Organic acids as efficient catalysts for group transfer polymerization of N,N-disubstituted acrylamide with silyl ketene acetal: polymerization mechanism and synthesis of diblock copolymers
Organic acids as efficient catalysts for group transfer polymerization of N,N-disubstituted acrylamide with silyl ketene acetal: polymerization mechanism and synthesis of diblock copolymers
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DOI：
10.1039/c5py01104c
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发表时间：
2015-01-01
影响因子：
4.6
通讯作者：
Kakuchi, Toyoji
中科院分区：
文献类型：
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作者：
Kikuchi, Seiya;Chen, Yougen;Kakuchi, Toyoji
使用 N-(三甲基甲硅烷基)双(三氟甲磺酰基)酰亚胺 (Me3SiNTf2)、1-(2,3,4,5,6-五氟苯基)-1,1-双(三氟甲磺酰基)甲烷 (C6F5CHTf2) 和[0072] 三(五氟苯基)硼烷(B(C6F5)(3))和1-甲氧基-1-(三甲基甲硅烷氧基)-2-甲基-1-丙烯(MeSKA)的甲硅烷基乙烯酮缩醛(SKA)、1-甲氧基-1-(三乙基甲硅烷氧基)-2-甲基-1-丙烯(EtSKA)， 1-甲氧基1-(三异丙基硅氧基)-2-甲基-1-丙烯(iPrSKA)和1-甲氧基-1-(三苯基硅氧基)-2-甲基-1-丙烯(PhSKA)，其中B(C6F5)(3)和EtSKA的组合对分子量分布具有相对较好的控制。然后从聚合动力学、扩链实验和 MALDI-TOF MS 分析方面深入研究了使用 B(C6F5)(3) 和 EtSKA 的 DEAA 的聚合行为，结果证明，尽管发生了数十分钟的诱导期，但聚合仍以活跃的方式进行。 B(C6F5)(3)-催化的GTP进一步扩展到各种N,N-二取代丙烯酰胺(DAA)，如N,N-二甲基丙烯酰胺(DMAA)、N,N-二正丙基丙烯酰胺(DnPAA)、N-丙烯酰哌啶(API)、N-丙烯酰吗啉(NAM)、N-(2-甲氧基乙基)-N-甲基丙烯酰胺(MMEAA)、N,N-双(2-甲氧基乙基)丙烯酰胺(BMEAA)、N,N-二烯丙基丙烯酰胺(DA1AA)和N-甲基-N-炔丙基丙烯酰胺(MPAA)。最后利用聚合活性合成了丙烯酰胺-丙烯酰胺嵌段共聚物和甲基丙烯酸酯-丙烯酰胺杂嵌段共聚物。
The group transfer polymerization (GTP) of N,N-diethylacrylamide (DEAA) was studied using various combinations of an organic acid of N-(trimethylsilyl) bis-(trifluoromethanesulfonyl) imide (Me3SiNTf2), 1-(2,3,4,5,6-pentafluorophenyl)-1,1-bis(trifluoromethanesulfonyl) methane (C6F5CHTf2), and tris(pentafluorophenyl) borane (B(C6F5)(3)) and a silyl ketene acetal (SKA) of 1-methoxy-1-(trimethylsiloxy)-2-methyl-1-propene (MeSKA), 1-methoxy-1-(triethylsiloxy)-2-methyl-1-propene (EtSKA), 1-methoxy1-(triisopropylsiloxy)-2-methyl-1-propene (iPrSKA), and 1-methoxy-1-(triphenylsiloxy)-2-methyl-1-propene (PhSKA), among which the combination of B(C6F5)(3) and EtSKA afforded a relatively better control over the molecular weight distribution. The polymerization behavior of DEAA using B(C6F5)(3) and EtSKA was then intensively investigated in terms of the polymerization kinetics, chain extension experiments, and MALDI-TOF MS analyses, by which the polymerization was proven to proceed in a living fashion though an induction period of tens of minutes occurred. The B(C6F5)(3)-catalyzed GTP was further extended to various N, N-disubstituted acrylamides (DAAs), such as N, N-dimethylacrylamide (DMAA), N, N-di-n-propylacrylamide (DnPAA), N-acryloylpiperidine (API), N-acryloylmorpholine (NAM), N-(2-methoxyethyl)-N-methylacrylamide (MMEAA), N, N-bis(2-methoxyethyl) acrylamide (BMEAA), N, N-diallylacrylamide (DAlAA), and N-methyl-N-propargylacrylamide (MPAA). Finally, the livingness of the polymerization was used to synthesize acrylamide-acrylamide block copolymers and methacrylate-acrylamide hetero-block copolymers.