세라믹 전구체 Polytitanomethylsilane의 합성과 열분해

김동표; 홍승표; 이익모; 이재도

Polymer(Korea), Vol.20, No.1, 10-16, January, 1996

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세라믹 전구체 Polytitanomethylsilane의 합성과 열분해

Synthesis and Pyrolysis of Preceramic Polytitanomethylsilanes

김동표, 홍승표, 이익모, 이재도

초록

열분해 수율은 매우 낮으나 반응성이 강한 Si-H을 많이 포함한 polymethylsilane (PMS)과 titanium tetrabutoxide (Ti(OBu)₄)를 반응시켜 polytitanomethylsilanes (PTMS)을 합성한 뒤 IR, NMR, GPC, TGA를 사용하여 세라믹 전구체로서의 물성을 분석하였다. 세라믹 수율이 최고 83%까지 개선된 PTMS는 불활성 분위기와 1300℃ 이상에서 열분해하여 carbide와 oxide를 포함한 복합 세라믹으로 전이되었다. 세라믹 조성은 Ti(OC₄H₉)₄/PMS의 반응 몰비가 6%일때는 SiC /TiC/SiO₂의 3성분 세라믹스가 얻어졌고 15%인 경우 TiO₂를 형성하여 4성분 세라믹스를, 그리고 반응 몰비가 33%일 때는 Ti의 상대적 함량이 큰 Ti₃O₅이 형성되어 β-SiC/TiC/SiOM₂/Ti₃O₅/α-Sic 5성분 세라믹스가 얻어졌다.

Polytitanomethylsilanes (PTMS) were synthesized by the reaction of titanium tetrabutoxide (Ti(OC₄H₉)₄) and polymethylsilane (PMS) which showed low ceramic yield but contained highly reactive Si-H bonds. Then PTMS, ceramic precursors, were characterized by R, NMR, GPC and TGA, resulting in much improved ceramic yield up to 83%. Precerarmic PTMS were converted to cerarmic composites of carbides and oxides when heated over 1300℃ under inert atmosphere. That is, SiC/TiC/SiO₂ ceramic mixture was obtained for 6 mole% of Ti(OC₄H₉)₄/PMS, and four-components ceramics containing TiO₂ for 15 mole%, and β-SiC/TiC/SiO₂/Ti₃O₅/α-SiC was Produced for 33 mole% .

[References]

Laine RM, Babonneau F, Chem. Mater., 5, 260 (1993)
Fagan JG, Amarakoon VRW, Am. Ceram. Soc. Bull., 72, 70 (1993)
Yajima S, Am. Ceram. Soc. Bull., 62, 893 (1983)
Yajima S, Okamura K, Hasegawa Y, Yamamura T, U.S. Patent, 4,336,215 (1982)
Yajima S, Okamura K, Hayashi J, J. Am. Ceram. Soc., 58, 1209 (1975)
Peuckert M, Vaahs T, Bruck M, Adv. Mater., 2, 398 (1990)
Yajima S, Shishido T, Okamura K, Am. Ceram. Soc. Bull., 56, 1060 (1977)
Shriver DF, Drezdzon MA, "The Manipulation of Air-Sensitive Compounds," 2nd, John Wiley and Sons, New York (1986)
Seyferth D, Sobon CA, Borm J, New J. Chem., 14, 545 (1990)
Bacque E, Pillot J, Birot M, Dunogues J, Macromolecules, 21, 30 (1988)
Seyferth D, Yu YF, U.S. Patent, 4,639,501 (1987)
West R, J. Org. Chem., 300, 327 (1986)
Boury B, Carpenter L, Corriu RJP, Angew. Chem.-Int. Edit., 29, 785 (1990)
Raberer JA, Lipowitz J, Lu PP, U.S. Patent, 5,051,215 (1991)
Hasegawa Y, Okamura K, J. Mater. Sci., 18, 3633 (1980)
Yajima S, Iwai T, Yamamura T, Okamura T, Hasegawa Y, J. Mater. Sci., 16, 1349 (1981)
Song Y, Hasegawa Y, Yang S, Sato M, J. Mater. Sci., 23, 1911 (1988)

[Referenced By]

[1] Laine RM, Babonneau F, Chem. Mater., 5, 260 (1993)

[2] Fagan JG, Amarakoon VRW, Am. Ceram. Soc. Bull., 72, 70 (1993)

[3] Yajima S, Am. Ceram. Soc. Bull., 62, 893 (1983)

[4] Yajima S, Okamura K, Hasegawa Y, Yamamura T, U.S. Patent, 4,336,215 (1982)

[5] Yajima S, Okamura K, Hayashi J, J. Am. Ceram. Soc., 58, 1209 (1975)

[6] Peuckert M, Vaahs T, Bruck M, Adv. Mater., 2, 398 (1990)

[7] Yajima S, Shishido T, Okamura K, Am. Ceram. Soc. Bull., 56, 1060 (1977)

[8] Shriver DF, Drezdzon MA, "The Manipulation of Air-Sensitive Compounds," 2nd, John Wiley and Sons, New York (1986)

[9] Seyferth D, Sobon CA, Borm J, New J. Chem., 14, 545 (1990)

[10] Bacque E, Pillot J, Birot M, Dunogues J, Macromolecules, 21, 30 (1988)

[11] Seyferth D, Yu YF, U.S. Patent, 4,639,501 (1987)

[12] West R, J. Org. Chem., 300, 327 (1986)

[13] Boury B, Carpenter L, Corriu RJP, Angew. Chem.-Int. Edit., 29, 785 (1990)

[14] Raberer JA, Lipowitz J, Lu PP, U.S. Patent, 5,051,215 (1991)

[15] Hasegawa Y, Okamura K, J. Mater. Sci., 18, 3633 (1980)

[16] Yajima S, Iwai T, Yamamura T, Okamura T, Hasegawa Y, J. Mater. Sci., 16, 1349 (1981)

[17] Song Y, Hasegawa Y, Yang S, Sato M, J. Mater. Sci., 23, 1911 (1988)