화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.20, No.10, 1037-1043, October, 2012
DOI10.1007/s13233-012-0145-8  Export Citation
Monodisperse PS-b-PMMA Copolymers by Click Chemistry: A Mild Dehydrobromination of the PMMA End via Tetra-n-Butylammonium Fluoride
Jie Song, and Byoung-Ki Cho†
  • Department of Chemistry and Institute of Nanosensor and Biotechnology, Dankook University, Gyeonggi, 448-701, Korea
E-mail:
We reported a synthetic protocol of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) copolymers via dehydrobromination and click coupling reactions. The PS block (acetylene-PS) was prepared by anionic polymerization and end-functionalized with an acetylene group. The other PMMA block was synthesized by an atom transfer radical polymerization (ATRP) of MMA using an azido-initiator. It was found, unexpectedly, that the click reaction of acetylene-PS and the bromide-ended PMMA using Cu(I)Br yielded a byproduct with double the molecular weight of the product (PS-b-PMMA). This was attributed to the coupling of the bromide ends of block copolymers. This problem could be avoided by a dehydrobromination of the PMMA block into the olefin end (azido-PMMA-ene) using tetra-n-butylammonium fluoride (TBAF) at room temperature. Due to the mild dehydrobromination condition and the weak basicity of TBAF, no hydrolysis of PMMA esters occurred. After the click coupling of acetylene-PS and azido-PMMA-ene, the excess PS was removed by further click reaction using insoluble PS resins surface-functionalized with azide groups.
Keywords:click chemistry;dehydrobrominaiton;block copolymers;atom transfer radical polymerization.
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