High‐Molecular‐Weight Polyampholytes Synthesized via Daylight‐Induced, Initiator‐Free Radical Polymerization of Renewable Itaconic Acid

Abstract

Herein, it is reported for the first time that when mixed with choline chloride, itaconic acid (IA), normally a low‐reactive vinyl monomer, undergoes initiator‐free radical polymerization under normal daylight. Furthermore, the process results in the formation of abnormally high‐molecular‐weight poly(itaconic acid) derivatives with Mw greater than ≈800 000 g mol−1. Detailed 1D/2D NMR studies indicate that the polymers have two types of ionizable moieties, that is, anionic carboxylic and cationic choline ester groups in an average molar ratio of 12:1. Potentiometric titration shows polyampholyte behavior of the polymers. Tentative mechanistic studies reveal that the daylight‐induced polymerization is initiated by species generated via interactions of near UV light with IA. However, EPR findings show that choline also participates in secondary radical reactions. The obtained polyampholytes are useful bio‐based materials for fast and straightforward fabrication of polymer–clay nanocomposite hydrogels with excellent mechanical properties.

Electrical conductivity of an all-natural and biocompatible semi-interpenetrating polymer network containing a deep eutectic solvent

“…35,36 Formation of the semi-IPNs comprising poly(IA-co-BAA)/inulin -PIA-BAA/inulin-and poly(IA-co-PETA)/inulin -PIA-PETA/inulinwere proved by ATR-FTIR and solid state 13 C NMR upon extraction of the inert DES components (glycerol and choline chloride), and unreacted monomers with water. The spectra of the semi-IPN in Figure 3A show the typical signals of the carbonyls groups characteristic of pure PIA, as previously reported; 29,37 as well as the bands related with OH and COC typical of inulin. 38 Characteristic bands of PIA include those due to C=O stretching at 1720 cm -1 , CH2 bending at 1430 cm -1 , O-H bending at 1400 cm -1 , and C-O stretching at 1200 cm -1 .…”

Construction and Application of Biobased PDES Ionic Gels with a Soft–Hard Segment

“…This might be due to the lack of ChCl−Gly DES; the steric hindrance of the monomer IA made polymerization very difficult. 28 Interestingly, compared with the preparation time of P(IA1-co-AM1.1)-W hydrogels, the preparation time of P(IA1-co-AM1.1) ionic gels was significantly shortened, which also indicated that the hydrogen bond network in DES had a certain promotion effect on gel formation. 23 Frost Resistance and Stability Analysis of the P(IA-co-AM) Ionic Gel.…”

“…In addition, the chloride and choline ions in choline chloride (ChCl) DES can generate mobile charges and have high ionic conductivity (glycerin–ChCl DES exhibits 1.05 mS/cm at 20 °C) . Meanwhile, polymerization of IA-based DES results in higher monomer conversion and a higher molecular weight as compared to water . In summary, DES exhibits superior performance over traditional organic solvents or even ionic liquids, in terms of flexible ionic gels.…”

Transforming nature into the next generation of bio-based flexible devices: New avenues using deep eutectic systems

“…Higher reactivity toward free-radical ll polymerization, lower reaction temperature, higher molecular weight, and denser crosslinking results from its transformation into a DES as compared with its freeradical polymerization in water. 63,64 Incorporation of polymers and biomacromolecules to DESs Incorporation of polymers and biomacromolecules to a DES to prepare gels is a strategy that is gaining considerable interest because it allows for the straightforward preparation of flexible materials containing DESs without the need for a chemical reaction, such as the polymerization processes described previously.…”