Synthesis of reduction sensitive comb‐like polyurethanes using click chemistry

Abstract

The synthesis and characterization of new highly biodegradable multipropargyl and comb-like copolyurethanes have been successfully achieved by the combination of stepgrowth polymerization and click chemistry. This work discloses a simple, accurate, and straightforward method to generate brush polymers with an excellent control of the branch nature, distribution, and density in the final materials. The introduction of controlled branching has led to a great variety of polymers, whose hydrophilic/lipophilic characters were adjusted as required. Furthermore, their stiffness, semicrystalline nature, and degradability were fine-tuned by appropriate selection of the monomers and their feed ratios. The presence of propargyl functional groups in the (co)polymers was confirmed by the presence of a thermal degradation step in the range from 450 8C to 455 8C.A new approach is proposed herein: the preparation of graft or comb-like PU with long side chains able to generate homogeneous hydrophilic/hydrophobic phases when assembled. This work discloses a simple, accurate, and straightforward method to synthesize graft or comb-like polyurethanes Additional Supporting Information may be found in the online version of this article.

Bio‐Based Polyurethanes from Carbohydrate Monomers

“…In this sense, click chemistry (CC) is the most popular approach to achieve chemical transformations; for instance, the thiol-ene coupling reaction of a thiol and an alkene/alkyne and the alkyne-azide cycloaddition reaction. Aspects of Polyurethanes monomer 49, a series of new biodegradable comb-like copolyurethanes was achieved by the combination of step-growth polymerization and click chemistry [30]. Stiffness, hydrophilic/lipophilic character, and degradability could be adjusted by the appropriate selection of the comonomers and their feed ratios.…”

“…Similarly, the preparation of PU with well-defined "tunable" macromolecular comb-like architectures was successfully accomplished [30] by means of a two-step procedure: preparation of multipropargyl copolyurethanes based on the tri-O-propargyl-L-arabinitol derivative 49 and DiT and their subsequent derivatization via alkyne-azide click reaction with chemically diverse azides-dodecyl azide, triethylene glycol azide, and polyethylene glycol azide. This methodology allowed the generation of PU with an extensive chemical diversity that has been unapproachable until now.…”

Hydrolytic degradation of d-mannitol-based polyurethanes

“…obtained from easily accessible monosaccharides [17][18][19] by either hydrolytic or enzymatic processes [20][21][22][23][24][25] are biocompatible and degradable materials. Those PUs containing disulfide bonds and carbohydrate moieties in the backbone repeating units were degraded by GSH [22][23][24][25]. It was demonstrated that a pair of structural properties such as the degree of crystallinity and hydrophilicity of these materials are of relevance for degradation rate.…”

Polymeric Nanoparticles for Drug Delivery: Recent Developments and Future Prospects

“…In order to accomplish certain properties, polymeric tailoring could be carried out directly on biopolymers by chemical derivatization [ 7 , 8 ]. Another option is the preparation of synthetic polymers from their corresponding monomers which can lead to a large range of structures and applications [ 9 , 10 , 11 , 12 ]. These are the reasons why polymeric materials are gaining great relevance in nanotechnology in general and are being used as NP precursors for DDSs.…”