Poly(ethylene-co-methacrylic acid)-Zinc 이오노머의 수소결합에 관한 연구

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Polymer(Korea), Vol.18, No.1, 46-54, January, 1994

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Poly(ethylene-co-methacrylic acid)-Zinc 이오노머의 수소결합에 관한 연구

Hydrogen Bonding in Poly (ethylene-co-methacrylic acid)-Zinc Ionomer

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초록

부분적으로 중성화된 에틸렌-메타크릴산 공중합체(EMAA)-Zn 이오노머의 수소결합 형성에 대한 온도 의존성을 적외선 분광분석으로 조사하였다. EMAA-Zn 이오노머의 이온화되지 않은 상태로 남아있는 카르복실산들은 acid dimer를 형성하거나 carboxylic acid salt 형태의 수소결합을 한다. 카르복실산 C=0 흡수 피크의 면적으로부터 이들 수소결합생성에 관한 열역학적 파라미터를 계산하였다. 부분적으로 중성화된 EMAA-Zn 이오노머에서의 acid dimer 생성 엔탈피는 -4.55kcal/mol이었으며, carboxylic acid salt 생성 엔탈피는 -8.87kca1/mo1이었다. 부분적으로 중성화된 EMAA-Zn 이오노머에서의 acid monomer-dimer의 평형은 Carboxylic acid salt 형성에 의해서 영향 받는다는 것을 알 수 있었다.

Temperature dependences of hydrogen-bond formation in a partially neutralized poly(ethylene-co-methacrylic acid) (EMAA) -Zn ionomer have been investigated by infrared spectroscopy. Unionized carboxylic acid groups remaining in a partially neutralized EMAA-Zn ionomer form two types of hydrogen bonds : carboxylic acid dimers and carboxylic acid salts. Thermodynamic parameters for these hydrogen bond formations were calculated by using integrated absorbances of the carboxylic acid carbonyl peaks. Enthalpies of -4.55 and -8.87 kcal/mol for the acid dimerization and carboxylic acid salt formation in a partially neutralized EMAA-Zn ionomer, respectively, were obtained. It is shown that the carboxylic acid monomer-dimer equilibrium in the partially neutralized EMAA-Zn ionomers is affected by the carboxylic acid salt formation between carboxylic acid and carboxylate groups.

[References]

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[1] Eisenberg A, King M, "Ion Containing Polymers," Academic Press, New York (1977)

[2] MacKnight WJ, Earnest TR, J. Polym. Sci. Macromol. Rev., 16, 41 (1981)

[3] Holliday L, "Ionic Polymers," Applied Science Publishers, London (1975)

[4] Eisenberg A, "Ions in Polymers," Adv. Chem. Ser. No. 187, American Chemical Society, Washington D.C. (1980)

[5] Wilson AD, Prosser AD, "Developments in Ionic Polymers-1," Applied Science Publishers, London and New York (1983)

[6] Pineri M, Eisenberg A, "Structure and Properties of Ionomers," NATO ASI Series (1980)

[7] Eisenberg A, Bailey FE, "Coulombic Interactions in Macromolecular Systems," ACS Symp. Ser. No. 302, American Chemical Society, Washington, D.C. (1986)

[8] Eisenberg A, Macromolecules, 3, 147 (1970)

[9] Painter PC, Brozoski BA, Coleman MM, J. Polym. Sci. B: Polym. Phys., 20, 1069 (1982)

[10] Brozoski BA, Coleman MM, Painter PC, J. Polym. Sci. B: Polym. Phys., 21, 301 (1983)

[11] Brozoski BA, Coleman MM, Painter PC, Macromolecules, 17, 230 (1984)

[12] Brozoski BA, Painter PC, Coleman MM, Macromolecules, 17, 1591 (1984)

[13] Coleman MM, Lee JY, Painter PC, Macromolecules, 23, 2339 (1990)

[14] Vinogradov SN, Linnell RH, "Hydrogen Bonding," Van Nostrand, New York (1971)

[15] Pimentel GC, McCellan AL, "The Hydrogen Bond," W.H. Freeman, San Francisco and London (1960)

[16] Pimental GC, McCellan AL, Annu. Rev. Phys. Chem., 22, 347 (1971)

[17] Novak A, Struct. Bonding, 18, 177 (1974)

[18] Schuster P, Zundel G, Sandorfy C, "The Hydrogen Bond. Recent Developments in Theogy and Experiments," Vols. I-III, North Holland, New York (1976)

[19] Speakman JC, Struct. Bonding, 12, 141 (1972)

[20] Mauritz KA, Gray CL, Macromolecules, 16, 1279 (1983)

[21] Lee JY, Painter PC, Coleman MM, Macromolecules, 21, 346 (1988)

[22] Klemperer W, Pimentel GC, J. Chem. Phys., 22, 1399 (1954)