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• W2115638438 abstract "Abstract The N ‐(trimethylsilyl)bis(trifluoromethanesulfonyl)imide‐catalyzed (Me 3 SiNTf 2 ‐catalyzed) group transfer polymerization (GTP) of methyl methacrylate (MMA) has been studied for synthesizing stereospecific star‐shaped poly(methyl methacrylate)s (PMMAs). The catalytic property of Me 3 SiNTf 2 for the GTP of MMA using 1‐methoxy‐1‐trimethylsilyloxy‐2‐methyl‐propene as the initiator was confirmed by a kinetic investigation and matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry measurement. The initiating efficiency ( f ) of Me 3 SiNTf 2 was 0.94–1.00, which was estimated by the value of M n(calcd) / M n(SEC) . The Me 3 SiNTf 2 ‐catalyzed GTP of MMA was carried out using initiators possessing three, four, and six MTS groups (MTS 3 , MTS 4 , and MTS 6 , respectively) under the condition of [MMA] 0 /[MTS 3 , MTS 4 , or MTS 6 ] 0 = 120 at −55 °C. All the obtained PMMAs exhibited unimodal and narrow molecular weight distributions as M w / M n s = 1.03–1.04 and the M w(MALS) s of the 3‐, 4‐, and 6‐armed star‐shaped PMMAs (PMMA 3 , PMMA 4 , and PMMA 6 , respectively) were 12.9, 12.9, and 13.4 kgmol −1 , respectively, which fairly agreed with the calculated M w(calcd) values. The syndiotacticities, rr s, of PMMA 3 , PMMA 4 , and PMMA 6 were in the range of 87–89%. The stereoblock synthesis of PMMA 3 , PMMA 4 , and PMMA 6 was performed by the first and second polymerizations at −55 and 45 °C; the rr s of the first and second PMMA blocks were 87.0, 87.0, and 86.0% and 65.0, 65.0, and 64.0%, respectively. The glass transition temperatures ( T g s) were 118.1, 115.8, and 111.5 °C for the respective syndiotactic‐rich PMMA 3 , PMMA 4 , and PMMA 6 and 111.5, 109.7, and 107.6 °C for the respective stereoblock ones. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012" @default.
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• W2115638438 date "2012-05-16" @default.
• W2115638438 modified "2023-10-18" @default.
• W2115638438 title "Synthesis of syndiotactic-rich star-shaped poly(methyl methacrylate) by core-first group transfer polymerization using <i>N</i> -(trimethylsilyl)bis(trifluoromethanesulfonyl)imide" @default.
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• W2115638438 doi "https://doi.org/10.1002/pola.26123" @default.
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