Ionically conducting and photoresponsive liquid crystalline terpolymers: Towards multifunctional polymer electrolytes

Abstract

We have prepared a series of new ionically conducting polymer electrolytes consisting of side-chain liquid crystal terpolymers with mesogenic azobenzenes, sulfonic acid groups and methyl methacrylate. The poly[10-(4-methoxyazobenzene-4'-oxy)decyl methacrylate]-copoly[2-acrylamido-2-methyl-1-propanesulfonic acid]-co-poly[methyl methacrylate]s, 10-MeOAzB/AMPS/MMA terpolymers, were synthesised by a one-pot conventional radical polymerisation. All samples were characterised by NMR, GPC/SEC, FT-IR, POM, XRD, DSC, UV-visible spectrophotometry and EIS. The terpolymers have light responsive properties, and exhibit liquid crystallinity over a wide range of compositions. Above a certain threshold of AMPS content, the 10-MeOAzB/AMPS/MMA terpolymers exhibit ionic conductivities in the 10-8-10-4 S cm-1 range, with signs of decoupling of ionic mobility from segmental motions of the polymer.

Liquid Crystalline Copolymers Containing Sulfonic and Light-Responsive Groups: From Molecular Design to Conductivity

“…We note, however, that our polymers have reasonable Mw/Mn values (Mw/Mn < 2.1) and high molecular weights, in the 10-40k g mol −1 range. The addition of AMPS increases both the molecular weight and polydispersity, but it is noteworthy that our Mw/Mn values are smaller than other copolymers with comparable (moderate and high) sulfonic groups concentrations [37,40,[52][53][54]. This fact is particularly challenging, considering the different reactivity rates of the three monomers involved [41][42][43].…”

“…For the sake of comparison, we have synthesised one statistical terpolymer containing the three monomeric units, P(MeOAzB 0.18 -co-AMPS 0.47 -co-MMA 0.35 ), also obtained by RAFT polymerisation, P(A-co-S-co-M). We note that the structures of P(A-co-S) and P(A-co-S-co-M) can be compared to our previous materials studied in [40] and [37], respectively. Diblock copolymers PMeOAzB 25 -b-PMMA 22 (PA-b-PM) and PMMA 136 -b-PAMPS 471 (PM-b-PS) have been prepared as reference materials, by polymerising a second monomer to the corresponding macro-CTAs, PA and PM.…”

“…In the search to achieve anhydrous ionic conductivity, during the past few years we have prepared and characterised new liquid crystalline copolymers containing sulfonic groups [37][38][39][40]. In a recent contribution, we synthesised statistical side-chain terpolymers capable to form smectic phases with promising conductivity values in anhydrous conditions [37]. The use of conventional radical polymerisation, however, resulted in polymers with limited control over their chain compositions.…”

Molecular Recognition via Hydrogen Bonding in Supramolecular Complexes: A Fourier Transform Infrared Spectroscopy Study

“…Hydrogen bonding (HB) is at the core of the supramolecular chemistry involved in many natural processes [ 1 ]. It not only is the driving force to assemble the RNA and DNA helixes [ 2 , 3 ], but also plays a determining role in the transport of water and protonated species, such as crystallisation and dehydration of sugars [ 4 , 5 ] or the diffusion mechanisms of protons through fuel cell electrolytes [ 6 , 7 , 8 , 9 ]. HB is also a versatile tool to yield new synthetic complexes with tailor-made architectures [ 1 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 ].…”

Proton conductive ionic liquid crystalline poly(ethyleneimine) polymers functionalized with oxadiazole

“…[3][4][5][6][7][8] Thus, this strategy seems promising for the development of a wide range of efficient ion-conductive materials. [9][10][11] ILCs derived from dendritic polymers have attracted special interest because the large number of functional peripheral groups enables the attachment of different moieties that modify the macromolecule properties. In these ionic dendritic polymers, the LC order arises from the nanosegregation between charged groups and non-ionic regions of the molecule.…”