Thermal Decomposition Behavior of Blocked Diisocyanates Derived from Mixture of Blocking Agents

Jung Min Lee; Sankaraiah Subramani; Young Soo Lee; Jung Hyun Kim

Macromolecular Research, Vol.13, No.5, 427-434, October, 2005

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Thermal Decomposition Behavior of Blocked Diisocyanates Derived from Mixture of Blocking Agents

Jung Min Lee, Sankaraiah Subramani, Young Soo Lee, and Jung Hyun Kim^†

Nanosphere Process and Technology Laboratory, Department of Chemical Engineering, Yonsei University, Seoul 120-749, Korea

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To improve the performance and reduce raw material costs, blocked isocyanates were prepared with mixture of blocking agents in many industries. Three blocked isocyanates (adducts) namely ε-caprolactam/benzotriazole-blocked 4,4'-diphenylmethane diisocyanate (MDI), toluene-2,4-diisocyanate (TDI) and 4,4'-dicyclohexylmethane diisocyanate (H12MDI) were synthesized. Six reference adducts were also prepared by blocking MDI, TDI, and H12MDI with ε-caprolactam ( ε-CL) or benzotriazole. The reactions were carried out in acetone medium and dibutyltin dilaurate (DBTDL) was used as a catalyst. The progress of the blocking reaction was monitored by IR spectroscopy. De-blocking temperatures (dissociation temperatures) of these adducts were studied using DSC and TGA and the results were correlated. As expected, the thermal analysis data showed that de-blocking temperature of blocked aromatic isocyanates was lower than that of the blocked aliphatic isocyanates. The low de-blocking temperature of blocked aromatic isocyanate could be due to electron withdrawing benzene ring present in the blocked isocyanates. It was also found that benzotriazole-blocked adducts de-blocked at higher temperature compared with ε-CL-blocked adducts.

Keywords:blocked isocyanate;blocking agent;deblocking behavior;adducts;dissociation

[References]

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[Referenced By]

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[1] Wicks Z, Prog. Org. Coat., 3, 73 (1975)

[2] Wicks Z, Prog. Org. Coat., 9, 3 (1981)

[3] Lee HT, et al., Waterborne, High-Solids and Powder Coatings Symposium, New Orleans, LA, USA, Proceeds, pp 224-233 (February) (1995)

[4] Kwon JY, Kim EY, Kim HD, Macromol. Res., 12(3), 303 (2004)

[5] Kim BK, Seo JW, Jeong HM, Macromol. Res., 11(3), 198 (2003)

[6] Wicks DA, Wicks ZW, Prog. Org. Coat., 36, 148 (1999)

[7] Wicks DA, Wicks ZW, Prog. Org. Coat., 41, 1 (1999)

[8] Nitto Electric Ind., Japan. Pat. 72 51, 158; World Surf. Coat. Abstr., 46, 1202 (1973)

[9] Rye GN, Bhakuni RS, Cormany JL, Evans TE, Ger. Offen. 1,921,672; C.A., 73, 46449 (1970)

[10] Dupont EI, Brit. Pat. 987,600; C.A., 63, 3148 (1965)

[11] Bayer AG, Germany, Fr. Pat. 1,525,628; C.A., 38, 4365 (1969)

[12] Picard J, Hantzer P, Fr. Pat. 1,414,808; C.A., 64, 5268 (1966)

[13] McKillip WJ, Sedor EA, Culbertson BM, Wawzonek S, Chem. Rev., 73, 255 (1973)

[14] Bayer AG, Germany, Eur. Pat. 741, 157; C.A., 125, 331661 (1996)

[15] Dieter JA, Frisch KC, Wolgemuth LG, Coatings and Plastics Preprints, Los Angeles ACS Meeting, p. 703 (April) (1974)

[16] Ferrocorp PCT Int. Appl. WO 7518,838 C.A., 123, 341245 (1995)

[17] Morak AJ, US. Pat. 3, 492, 081; C.A., 72, 102044 (1970)

[18] Howell CH, Jr., US. Pat. 3,519,478; C.A., 73, 78733 (1970)

[19] Habib E, Nimoy M, US. Pat. 3,238,010 (1966); C.A., 64, 17858 (1966)

[20] Levy JF, Kusean J, US. Pat. 3,705,119; C.A., 78,59887 (1973)

[21] Elkin HL, US. Pat. 3,384,506; C.A., 69,20349 (1968)

[22] Dupont EI, Brit. Pat. 1,085,454; C.A., 67, 117905 (1967)

[23] Schaeffer PR, Steely NE, US. Pat. 3,511,893; C.A., 73,4740 (1970)

[24] Ahn JS, Choi DH, Rhee TH, Kim N, Polym.(Korea), 22(1), 150 (1998)

[25] Schmelzer G, Gruber H, Degener E, Zeicher W, Brit. Pat. 1,200,718; C.A., 73,67337 (1970)

[26] Kolodzoejczyk A, Prelicz D, Sucharda-Sobczyk A, Acta Pol. Pharm., 28, 279 (1971)

[27] Kolodzoejczyk A, Prelicz D, Sucharda-Sobczyk A, 76, 33917 (1972)

[28] Levine AW, Fech J, J. Paint Tech., 45, 56 (1973)

[29] Frisch KC, Damusis A, US. Pat. 4,096,128 (1978)

[30] Graw N, Ger. Offen. 2,830,590 (1980)

[31] Sultan Nasar A, Jaisankar SN, Subramani S,Radha Krishnan G, J. Macromol. Sci.-Pure Appl. Chem., A34, 1237 (1997)

[32] Sultan Nasar A, Subramani S, Radhakrishnan G, Polym. Int., 48, 614 (1999)

[33] Sultan Nasar A, Subramani S, Radhakrishnan G, Polym. Int., 49, 546 (2000)

[34] Bayer. A-G Germany, DE 4416750 (May) (1994)

[35] Subramani S, Park YJ, Lee YS, Kim JH, Prog. Org. Coat., 48, 71 (2003)

[36] Subramani S, Park YJ, Cheong IW, Kim JH, Polym. Int., 53, 1145 (2004)

[37] Subramani S, Cheong IW, Kim JH, Prog. Org. Coat., 51, 329 (2004)

[38] Subramani S, Cheong IW, Kim JH, Eur. Polym. J., 40, 2745 (2004)

[39] Hartz RE, J. Appl. Polym. Sci., 19, 795 (1975)

[40] Damusis A, Frisch KC, Treatise on Coatings, R. R. Myers and J. S. Long, Eds., Dekker, New York, NY, Vol.I, Part I, pp 435-516 (1967)

[41] Anagnostou T, Jaul E, J. Coat. Technol., 53, 35 (1981)

[42] Thomas P, Waterborne and Solvent based Surface Coating Resins and their Applications - Polyurethanes, Sita Technology Ltd., London, pp 141-158 (1999)