Article
  • Discrimination of the Copolymerization Kinetic Model Using a Pulsed Laser-induced Polymerization Technique
  • Kim Y, O'Driscoll KF
  • 펄스 레이저유도 중합 기법을 이용한 공중합 반응역학 모델의 규명
  • 김양수, O'Driscoll KF
Abstract
In an effort to discriminate the copolymerization kinetic model, the overall propagation rate constant (κp) depending upon the feed monomer composition was determined by analyzing the copolymer formed using a pulsed UV-laser light source. A reliability of the copolymer ㏖ecular weight estimation was improved by carrying out the combined analysis of UV/DRI and on-line viscormeter as a multi-detector in the GPC analysis of the copolymer produced. The butyl acrylate (BA)-methyl methacrylate (MMA) copolymerization was characterized by the terminal model with respect to the copolymer composition, however, it conformed to the penultimate model regarding κp. The relationship, r1r2=s1s2, which is known to be held in the most copolymerization systems characterized by the penultimate propagation model, has been also proved in the BA-MMA copolymerization. The application of a PLP technique to the ST-MMA copolymerization in the presence of zinc chloride showed the terminal model different from the same copolymerization system in the absence of Lewis acid which is characterized by the penultimate model with respect to theoverall propagation rate constant. It has been also shown that the addition of zinc chloride causes to increase the propagation rate remarkably.

공중합 반응모델을 규명하기 위하여 pulsed UV-laser light source를 이용하여 얻어진 공중합체의 GPC chromatogram 분석을 수행함으로써 반응초기의 단량체 혼합물 조성에 따라 변화하는 공중합 반응의 총괄 성장반응 속도상수 (κp)값을 결정하였다. 이때 공중합체 분자량 결정의 신뢰성을 높이기 위하여 GPC 분석은 UV/DRI 및 on-line viscometer를 multidetector로 이용하였다. Butylacrylate (BA)-methyl methacrylate (MMA) 공중합의 경우 공중합 조성의 관점에서는 terminal model을 잘 따르나 κp에 대하여는 penultimate model에 의하여 공중합 성장반응이 설명되어졌으며, 대부분의 penultimate model을 따르는 공중합계에서와 마찬가지로 BA-MMA계에서도 r1r2=s1s2의 관계가 성립되었다. 한편, Lewis acid로서 zinc chloride가 소량 첨가된 styrene (ST)-MMA 공중합계에 PLP 방법을 적용한 결과 κ2에 관하여 terminal model이 적용되었으며 이것은 동일한 공중합계에 Lewis acid를 첨가하지 않았을 경우와 전혀 다른 결과를 보여주었다. 공중합 반응의 성장반응 속도는 Lewis acid를 첨가함으로써 크게 증가되었다.

Keywords: copolymerization model; terminal model; penultimate model; overall prpagation rate constant; copolymer composition

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  • Polymer(Korea) 폴리머
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    ISSN 2234-8077(Online)
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This Article

  • 1996; 20(3): 462-469

    Published online May 25, 1996