폴리우레탄 절연전선도료 제조시 TDI와 MDI의 Blocking 반응에 미치는 여러가지 반응조건의 영향에 관한 연구

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Journal of the Korean Industrial and Engineering Chemistry, Vol.8, No.2, 308-314, April, 1997

A Study on the Effects of Various Reaction Conditions on the Blocking Reactions of TDI and MDI in the Preparation of Polyurethane Varnishes

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초록

폴리우레탄 전선도료 제조시의 TDI와 MDI의 blocking 반응에 미치는 촉매와 blocking reagents(BR)의 영향에 대하여 조사하였다. 1,4-diazabicyclo[2.2.2]octane(DABCO)와 tetramethyl guanidine(TMG)와 같은 촉매들은 NCO의 blocking 반응을 완결시키는데 필요한 것으로 나타났다. TMG는 DABCO에 비해 매우 빠른 반응속도를 보였다. TMG의 농도는 1%까지 반응도에 대하여 정량적으로 비례하였다. DABCO의 경우는 0.25%의 농도에서 가장 높은 반응도를 나타내었다. BR의 입체영향을 알아보기 위해 phenol, p-dresol, m-cresol, o-cresol, 2,4-xylenol과 같은 BR 등을 사용하였다. 예측한대로 입체장애가 적은 BR이 높은 반응도를 보였다. 또한 이 반응 시스템에서는 온도와 BR의 농도가 증가할수록 반응도가 증가하였다.

The effects of catalyst and blocking reagents(BR) on the blocking reactions of TDI and MDI in the preparation of polyurethane varnishes have been studied. It was foung that certain types of catalysts, such as 1,4-diazabicyclo[2.2.2]octane(DABCO) and tetramethy1 guanidine(TMG), were necessary to complete the NCO blocking reactions. Blocking rate of TMG was shown much faster than that of DABCO. Reactivity increased with the increase of TMG concentration, at least to the concentration of 1%. In case of DABCO, the 0.25% concentration of catalyst showed the highest reactivity. In order to study the steric effects of BR on the blocking reactions, phenol, p-cresol, m-cresol, o-cresol, 2,4-xylenol were used as blocking reagents. As expected, BR which has less steric hindrance showed higher reactivity. The increase in BR concentration and reaction temperature increased the productivity of polyurethanes in this reaction system.

[References]

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[1] Braun D, Cherdron H, Kern W, "Techniques of Polymer Synthesis and Characterization," John Wiley and Sons, New York (1972)

[2] Collins EA, Bares J, Billmeyer FW, "Experiments in Polymer Science," John Wiley and Sons, New York (1973)

[3] 김강재, 폴리 우레탄 수지, 대림서원 (1976)

[4] David DJ, Staley HB, "Analytical Chemistry of the Polyurethanes," John Wiley and Sons, New York (1969)

[5] Hepburn C, "Polyurethane Elastomers," 2nd ed., Applied Science Publishers (1992)

[6] Doyle EH, "The Development and Use of Polyurethane Products," McGraw-Hill (1974)

[7] Bayer O, "Bayer Products for Wire Enamels and Impregnating Varnishs," Resislherm, Bayer (1980)

[8] 애경유지, "우레탄 도료용수지, 도료와 도장," (1993)

[9] Kresta JE, Frisch KC, "Advance in Urethane Science and Technology," Technomic (1979)

[10] Odian G, "Principles of Polymerization," John & Wiley (1991)

[11] Allcock HR, Lampe FW, "Contemporary Polymer Chemistry," Prentice-Hall (1989)

[12] Polyurethane Division, "Polyurethane 89," Technomic Publishing Co. (1989)