m-, p-크레졸/포름알데히드 노볼락 수지의 합성과 물성에 관한 연구

이석규; 이해원

Polymer(Korea), Vol.16, No.6, 662-668, November, 1992

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m-, p-크레졸/포름알데히드 노볼락 수지의 합성과 물성에 관한 연구

Synthesis and Properties of Mixed meta-and para-Cresol/Formaldehyde Novolak Resins

이석규, 이해원

초록

m-크레졸과 p-크레졸 및 포름알데히드를 옥살산 촉매로 사용하여 축합중합반응으로 혼합 크레졸 노볼락 수지를 합성하였으며, 합성된 노볼락 수지를 H2O/MeOH로 용매 처리하여 열적 성질의 향상을 시도하였다. 노볼락 수지의 구조는 1H-NMR과 13C-NMR을 이용하여 분석하였다. 메틸렌의 양성자 피크는 1H-NMR의 경우에 3.4~4.3ppm에서 나타나고 13C-NMR의 경우에 31.8~37.7ppm에서 관찰되었으나, 용매처리에 의한 노볼락의 피크 변화는 없었다. 모든 노볼락의 초기 열분해 온도(Tid)는 160~250℃에서 나타났고, Tg는 90~115℃에서 관찰되었으며 낮은 H2O/MeOH의 비로 침지시킨 노볼락일수록 Tg가 높아지는 경향을 보였다. 노볼락 수지의 평균 분자량(Mw)은 높은 H2O/MeOH의 비로 침전시킬수록 감소하였으며, 분자량 분포(Mw/Mn)는 물의 양에 관계없이 3.4~3.6정도의 비슷한 경향을 보였다.

Novolak resin was synthesized by an acid catalyzed condensation of m-/p-cresol with 37% formaldehyde and then treated with the mixture of methanol and water as solvents in order to get improved thermal properties of novolak. The composition of novolak was identified with ¹H∼/l3C-NMR spectroscopy. In ¹H-NMR spectra, methylene proton peaks of novolak resin were observed in the range of 3.4∼4.3ppm. In ¹³C-NMR spectra, methylene carbon peaks were observed in the range of 31.8∼37.7ppm, but there were no prominent changes before and after solvent treatments. The initial decomposition temperature(T_id) of novolaks was obsered in the range of 160∼250℃. The glass transition temperature(T_g) of novolaks was varied on the change of mixing ratio of H₂O/MeOH. The highest glass transition temperature was 115℃ when the synthetic novolak resin were treated with the mixture of 2parts of methanol and 1part of water. The average molecular weight(M_w) of novolaks decreased with increasing the mixing ratio, however the molecular weight distribution(M_w/M_n) of solvent-treated novolaks was almost the same on the change of mixing ratio.

[References]

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[1] Knop A, Pilato LA, "Phenolic Resin," Spinger-Verlag, Berlin, p. 1 (1986)

[2] Chiantore O, Guaita M, J. Appl. Polym. Sci. Appl. Polym. Symp., 48, 431 (1991)

[3] Miura K, Ochiai T, Kameyama Y, U.S. Patent, 4,719,167 (1988)

[4] Sarubbi T, Blakeney A, Sizensky J, Greene N, Proc. SPIE, 1262, 273 (1990)

[5] Kajita T, Ota T, Nemoto H, Yumoto Y, Miura T, Proc. SPIE, 1466, 161 (1991)

[6] Dossel KF, Dammel R, Lingnau J, Schmitt A, European Patent, 0,335,219 A2 (1989)

[7] Hanabata M, Oi F, Furuta A, Proc. SPIE, 1466, 132 (1991)

[8] Zampini A, Turci P, Cernigliaro GJ, Sandford HF, Swanson GJ, Meister CC, Sinta R, Proc. SPIE, 1262, 501 (1990)

[9] Hosaka Y, Kamoshida Y, Harita Y, Harada K, European Patent, 0,092,444 (1983)

[10] Pethrick RA, Thomson B, Br. Polym. J., 18, 380 (1986)

[11] Noguchi T, Tomita H, Proc. SPIE, 1466, 149 (1991)

[12] Pampalone TR, Solid State Technol., 115 (1984)

[13] Fitzgerald EA, J. Appl. Polym. Sci., 41, 1809 (1990)

[14] Bogan LE, Macromolecules, 24, 4807 (1991)