Synthesis of Syndiotactic-Rich Star-Shaped Poly(methyl methacrylate) by Core-First Group Transfer Polymerization Using N-(Trimethylsilyl)bis(trifluoromethanesulfonyl)imide
Synthesis of Syndiotactic-Rich Star-Shaped Poly(methyl methacrylate) by Core-First Group Transfer Polymerization Using N-(Trimethylsilyl)bis(trifluoromethanesulfonyl)imide
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N-(三甲基硅基)双(三氟甲磺酰基)亚胺通过先核基团转移聚合合成间同立构星形聚甲基丙烯酸甲酯
DOI：
10.1002/pola.26123
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发表时间：
2012
期刊：
影响因子：
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通讯作者：
陳友根
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作者：
小野口真広;小野口真広;小林亮介;小林亮介;小林亮介;小林亮介;小林亮介;小林亮介;小林亮介;小林亮介;小林亮介;小林亮介;小林亮介;小林亮介;小林亮介;小林亮介;小林亮介;Ryosuke Kobayashi;小林亮介;小林亮介;陳友根
研究了甲基丙烯酸甲酯的TheN‐(trimethylsilyl)bis(trifluoromethanesulfonyl)imide‐catalyzed(Me3SiNTf2催化)基团转移聚合反应，合成了立体定向星形聚甲基丙烯酸甲酯S(PMMA)。通过动力学研究和基质辅助激光解吸电离飞行时间质谱仪测定了Me_3SiNTf_2对甲基丙烯酸甲酯以1‐methoxy‐1‐trimethylsilyloxy‐2‐methyl‐propene为引发剂的GTP的催化性能。Me_3SiNTf_2的引发效率(F)为0.94-1.00，用Mn(Calcd)/Mn(Sec)值估算。在−为55°C，[MMA]0/[MTS_3，MTS_4，或MTS_6]=120的条件下，Me_3SiNTf_2催化甲基丙烯酸甲酯的GTP反应中，具有三个、四个和六个MTS基团(分别为MTS_3、MTS_4和MTS_6)的引发剂催化Me_3SiNTf_2催化的甲基丙烯酸甲酯的GTP。得到的PMMA呈现单峰窄相对分子质量分布，Mw/MNS=1.03~1.04，3-、4-和6-臂星形PMMA(PMMA3、PMMA4和PMMA6)的Mw(MAL)S分别为12.9、12.9和13.4kgmol−这与计算的Mw(Calcd)值相当吻合。PMMA3、PMMA4和PMMA6的相对标准偏差在87-%之间。PMMA3、PMMA4和PMMA6的立体嵌段合成分别在−55℃和45℃下进行，第一次和第二次聚合的产率分别为87.0%、87.0%和86.0%，分别为65.0%、65.0%和64.0%。富间规PMMA3、PMMA4和PMMA6的玻璃化转变温度(Tg)分别为118.1、115.8和111.5℃，立构嵌段PMMA3、PMMA4和PMMA6的玻璃化转变温度分别为111.5、109.7和107.6℃。2012 Wiley期刊公司J Polym Sci Part A：Polym Chem，2012
TheN‐(trimethylsilyl)bis(trifluoromethanesulfonyl)imide‐catalyzed (Me3SiNTf2‐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 Me3SiNTf2for 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 Me3SiNTf2was 0.94–1.00, which was estimated by the value ofMn(calcd)/Mn(SEC). The Me3SiNTf2‐catalyzed GTP of MMA was carried out using initiators possessing three, four, and six MTS groups (MTS3, MTS4, and MTS6, respectively) under the condition of [MMA]0/[MTS3, MTS4, or MTS6]0= 120 at −55 °C. All the obtained PMMAs exhibited unimodal and narrow molecular weight distributions asMw/Mns = 1.03–1.04 and theMw(MALS)s of the 3‐, 4‐, and 6‐armed star‐shaped PMMAs (PMMA3, PMMA4, and PMMA6, respectively) were 12.9, 12.9, and 13.4 kgmol−1, respectively, which fairly agreed with the calculatedMw(calcd)values. The syndiotacticities,rrs, of PMMA3, PMMA4, and PMMA6were in the range of 87–89%. The stereoblock synthesis of PMMA3, PMMA4, and PMMA6was performed by the first and second polymerizations at −55 and 45 °C; therrs 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 (Tgs) were 118.1, 115.8, and 111.5 °C for the respective syndiotactic‐rich PMMA3, PMMA4, and PMMA6and 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