Synthesis of ionic polymers by free radical polymerization using aprotic trimethylsilylmethyl‐substituted monomers

Abstract

Aprotic ionic polymers containing trimethylsilylmethyl-substituted imidazolium structures are synthesized using free radical polymerization of monomers comprising a vinyl group either at the cation or at the anion. Bulk polymerization is used for the room temperature ionic liquid monomer 1-trimethylsilylmethyl-3-vinylimidazolium bis(trifluoromethylsulfonyl)imide. In contrast to this, solution polymerization is applied for 1-trimethylsilylmethyl-3-methylimidazolium p-styrene sulfonate because this monomer undergoes self-polymerization during melting at a higher temperature than selected for bulk polymerization.Glass transition temperature (T g ) of the ionic polymers and intrinsic viscosity measurements indicate differences between these polymers, which are composed either of a polycation with a trimethylsilylmethyl substituent at each vinylimidazolium segment of the polymer chain and mobile bis(trifluoromethylsulfonyl)imide (NTf 2 − ) anions or a polyanion containing p-styrene sulfonate segments and mobile 1-trimethylsilylmethyl-3methylimidazolium cations. The new aprotic ionic polymers containing trimethylsilylmethyl substituents may be interesting for application in adhesive, interlayer and membrane manufacturing.free radical polymerization, glass transition temperature, intrinsic viscosity, ionic liquid monomers, polymerizable cation, polymerizable anion, trimethylsilylmethyl substituted ionic liquids

Synthesis and photoinitiated polymerization of new ionic liquid methacrylates

“…1-trimethylsilylmethyl-3-vinylimidazolium bis(trifluoromethyl sulfonyl)imide (SiVIm-NTf 2 ), and 1-trimethylsilylmethyl-3-methylimidazolium styrene sulfonate (SiMIm-Su) is described elsewhere. 9,16 2.3 | Synthesis of ionic liquid dimethacrylates 2.3.1 | 1,4-Bis-(N,N-dimethyl-N-2-methacryloyloxyethyl ammonio) butane diiodide 1,4-Bis-(N,N-dimethyl-N-2-methacryloyloxyethyl ammonio) butane diiodide (ILDiMA-I) was made from 2-(dimethylamino)ethyl methacrylate (45.36 g, 0.289 mol, 2.0 equiv.) dissolved in 100 ml t-butyl methyl ether and 1,4-diiodobutane (44.71 g, 0.144 mol, 1.0 eq.)…”

“…Furthermore, synthesis of 1-trimethylsilylmethyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide (SiMIm-NTf 2 ) is described elsewhere. 16 2.5 | Methods 1 H NMR (300 MHz) and 13 C NMR (75 MHz) spectra were taken with a Bruker Fourier 300 spectrometer. Infrared spectra were recorded on a Bruker FT-IR ALPHA instrument.…”

“…T A B L E 2 Maximum of the polymerization rate (R p max ), time (t max ) to obtain the R p max value, final conversion determined by both photo-DSC and 1 H NMR spectroscopy after 10 min irradiation of the ionic liquid methacrylates comprising NTf 2 as anion and a variation of the alkyl substituent at the ammonium ion (methyl (ILMA-M-NTf 2 ), ethyl (ILMA-E-NTf 2 ), propyl (ILMA-P-NTf 2 ), butyl (ILMA-B-NTf 2 ), and hexyl (ILMA-H-NTf 2 )) and the ionic liquid dimethacrylate (ILDiMA-NTf 2 ), a mixture of ILMA-B-NTf 2 and ILDiMA-NTf 2 as well as vinylimidazolium based ionic liquids such as N-butyl-N 0 -vinylimidazolium bis(trifluoromethylsulfonyl)imide (BVImNTf 2 ) and Ntrimethylsilylmethyl-N 0 -vinylimidazolium bis(trifluoromethylsulfonyl)imide (SiVImNTf 2 ) at 40 C in the presence of bis-4-(methoxybenzoyl) diethylgermane as photoinitiator using a LED emitting at 395 nm, and the glass transition temperature (T g ) of the polymers determined by DSC SiVImNTf 2 (T g : À20 C) 16 0.0005 149 9 n.d. 61 16 3.4 | Photoinitiated polymerization of ionic liquid monomers in solution using an ionic liquid as solvent…”

“…Furthermore, ionic liquids substituted with at least one polymerizable functional group are called ionic liquid monomers 8–16 . Mostly, imidazolium or ammonium based ionic liquid monomers have been investigated comprising one polymerizable functional group.…”

“…7 Furthermore, ionic liquids substituted with at least one polymerizable functional group are called ionic liquid monomers. [8][9][10][11][12][13][14][15][16] Mostly, imidazolium or ammonium based ionic liquid monomers have been investigated comprising one polymerizable functional group. Furthermore, bis(trifluoromethylsulfonyl)imide was selected as anion in many examples.…”