환상 지방족 Isocyanate 및 Polytetramethylene Glycol로 제조한 수성 Polyurethane: 1.음 Ion 함량이 분산 및 Film 물성에 미치는 영향

이영민; 김병규; 신영조

Polymer(Korea), Vol.15, No.6, 664-669, December, 1991

Aqueous Polyurethanes from Cycloaliphatic Diisocyanate and Polytetramethylene Glycol : 1. Effect of Anionic Content on Dispersion and Film Properties

이영민, 김병규, 신영조

초록

환상 지방족 isocyanate (methylene bis(4-cyclohexyl isocyanate) (H₁₂MDI) 및 isophoron diisocyanate(IPDI)와, polytetramethylene glycol(PTMG) 및 dimethylol propionic acid(DMPA, 쇄연장제)로부터 polyurethane(PU) ionomer를 제조, 이를 물에 분산시킴으로써 안정된 수성 PU를 제조하였으며, 음 ion center의 함량이 분산 입경 및 emulsion cast film의 물리적 성질에 미치는 영향을 검토하였다. DMPA의 함량이 증가할수록 유화입경은 점근적으로 감소하였으며, 인장 물성(탄성률 및 강도)은 증가하였고, α-완화는 고온으로 이동되었으며 무정영역의 상호인력 역시 증가함을 알 수 있었다. 전반적으로 H₁₂MDI계 PU가 IPDI계 PU에 비해 유화입경이 작고, 기계물성이 우수하게 나타났다.

Polyurethane(PU) ionomers were prepared from cycloaliphatic diisocyanate(methylene bis(4-cyclohexyl isocyanate) (H₁₂MDI) and isophoron diisocyanate(IPDI)) and polytetramethylene glycol(PTMG) using an anionic type chain extender, viz. dimethylol propionic acid(DMPA). The effect of ionic content on the state of dispersion and physical properties of emulsion cast film was determined using Autosizer, transmission electron microscopy(TEM), Instron, and Rheovibron. With more incorporation of DMPA in PU, particle size of emulsion decreased asymptotically, tensile modulus and strength increased, and the α-transition moved toward the higher temperature with more amorphous interactions. With regard to the structural effect of the isocyanate, H₁₂MDI gave finer dispersion, and better mechanical properties over IPDI.

[References]

U.S. Patent, 2,968,757, Du Pont (1954)
U.S. Patent, 3,437,624, Wyandotte (1964)
U.S. Patent, 4,408,008 (1983)
U.S. Patent, 4,237,246 (1980)
U.S. Patent, 4,238,378 (1980)
Ger. Offen. 1,495,745, Bayer A.G. (1963)
Hsu SL, Xiao HX, Szmant HH, Frisch KC, J. Appl. Polym. Sci., 29, 2467 (1984)
Dieterich D, Keberle W, Witt H, Angew. Chem.-Int. Edit., 9, 40 (1970)
Al-Salah HA, Frisch KC, Xiao HX, McLean JA, J. Polym. Sci. A: Polym. Chem., 25, 2127 (1987)
Matsuda K, Ohmura H, Tanaka Y, Sakai T, J. Appl. Polym. Sci., 23, 141 (1979)
Chan WC, Chen SA, Polymer, 29, 1995 (1988)
David DJ, Staley HB, "Analytical Chemistry of Polyurethanes," High Polymer Series, X VI, Part III, Wiley-Interscience, New York (1969)
Vervey EJW, Overbeek JG, "Theory of Stability of Lyophobic Colloids," Elsevier Publishing Co., Amsterdam (1952)
Krieger IM, Polymer Colloid, R. Buscall, T. Corner, and I.F. Stageman (Eds.), Elsevier, New York (1985)
Dieterich D, Keberle W, Wuest R, J. Oil Col. Chem. Assoc., 63, 363 (1970)
Dieterich D, Angew. Makromol. Chem., 26, 85 (1972)
Lorenz O, Havlona F, Kleborn D, Angew. Makromol. Chem., 33, 159 (1973)
Lorenz O, Rose G, Angew. Makromol. Chem., 45(1), 85 (1975)
Kozak JJ, Penczek P, Pol. Patent, 84017 (1976)
Lorenz O, August HJ, Hick H, Triebs F, Angew. Makromol. Chem., 63, 11 (1977)
Lorenz O, Hugo H, Angew. Makromol. Chem., 72, 115 (1978)
Sukhorukova SA, Levchenko NJ, Grekov AP, Ukr. Khim. Zh., 47, 286 (1981)
Lipatov YS, Karabarova LV, Sergeava LH, Gorichko EY, Vysokomol. Soedin Ser. A, 24, 110 (1982)
Lipatov YS, Karabarova LV, Sergeava LH, Gorichko EY, Chem. Abstr., 96, 16360 (1982)
VanBogart JWC, Bluemke DA, Cooper SL, Polymer, 22, 1428 (1981)
Cunliffe AV, Davis A, Farey M, Wright J, Polymer, 26, 301 (1985)
Vankrevelen DW, Hoftyzer PJ, "Properties of Polymers," Elsevier, New York, Part II (1976)

