Institute for Chemical Research, Kyoto University, Uji, Kyoto, 611-0011, Japan; Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency, Tokyo, 102-0076, Japan.
Macromol Rapid Commun. 2014 Mar;35(6):642-8. doi: 10.1002/marc.201300855. Epub 2014 Feb 3.
The direct synthesis of structurally well-defined protic polymeric ionic liquid (PIL) with controlled molecular weight and molecular weight distribution is examined using N,N-diethyl-N-(2-methacryloylethyl) ammonium bis(tri-fluoromethylsulfonyl)imide (DEMH-TFSI) as a monomer. Three polymerization methods, namely, atom transfer radical polymerization (ATRP), activators regenerated by electron transfer (ARGET)-ATRP, and organotellurium-mediated living radical polymerization (TERP) are employed in this study. While the polymerization by ATRP is slow and does not reach high monomer conversion that under ARGET-ATRP and TERP proceeds smoothly and affords structurally well-defined poly(DEMH-TFSI)s. TERP is especially efficient for the control and poly(DEMH-TFSI)s with low to high molecular weights (M¯(n) = 49 100-392 500) and narrow molecular weight distributions (M¯(w)/M¯(n) = 1.17-1.46) are obtained. These results represent the first example of synthesis of a structurally well-defined protic, ammonium PIL by direct polymerization of the protic ionic liquid monomer. The polymerization of N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide (DEMM-TFSI), which possesses a quaternary ammonium salt, also proceeds in a highly controlled manner under TERP conditions. A diblock copolymer, polystyrene-block-poly(DEMH-TFSI), is also successfully synthesized by TERP.
采用 N,N-二乙基-N-(2-甲基丙烯酰基乙基)铵双(三氟甲基磺酰基)亚胺(DHME-TFSI)作为单体，研究了具有可控分子量和分子量分布的结构明确的质子聚合物离子液体（PIL）的直接合成。本研究采用三种聚合方法，即原子转移自由基聚合（ATRP）、电子转移再生剂（ARGET）-ATRP 和有机碲介导的活性自由基聚合（TERP）。虽然 ATRP 聚合速度较慢，且未达到高单体转化率，但 ARGET-ATRP 和 TERP 聚合则进行得很顺利，可得到结构明确的聚（DHME-TFSI）。TERP 特别适用于控制和聚合低至高分子量（M¯(n) = 49 100-392 500）和窄分子量分布（M¯(w)/M¯(n) = 1.17-1.46）的聚（DHME-TFSI）。这些结果代表了首例通过直接聚合质子离子液体单体合成结构明确的质子型、铵基 PIL 的实例。具有季铵盐的 N,N-二乙基-N-(2-甲基丙烯酰基乙基)-N-甲基铵双（三氟甲基磺酰基）亚胺（DEMM-TFSI）的聚合在 TERP 条件下也以高度可控的方式进行。还通过 TERP 成功合成了聚苯乙烯嵌段聚（DHME-TFSI）的两嵌段共聚物。
