Synthesis of traditional and ionic polymethacrylates by anion catalyzed group transfer polymerization

Abstract

The hydrophobic ionic liquid 1-butyl-1methylpyrrolidinium bis(trifluoromethylsulfonyl)imide was successfully used as solvent in group transfer polymerization of traditional methacrylates (methyl methacrylate, n-butyl methacrylate, and benzyl methacrylate) and of ionic liquid methacrylates (ILMAs). This demonstrates that this ionic liquid makes reaction conditions, which do not require the use of ultra-dried solvents. The ILMAs were N-[2-(methacryloyloxy)ethyl]-N,N-dimethyl-N-alkylammonium bis(trifluoromethylsulfonyl)imides bearing methyl, ethyl, propyl, butyl, or hexyl substituents. Increasing size of the alkyl substituent at the cation results in decreasing glass transition temperature in case of both ionic liquid methacrylates and polymers derived of them. Furthermore, the glass transition temperature is significantly higher for these polymers compared with the ionic liquid methacrylates, and the effect of glass transition temperature reduction with increasing size of the alkyl substituent is stronger for the polymers. A mechanism was proposed explaining the catalytic function of the ionic liquid used as solvent for polymerization.

Effects of Ionic Liquids on the Nucleofugality of Chloride

“…(lit. 84 1 -B u t y l -1 -m e t h y l p y r r o l i d i n i u m B i s -(trifluoromethanesulfonyl)imide7. 82 1-Butyl-1-methylpyrrolidinium bromide (35.2 g, 0.158 mol) and lithium bis-(trifluoromethanesulfonyl)imide (49.9 g, 0.174 mol) were dissolved in water (150 mL) and the resultant mixture was stirred at room temperature for 20 h. During this time, two immiscible layers formed.…”

An Architype-Cation-Based Room Temperature Ionic Liquid: Aliphatic-Primary-Ammonium Bis(Trifluoromethylsulfonyl)Imide as An Additive for Hole Transport Layers in Perovskite Solar Cells Allowing Spontaneous Passivation of The Perovskite Layer

“…The OA-TFSI was synthesized via an ion exchange method 24 between Li-TFSI and n-octyl-ammonium chloride, followed by purification. (See SI for the details) The remained Li amount in the synthesized sample was measured by inductively coupled plasma (ICP) and estimated to be only 2.8 ppm, and hence, the OA-TFSI formation via the ion exchange successfully proceeded.…”

Archetype-Cation-Based Room-Temperature Ionic Liquid: Aliphatic Primary Ammonium Bis(trifluoromethylsulfonyl)imide as a Highly Functional Additive for a Hole Transport Material in Perovskite Solar Cells

“…The OA-TFSI RTIL was synthesized via an ion exchange between Li-TFSI and n -octylammonium chloride, followed by purification (see the Supporting Information). The amount of Li remaining in the product was measured by using inductively coupled plasma, which was found to be only 2.8 ppm.…”