화학공학소재연구정보센터
Polymer(Korea), Vol.45, No.3, 428-436, May, 2021
백금계 촉매와 Hydrosilane 개시제를 이용한 아세트산 비닐 합성
Polymerization of Vinyl Acetate Initiated by Hydrosilane in the Presence of Platinum Complex
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In this work, a series of hydrosilanes including phenylsilane, diphenylsilane, triethylsilane (TES), and tris(trimethylsilyl)silane combined with catalytical amount of platinum complex such as dichloro(1,5-cyclooctadiene) platinum (COD) and dichloro(dicyclopentadienyl)platinum have been used to initiate the polymerization of vinyl acetate (VAc) at 70-95 ºC. An ultrahigh molecular weight PVAc with number-average molecular weight (Mn) up to 1.17×106 Da and polydispersity index (PDI) of 2.59 has been synthesized using TES as an initiator in the presence of 9.7 ppm of COD. A kinetic study indicates that the polymerization at VAc/TES/COD molar ratio = 3.0×105 : 60 : 1 smoothly reached 81.0% conversion in 28.0 h at 85 ºC, producing PVAc with Mn increasing linearly from 1.41×105 to 6.01×105 Da with the increase of monomer conversion. A mechanistic investigation revealed that COD was firstly reduced by reductive TES, producing Pt nanoparticles and corresponding silane radicals to initiate the polymerization of VAc.
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