Far beyond primary poly(vinylamine)s through free radical copolymerization and amide hydrolysis

Abstract

Due to their affinity for many supports, their pH responsiveness, metal binding capacity and polyelectrolytes complexation, poly(vinylamine) derivatives have attracted attention for many applications including coatings, water purification, or gas membrane separation. Nevertheless, most of them possess only pendant primary amines despite the possible benefits of incorporating different amino groups along the chain. In this work, a straightforward and scalable synthesis route towards polymers bearing primary and secondary amines, as well as imidazole groups, is reported. The general strategy relies on the radical copolymerization of different vinylamides and vinyl imidazole followed by the hydrolysis of the resulting poly(vinylamide) derivatives. Binary and ternary free radical copolymerizations of Nvinylacetamide (NVA), N-methyl vinylacetamide (NMVA) and 1-vinylimidazole (VIm) were investigated and the reactivity ratios for each copolymerization system were determined. Thanks to these values a series of statistical copolymers with predictable composition and low deviation over the chain distribution could then be synthesized. Finally, the acidic hydrolysis of the acetamide functions towards the corresponding amine was performed and optimized. Copolymers containing various pendant amino groups and with low dispersity in the chain composition could be obtained, which opens new perspectives for the above mentioned applications.polyvinylimidazole 55 , as well as the dependence of the antimicrobial efficiency on the charge density and hydrophobicity. 54 Finally, these novel polyamines might also outperform primary PVAm in applications like paper strengthening or coating applications 9-11 . In other words, much can be expected from this poly(vinylamine) based synthetic platform. Notes and references

Poly(N‐methylvinylamine)‐Based Copolymers for Improved Gene Transfection

“…In order to obtain the desired pendant amino groups, the polyvinylacetamido precursors were hydrolyzed using two conditions. The first one called soft condition, (2 n HCl, 120 °C, 14 h) reported by Akashi et al, led to copolymers having a global degree of deacetylation between 76% and 83%, while the second condition, (6 n HCl, 120 °C, 64 h) referred to as harsh conditions, gave global degree of deacetylation between 87% and 92% depending on the copolymer composition, i.e., the ratio between the primary and secondary amides . The hydrolysis level was confirmed by 1 H NMR (Figure S1, Supporting Information) and the final composition of the copolymers was determined by EA (Table S1, Supporting Information).…”

“…Imidazole moieties, supposed to play a proton sponge role in the endosome during transfection, were inserted along the PMVAm backbone by statistical radical copolymerization of NMVA with VIm. A subsequent acidic hydrolysis led to P(MVAm‐ co ‐VIm) . Terpolymers composed of vinylimidazole, primary and secondary amines, i.e., P(MVAm‐ co ‐VAm‐ co ‐VIm) (Figure C), where obtained by copolymerizing NMVA, NVA, and VIm and successive hydrolysis.…”

“…The copolymers containing vinylimidazole moieties were hydrolyzed in the same conditions (harsh conditions, indicated by the suffix h in the abbreviated polymer name). In contrast, the hydrolysis the PNVA homopolymer was performed under milder conditions (5% w/v, 2 n HCl, 120 °C, 14 h, soft conditions, indicated by the suffix s) according to Dréan et al P(NMVA‐ co ‐NVA) copolymers were hydrolyzed by both the sets of conditions. Finally, the PMVAm for guanidinylation was hydrolyzed using 3 n HCl at 100 °C (medium conditions, suffix m, Table , entry 3) .…”

“…Indeed, we reported that polymethylvinylamine (PMVAm)‐based pDNA polyplexes reached transfection efficiency in the same order as the gold standard lPEI, yet with improved cell viability (>60%) . PMVAms were readily obtained by free radical polymerization (FRP) of N ‐methylvinylacetamide (NMVA), followed by acidic hydrolysis of the amide groups . A series of PMVAms with controlled molar masses and low molar mass distribution prepared by organometallic mediated radical polymerization (OMRP) of NMVA and subsequent acidic hydrolysis was tested .…”

Polycarboxylate superplasticizers of acrylic acid–isobutylene polyethylene glycol copolymers: monomer reactivity ratios, copolymerization behavior and performance

“…Moreover, this study also explored specific copolymerization behavior of similar structure of copolymers with steric hindrance under penultimate copolymerization equation, More common polycarboxylate superplasticizers researches are focused on performance evaluations [4,5], but studies of monomer reactivity ratios and copolymerization behavior are relatively scarce. The VI-co-PyMMP copolymer has been designed and synthesized by a freeradical copolymerization of VI and PyMMP as well as characterized by ultraviolet (UV), and the monomer reactivity ratios are determined by two methods of FinemanRoss [6][7][8] and Kelen-Tüdös [9][10][11]. The styrene (S)/ acrylonitrile (AN) copolymers were synthesized with a unimolecular initiator, and the monomer reactivity ratios are determined by Fineman-Ross [12], Kelen-Tüdös [11], and error-in-variables [13] methods [14].…”