Elastomers and Composites

The Rubber Society of Korea (한국고무학회)
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Dispersion Polymerization of Acrylate Monomers in Supercritical $CO_2$ using GMA-functionalized Reactive Surfactant

초임계 이산화탄소에서 Glycidyl methacrylate 반응성 계면활성제를 이용한 아크릴레이트의 분산중합

  • Received : 2010.07.20
  • Accepted : 2010.10.18
  • Published : 2010.12.31
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Abstract

Dispersion polymerization of methyl acrylate, ethyl acrylate, butyl acrylate, and glycidyl methacrylate were performed in supercritical $CO_2$ at $80\;^{\circ}C$ and 346 bar. Glycidyl methacrylate linked poly(dimethylsiloxane) (GMS-PDMS) surfactant, which was prepared by linking glycidyl methacrylate to monoglycidyl ether terminated PDMS with amino-propyltriethoxysilane, was used as surfactant for the dispersion polymerization in $CO_2$. The yield of the poly(alkyl acrylate) polymers, synthesized in $CO_2$ medium, decreased as the alkyl tail of the acrylate monomers increased. Poly(glycidyl methacrylate) and poly(methyl acrylate) were produced in bead form whereas poly(ethyl acrylate) and poly(butyl acrylate) were viscous liquid. The poly(glycidyl methacrylate) particles had a number average diameter of 2.45 ${\mu}m$ and monodisperse distribution. The poly(methyl acrylate) had a number average diameter of 0.52 ${\mu}m$ and the particle size distribution was bimodal. The glass transition temperatures ($T_g$) of the poly(glycidyl methacrylate) and the poly(alkyl acrylate) products were 4~9 K higher than the $T_g$ of the corresponding acrylate polymers synthesized in conventional processes.

[ $80\;^{\circ}C$ ] 346 bar 상태의 초임계 이산화탄소 내에서 methyl acrylate, ethyl acrylate, butyl acrylate와 glycidyl methacrylate을 중합하였다. 초임계 이산화탄소 분산매에서의 중합을 위하여 aminopropyltriethoxysilane을 사용하여 glycidyl methacrylate를 monoglycidyl ether terminated PDMS에 결합시킨 glycidyl methacrylate linked poly(dimethylsiloxane)(GMS-PDMS)를 계면활성제로 사용하였다. $CO_2$에서 합성된 Poly(alkyl acrylate)의 수율은 acrylate 단량체의 알킬기가 커질수록 낮아졌다. Poly(glycidyl methacrylate)와 poly(methyl acrylate)는 구형으로 만들어진 반면, poly(ethyl acrylate)와 poly(butyl acrylate)는 점성의 액상으로 합성되었다. Poly(glycidyl methacrylate) 입자의 수평균직경은 2.45 ${\mu}m$이며 입자 직경의 분포는 매우 좁았다. poly(methyl acrylate)의 수평균직경은 0.52 ${\mu}m$이며 입자크기는 bimodal로 분포되었다. 초임계 이산화탄소에서 중합된 poly(glycidyl methacrylate)와 poly(alkyl acrylate)들의 유리전이온도는 통상의 방법으로 중합된 poly(glycidyl methacrylate)와 poly(alkyl acrylate)의 유리전이온도보다 4~9 K 높게 측정되었다.

Keywords

References

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