, 13th COnf., Carbon, 199 (1977)

[12] Kfoury F, Gasparoux H, Delhaes P, Albugues F, Grenie Y, 16th Conf., Carbon, 80 (1983)

[13] Berger W, Kammer HW, Kummerlowe C, Makromol. Chem., 8(S), 101 (1982)

[14] Paul DR, Newman S, "Polymer Blends," vol. 1, Academic Press, New York (1978)

[15] Southern JH, Ballman RL, J. Appl. Polym. Sci., 20, 175 (1973)

[16] Japan Patent, 05,283,060 (1993)

[17] Nagamra T, Tozawa K, Prog. Batteries Solar Cells, 9, 209 (1990)

[18] Matsumura Y, Wang S, Mondori J, Carbon, 33, 10 (1995)

[19] Sato K, Noguchi M, Demachi A, Oki N, Endo M, Science, 264(5158), 556 (1994)

[20] ASTM D3104 (Mettler Softening Point Method)

[21] Yang KS, Kim C, Choi JH, Kumagai H, Sanada Y, 22nd Biennial Conference on Carbon, San Diego, p. 212-213, July 16-21 (1995)

[22] Whittaker MP, Grindstaff LI, Carbon, 10, 165 (1972)

[23] Riggs DM, Ph.D. Dissertation, Rensselaar Polytechnic, Troy, New York (1979)