N,N-Diallylglycidylamine: A Key Monomer for Amino-Functional Poly(ethylene glycol) Architectures

Abstract

The first application of N,N -diallylglycidylamine (DAGA) as a monomer for anionic ring-opening polymerization is presented. The monomer is obtained in a one-step procedure using epichlorohydrin and N,N -diallylamine. Both random and block copolymers consisting of poly(ethylene glycol) and poly( N,N -diallylglycidylamine) with adjusted DAGA ratios from 2.5 to 24% have been prepared, yielding well-defined materials with low polydispersities (M w/M n) in the range 1.04–1.19. Molecular weights ranged between 2600 and 10 300 g mol–1. Isomerization of allylamine to enamine structures during polymerization depending on time, temperature, and counterion has been realized. The kinetics of the formation of the copolymer structure obtained by random copolymerization was investigated, using time-resolved 1H NMR measurements and 13C NMR triad sequence analysis. A tapered character of the monomer incorporation was revealed in the course of the concurrent copolymerization of EO and DAGA. The thermal behavior of the copolymers in both bulk and aqueous solution has been studied, revealing LCSTs in the range 29–94 °C. Quantitative removal of protective groups via double-bond isomerization mediated by Wilkinson’s catalyst and subsequent acidic hydrolysis yielded multiamino-functional PEG copolymers with tapered or block structure. Accessibility of liberated primary amines for further transformation was demonstrated in a model reaction by derivatization with acetic anhydride. In contrast to previous approaches, the DAGA monomer permits the synthesis of block copolymers with PEG block combined with multiamino-functional polyether block.

Aliphatic Polyethers: Classical Polymers for the 21st Century

“…Starting materials are easily accessible and common in chemical industry which renders these materials interesting for different applications. The functional epoxide is obtained via intramolecular nucleophilic substitution (S N i) when ECH and the respective alcohol or amine are used as the starting materials . Another route is the protection of the hydroxyl group of glycidol with ethyl vinyl ether under acidic catalysis …”

“…They are of interest with respect to biomedical applications due to their pH‐responsivity in addition to potential cloud point temperatures (compare below). N,N ‐dibenzyl glycidyl amine (DBAG) and N,N ‐diallyl glycidyl amine (DAGA) carry protected amines which can be deprotected after polymerization and enable the introduction of free amine moieties. The use of N,N ‐diethyl glycidyl amine (DEGA), N,N ‐di( n ‐alkyl) glycidyl amines (DXGA), and N,N ‐diisopropyl amino ethyl glycidyl ether (DEGE) allows the synthesis of cationic polyelectrolytes as the amine groups can be quaternized.…”

“…Under certain reaction conditions the copolymerization of glycidyl derivatives with EO is perfectly random, but also gradient copolymers, especially for the amino‐derivatives have been reported …”

Polyoxazolines for Nonfouling Surface Coatings — A Direct Comparison to the Gold Standard PEG

“…A comprehensive review of the preparation of multifunctional PEGs and POXs is out of scope of the present feature. Multifunctional PEGs have been strongly advanced and reviewed by Frey and co‐workers80–84 in recent years. Excellent reviews on the polymerization of 2‐oxazolines with an emphasis on the preparation of multifunctional POXs have also been reported recently by several groups 85–90.…”

Synthesis, characterization and targeted cell imaging applications of poly(p-phenylene)s with amino and poly(ethylene glycol) substituents

“…[24][25][26][27][28][29][30][31][32][33] Besides the effective role of PEG in bio-applications, advances in the field of bio-imaging have profoundly impacted the use of water soluble bio-polymers and concerns significantly focused on the fabrication of fluorescence-based organic conjugated polymers relying on π-electron delocalization features. Water solubility can be achieved by water soluble supports such as poly(ethylene glycol) (PEG), which comes to the forefront from a highly versatile class of polyethers.…”