비닐에스테르 수지의 합성촉매에 관한 연구

홍석표; 최상구

Journal of the Korean Industrial and Engineering Chemistry, Vol.2, No.3, 229-237, September, 1991

Export Citation

비닐에스테르 수지의 합성촉매에 관한 연구

A Study on Synthesis Catalysts for Vinylester Resin

홍석표, 최상구

초록

합성촉매로 triethylamine(TEA), triethylbenzyl ammonium chloride(TEBAC), cetyltrimethyl ammonium bromide(CTMAB) 등의 아민 및 chromium acetyl acetate(CAA), triphenylantimony(TPA) 등의 유기금속화합물을 사용하여 합성촉매가 비닐에스테르수지의 합성 및 물성에 미치는 영향을 연구하였다. 반응성, 경화시간, 저장안정성 등을 고려해 볼 때, 촉매의 적절한 사용량은 methacrylic acid(MAA)에 대하여 아민계의 경우에는 1.7∼2.2%(중량 %), 유기금속계의 경우에는 2.5∼3.1%(중량 %)였다. 촉매의 반응성은 TEA > TEBAC > CTMAB > CAA > TPA의 순이었으며, 촉매의 온도의존성은 110 ℃이상에서 크게 나타났다. 수지의 저장안정성은 합성 후 TPA를 MAA에 대하여 2.0% (중량 %) 이내의 범위에서 첨가하였을 때, 경화시간의 지연됨이 없이 개량되었다.

Vinylester was syntheszed in the presence of amine and metal catalysts, such as triethylamine(TEA), triethylbenzyl ammonium chloride (TEBAC), cetyltrimethyl ammonium bromide (CTMAB), chromium acety] acetate (CAA), and triphenylantimony (TPA). Apropriate use of amine and organometal catalysts were 1.7∼2.2 % (Wt. %), 2.5∼3.1 % (Wt %) of charged methacrylic acid (MAA) in respect of reactivity, gel-time, and storage stability. The Order of reactivity was TEA > TEBAC > CTMAB > CAA > TPA. Temperature independence of catalyst showed more large deviation above 110 ℃. Storage stability could be improved without delay of gel-time by adding TPA in 2.0 % (Wt %) of charged MAA after synthesis.

[References]

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[1] Dow Chemical Co., Technical Bull (1987)

[2] U.S. Patent, 3,301,743

[3] U.S. Patent, 3,594,247

[4] Linow WH, Bearden CR, 21st SPI Reinforced Plastics/Composites Conference, Paper 1-D (1966)

[5] Varma IK, Angew. Makromol. Chem., 130, 191 (1985)

[6] Yoshino M, Shibata M, J. Paint Tech., 44, 116 (1972)

[7] Japan Patent, 45-15,988

[8] Barker NG, Cromwell NH, J. Am. Chem. Soc., 73, 1051 (1951)

[9] Leblainvaux F, Madec PJ, Polym. Bull., 13, 237 (1985)

[10] Awaji T, Atobe D, U.S. Patent, 129,609 (1978)

[11] Levy LB, J. Polym. Sci. A: Polym. Chem., 23, 1505 (1985)

[12] Kurland JJ, J. Polym. Sci. A: Polym. Chem., 18, 1139 (1980)

[13] Eastman Chemical Co., Technical Bull. (1986)

[14] UK Patent, GB 2,025,996A

[15] Rao BS, Madec PJ, Marechal E, Polym. Bull., 16, 153 (1986)

[16] U.S. Patent, 4,200,705

[17] Banthia AK, Yilgor I, Polym. Prepr., 22, 209 (1981)

[18] Alexander GA, "Catalysis, in Encyclopedia of Chemical Technolog," Vol. 4, 2nd ed., Interscience Publishers, John Wiley and Sons, Inc., New York, p. 534 (1964)

[19] Greenley RZ, "Free Radical Copolymerizations of Vinyl Monomer," Polymer Handbook, 3nd, Interscience Publication, John Wiley and Sons, Inc., New York, p. 267 (1989)

[20] U.S. Patent, 3,256,226

[21] U.S. Patent, 4,246,498

[22] Pruett RL, Adv. Organometal. Chem., 17, 1 (1979)

[23] Baker JW, "Electronic Theories of Organic Chemistry," Oxford University Press, p. 105 (1966)