[Referenced By]

[1] U.S. Patent, 2,968,757, Du Pont (1954)

[2] U.S. Patent, 3,437,624, Wyandotte (1964)

[3] U.S. Patent, 4,408,008 (1983)

[4] U.S. Patent, 4,237,246 (1980)

[5] U.S. Patent, 4,238,378 (1980)

[6] Ger. Offen. 1,495,745, Bayer A.G. (1963)

[7] Hsu SL, Xiao HX, Szmant HH, Frisch KC, J. Appl. Polym. Sci., 29, 2467 (1984)

[8] Dieterich D, Keberle W, Witt H, Angew. Chem.-Int. Edit., 9, 40 (1970)

[9] Al-Salah HA, Frisch KC, Xiao HX, McLean JA, J. Polym. Sci. A: Polym. Chem., 25, 2127 (1987)

[10] Matsuda K, Ohmura H, Tanaka Y, Sakai T, J. Appl. Polym. Sci., 23, 141 (1979)

[11] Chan WC, Chen SA, Polymer, 29, 1995 (1988)

[12] David DJ, Staley HB, "Analytical Chemistry of Polyurethanes," High Polymer Series, X VI, Part III, Wiley-Interscience, New York (1969)

[13] Vervey EJW, Overbeek JG, "Theory of Stability of Lyophobic Colloids," Elsevier Publishing Co., Amsterdam (1952)

[14] Krieger IM, Polymer Colloid, R. Buscall, T. Corner, and I.F. Stageman (Eds.), Elsevier, New York (1985)

[15] Dieterich D, Keberle W, Wuest R, J. Oil Col. Chem. Assoc., 63, 363 (1970)

[16] Dieterich D, Angew. Makromol. Chem., 26, 85 (1972)

[17] Lorenz O, Havlona F, Kleborn D, Angew. Makromol. Chem., 33, 159 (1973)

[18] Lorenz O, Rose G, Angew. Makromol. Chem., 45(1), 85 (1975)

[19] Kozak JJ, Penczek P, Pol. Patent, 84017 (1976)

[20] Lorenz O, August HJ, Hick H, Triebs F, Angew. Makromol. Chem., 63, 11 (1977)

[21] Lorenz O, Hugo H, Angew. Makromol. Chem., 72, 115 (1978)

[22] Sukhorukova SA, Levchenko NJ, Grekov AP, Ukr. Khim. Zh., 47, 286 (1981)

[23] Lipatov YS, Karabarova LV, Sergeava LH, Gorichko EY, Vysokomol. Soedin Ser. A, 24, 110 (1982)

[24] Lipatov YS, Karabarova LV, Sergeava LH, Gorichko EY, Chem. Abstr., 96, 16360 (1982)

[25] VanBogart JWC, Bluemke DA, Cooper SL, Polymer, 22, 1428 (1981)

[26] Cunliffe AV, Davis A, Farey M, Wright J, Polymer, 26, 301 (1985)

[27] Vankrevelen DW, Hoftyzer PJ, "Properties of Polymers," Elsevier, New York, Part II (1976)