Article
  • Kinetics of Polymerization of L-Proline NCA
  • Kim KY, Suh HS, Lee YM, Chung WC
  • L-Proline NCA의 중합반응속도
  • 김계용, 서한수, 이영무, 정우창
Abstract
Rate constants of polymerization of L-proline NCA initiated by n-butylamine in acetonitrile and benzene were determined by measuring the CO2 evolved in the reaction. Although the reaction systems were heterogeneous (both acetonitrile and benzene were nonsolvent for poly-L-proline), the rate of polymerization could be represented as second order rate equation which was first order with respect to monomer and initiator concentrations respectively. The polymerization rate of L-proline NCA proceeded fast at the early stage of polymerization(up to about 30 minutes) but considerably slow in the ensuing stage of polymerization. The reaction rate constants were obtained at temperatures ranging from 0℃ to 35℃. The activation energies for fast and slow polymerization, Ef and Es were determined; in acetonitrile, Ef=8.1kcal/mole and Es=2.2kcal/mole, and in benzene E''f=5.3kcal/mole and E''s=2.5kcal/mole, respectively. The polymerization rate of L-proline NCA in benzene showed lower transition point than that in acetonitrile at low degree of polymerization. It was postulated that the structures of polymers obtained in acetonitrile and benzene solvents might be different.

아세토니트릴 및 벤젠 용매중에서 각각 n-부틸아민에 의해 개시되는 L-proline NCA의 중합반응속도를 반응중 발생하는 CO2량을 측정함으로서 구하였다. 아세토니트릴 및 벤젠은 poly-L-proline의 용매가 아니므로 불균일반응계이지만 중합속도는 모노머와 개시제의 농도에 각각 1차로 표시되었다. 아세토니트릴 및 벤젠 용매중에서 각각 중합초기의 성장속도는 상당히 빠르며 중합이 어느정도 진행된 후에는 중합속도가 느려지는 현상을 나타내었다. 반응속도가 빠른 단계와 느린 단계에서의 속도정수를 0~35℃에서 구하였다. 중합속도가 빠를때의 활성화에너지(Es)와 느릴때의 활성화에너지(Ef)를 측정한 결과 아세토니트릴 용매에서는 Ef=8.1kcal/mole 및 Es=2.2kcal/mole이고 벤젠용매에서는 E''f=5.3kcal/mole 및 E''s=2.5kcal/mole이었다. 벤젠용매에서의 중합시가 아세토니트릴용매에서 보다 중합도가 낮은 점에서 반응속도가 느려지는 것을 알 수 있는데 이것은 중합시 생성하는 poly-L-proline의 구조 차이에서 오는 결과로 간주된다.

Keywords:

  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2022 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 1978; 2(4): 197-203

    Published online Aug 25, 1978

  • 10.7317/pk.
  • Received on Nov 30, -0001
  • Revised on Nov 30, -0001
  • Accepted on Nov 30, -0001

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