Kumada catalyst transfer polycondensation for controlled synthesis of polyfluorenes using 1,3-bis(diarylphosphino)propanes as ligands
文献类型：期刊论文
| 作者 | Sui, Aiguo1,2; Shi, Xincui1; Wang, Yongxia1; Geng, Yanhou1; Wang, Fosong1 |
| 刊名 | POLYMER CHEMISTRY
 |
| 出版日期 | 2015 |
| 卷号 | 6期号:26页码:4819-4827 |
| 英文摘要 | Three new bis(diphenylphosphino) propane (dppp) derivatives, i.e., 1,3-bis(di(4-methylphenyl)phosphino)propane (L1), 1,3-bis(di(3-methylphenyl)phosphino)propane (L2) and 1,3-bis(di(2-methylphenyl)phosphino)propane (L3), were synthesized for studying the effect of the ligand on the Kumada catalyst transfer polycondensation (KCTP) of 7-bromo-9,9-dialkylfluorenylmagnesium chloride (M1) using Ni(acac)(2)/L (L = dppp, L1, L2 or L3) as the catalyst. Ni(acac)(2)/L1 exhibited a polymerization performance comparable to Ni(acac)(2)/dppp, and the polymerization could be well-controlled with >= 1 mol% catalyst. When the most hindered ligand L3 was used, the polymerization was out-of-control and only poly(9,9-dioctylfluorene)s (PF8s) with relatively low number-average molecular weights (M-n) and large polydispersity indices (PDIs) could be obtained. In contrast, the moderately hindered catalyst Ni(acac)(2)/L2 outperformed Ni(acac)(2)/dppp. The polymerization was well-controlled with a catalyst of >= 0.5 mol%, as confirmed by the linear correlation of M-n versus [monomer]/[Ni], and PF8s with M-n up to 91.1 kDa and fluorene-thiophene block copolymers (PF8-b-P3HTs) with M-n up to 78.4 kDa could be prepared in a controlled manner. Density functional theory (DFT) calculations, P-31 NMR spectroscopy studies and block copolymerizations revealed that the great performance of L2 can be attributed to the stronger affinity of the L2Ni(0)-polymer p-complex and the higher stability of active chain ends. The active chain ends of the high molecular weight polymers were unstable, probably owing to unknown side reactions assisted by chain aggregation or entanglement, which may be responsible for the out-of-control nature of the polymerization at low catalyst loadings. |
| 收录类别 | SCI |
| 语种 | 英语 |
| 公开日期 | 2015-11-02 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/27988]  |
| 专题 | 化学研究所_高分子物理与化学实验室 |
| 作者单位 | 1.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China 2.Chinese Acad Sci, Grad Sch, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Sui, Aiguo,Shi, Xincui,Wang, Yongxia,et al. Kumada catalyst transfer polycondensation for controlled synthesis of polyfluorenes using 1,3-bis(diarylphosphino)propanes as ligands[J]. POLYMER CHEMISTRY,2015,6(26):4819-4827. |
| APA | Sui, Aiguo,Shi, Xincui,Wang, Yongxia,Geng, Yanhou,&Wang, Fosong.(2015).Kumada catalyst transfer polycondensation for controlled synthesis of polyfluorenes using 1,3-bis(diarylphosphino)propanes as ligands.POLYMER CHEMISTRY,6(26),4819-4827. |
| MLA | Sui, Aiguo,et al."Kumada catalyst transfer polycondensation for controlled synthesis of polyfluorenes using 1,3-bis(diarylphosphino)propanes as ligands".POLYMER CHEMISTRY 6.26(2015):4819-4827. |
入库方式： OAI收割
来源：化学研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。