화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Korean Chemical Engineering Research, Vol.42, No.6, 735-740, December, 2004
Export Citation
실시간 In-situ IR분광법을 이용한 Isophorone Diisocyanate(IPDI)와 Dimethylol Alkanoic Acid계 폴리우레탄 프리폴리머의 반응 속도론 연구
Kinetic Studies on the Synthesis of Polyurethane Prepolymer with Isophorone Diisocyanate(IPDI) and Dimethylol Alkanoic Acids by Real-Time In-situ IR Spectroscopy
조항규, 김형집, 서교택1, 강신춘†
  • 한양대학교 공학대학 화학공학전공, 426-791 경기도 안산시 상록구 사1동 1271
  • 1충청대학 실용소재과, 363-792 충북 청원군 강내면 월곡리 330
Hang-Kyu Cho, Hyung Zip Kim, Gyo Taeg Seo1, and Shin Choon Kang†
  • Department of Chemical Engineering, Hanyang University, 1271, Sa-1 dong, Ansan, Gyeonggi-do, 426-791, Korea
  • 1Department of Applied Materials, Chung Cheong University, 330, Wolgok-ri, Gangnae-Myeon, Cheongwon-Gun, 363-792, Korea
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초록
폴리우레탄 생성을 위한 프리폴리머 중합의 속도론적 연구를 위하여 정량적 분석이 실시간으로 가능한 in-situ IR 분광법을 사용하고 isophorone diisocyanate(IPDI)와 dimethylol propionic acid(DMPA)의 용액중합(IP 반응)과 IPDI와 dimethylol butanoic acid(DMBA)의 용액중합(IB 반응)을 반응온도 60-90 ℃ 및 [NCO]/[OH]=1.0 하에서 수행하였다. 반응 속도는 일련의 IR 스펙트럼에서 NCO 신축진동흡수(2,265 cm-1)의 흡광도 변화를 모니터링하여 얻었다. 반응은 수산기와 이소시아네이트기의 농도에 대하여 각각 1차로 표시할 수 있었으며, 전체적으로는 2차 반응속도 법칙에 따랐다. 반응 속도 상수로부터 구한 활성화 파라미터는 IP 반응의 경우, 활성화 에너지(Eα)=42.2 kJ/mol, 활성화 엔탈피(ΔH‡)=39.3 kJ/mol 및 활성화 엔트로피 (ΔS‡)=-146.7 J/molㆍK이였으며, IB 반응은 Eα=36.9 kJ/mol, ΔH‡34.0 kJ/mol 및 ΔS‡=-163.3 J/molㆍK이었다.
Kinetics of pre-polymerization of polyurethane formation between isophorone diisocyanate (IPDI) and dimethylol propionic acid (DMPA) in solution state (IP reaction), and IPDI and dimethylol butanoic acid (DMBA) in solution state (IB reaction) were studied by using quantitative real-time in-situ IR spectroscopy at different temperatures in the range of 60-90 ℃ with [NCO]/[OH] ratio of 1.0. The reaction rate was obtained from monitoring the change of NCO (2,265 cm-1) stretching band in series IR spectra. The reaction was in accord with the first-order for the concentrations of hydroxyl groups and isocyanate groups respectively, which conformed to the second order law entirely. The activation parameters were obtained from the evaluation of kinetic data as follows. For IP reaction, activation energy (Ea)=42.2 kJ/mol, activation enthalpy (ΔΗ‡)=39.3 kJ/mol and activation entropy (ΔH‡)=-146.7 J/mol K. For IB reaction, Ea=36.9 kJ/mol, ΔH‡=34.0 kJ/mol and ΔS‡=-163.3 J/mol K.
Keywords:Real Time In-situ IR Spectroscopy;Urethane Formation;Kinetics;Dimethylol Propionic Acid;Dimethylol Butanoic Acid;Water-Borne Polyurethane
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