Article
  • Modification of Chlorinated Isotactic Polypropylene by Phase Transfer Reacton
  • Park IH, Song BK, Kim YW, Choi KY
  • 상간이동반응에 의한 염소화 이서탁틱 폴리프로필렌의 구조변환
  • 박인환, 김영운, 송봉근, 최길영
Abstract
The chemical modifications of chlorinated isotactic polypropylene(IPP) were performed by using two nucleophiles such as thiophenol and sodium cyanide in the presence of phase transfer catalysts. The modifications were influenced by the kinds of reaction solvents, nucleophiles and catalysts. That is, the modifications by using chlorinated aromatic solvents such as chlorobenzene and o-dichlo-robenzene were more effective than those by using chlorinated aliphatic solvents such as chloroform and carbon tetrachloride. Phenylthiolate ion as nucleophile was useful to get the modified polymers at temperatures below 60℃, whereas the polymers modified by using cyanide ion could be gained only at high temperatures above 90℃. The activity of phase transfer catalysts in the modifications increased in the order TBPB(tetrabutyl phosphonium bromide)>TBAB(tetrabutyl ammonium bromide)>Adogen 464(methyltrialkyl ammonium chloride). In DSC and TGA, all the modified polymers had one glass transition temperature(Tg) near Tg of chlorinated IPP, and began weight loss form decomposition above 185℃. The thermal stabilities of the polymers containing phenylthio groups compared to both the chlorinated IPP and the polymers containing cyano groups were relatively good. The polymers containing a lot of phenylthio gorups newly showed to be soluble in polar solvents such as MEK, cyclohexanone and 1,4-dioxane, but were insoluble in a nonpolar solvent like cyclohexane.

염소화 이소탁틱 폴리프로필렌(IPP)에 대한 구조변환이 상간이동촉매 존재하에서 치오페놀, 시안화나트륨등에 의한 친핵치환반응으로 이루어졌다. 그 변환은 반응용매, 친핵시약, 촉매등에 영향을 받았으며, 클로로포름, 사염화탄소등의 염소화 지방족용매에 비해 클로로벤젠. o-디클로로벤젠과 같은 염소화 방향족 용매가 더욱 효과적이었고, 페닐치올레이트 이온은 60℃ 이하의 온도에서도 변환용 친핵시약으로 유용하였지만 시아나이드 이온은 90℃이상의 높은 온도에서만 변환이 가능하였다. 촉매의 활동력은 TBPB(테트라부틸 포스포늄 브로마이드)>TBAB(테트라부틸 암모늄 브로마이드>Adogen 464(메틸트리알킬 암모늄 클로라이드)순이었다. DSC 및 TGA의 열분석에 의해서 구조변환된 모든 염소화 IPP수지들은 염소화 IPP의 Tg 근처에서 1개의 Tg를 가졌으며, 185℃이상의 온도에서 초기 열분해에 의한 중량감소를 보였다. 또 페닐치오기로 구조변환된 염소화 IPP의 열안정성은 염소화 IPP나 시아노기로 구조변환된 염소화 IPP에 비해 상대적으로 양호했다. 특히 페닐치오기로 구조변환된 염소화 IPP수지는 MEK, 시클로헥사논, 1.4-디옥산과 같은 극성용매들에도 새롭게 용해성을 가졌으면. 시클로헥산의 비극성용매에서는 불용해성이었다.

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

  • 1993; 17(1): 74-84

    Published online Jan 25, 1993