《Table 1 Characterization of PMMA macroinitiators initiated by TsCl or EBPA》

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《Effect of Halogen Chain End Fidelity on the Synthesis of Poly(methyl methacrylate-b-styrene) by ATRP》

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a[Initiator]/[CuX]/[bpy]/[MMA]/[anisole]=1/1/2/600/600；b[Initiator]/[CuX]/[bpy]/[MMA]=1/1/2/1200；c Measured by GPC using THF as eluent based on PMMA standards.All reactions were carried out at 60°C.

In order to compare the effect of the halogen chain end on the synthesis of PMMA-b-PS，EPBA and TsCl were chosen as the initiators to synthesize bromide/chloride terminated PMMA-Br and PMMA-Cl macroinitiators because they showed similar initiation rates under the same polymerization conditions and the resulting PMMAs had similar molecular weights and narrow PDIs（Scheme 1a）[22，23].The polymerization was performed both in bulk and in anisole solution and the target number-average molecular weight（Mn）was~50 kg/mol.The polymerization time and the conversion of MMA monomers were very close when the target Mn of PMMA was the same for the EPBA/CuBr/bpy and TsCl/CuCl/bpy initiation systems in bulk（Table 1）.However，when the polymerization was performed in anisole solutions，a shorter polymerization time was needed to achieve the same molecular weight for the EPBA/CuBr/bpy system.Compared to the TsCl/CuCl/bpy system，the monomer conversion was also lower for the EPBA/CuBr/bpy system，but it was proportional to the polymerization time.A lower monomer conversion required for the same molecular weight using theEPBA/CuBr/bpy system might be caused by a higher coupling rate.These two sets of data showed that the polymerization of MMA using the EPBA/CuBr/bpy and TsCl/CuCl/bpy initiation systems had similar polymerization rates.