University of Massachusetts Medical School Faculty Publications

Title

Well-controlled ATRP of 2-(2-(2-Azidoethyoxy)ethoxy)ethyl Methacrylate for High-density Click Functionalization of Polymers and Metallic Substrates

UMMS Affiliation

Department of Orthopedics and Physical Rehabilitation; Department of Cell and Developmental Biology

Date

5-1-2016

Document Type

Article

Disciplines

Biomaterials | Polymer Chemistry

Abstract

The combination of atom transfer radical polymerization (ATRP) and click chemistry has created unprecedented opportunities for controlled syntheses of functional polymers. ATRP of azido-bearing methacrylate monomers (e.g. 2-(2-(2-azidoethyoxy)ethoxy)ethyl methacrylate, AzTEGMA), however, proceeded with poor control at commonly adopted temperature of 50 degrees C, resulting in significant side reactions. By lowering reaction temperature and monomer concentrations, well-defined pAzTEGMA with significantly reduced polydispersity were prepared within a reasonable timeframe. Upon subsequent functionalization of the side chains of pAzTEGMA via Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click chemistry, functional polymers with number-average molecular weights (Mn) up to 22 kDa with narrow polydispersity (PDI < 1.30) were obtained. Applying the optimized polymerization condition, we also grafted pAzTEGMA brushes from Ti6Al4 substrates by surface-initiated ATRP (SI-ATRP), and effectively functionalized the azide-terminated side chains with hydrophobic and hydrophilic alkynes by CuAAC. The well-controlled ATRP of azido-bearing methacrylates and subsequent facile high-density functionalization of the side chains of the polymethacrylates via CuAAC offers a useful tool for engineering functional polymers or surfaces for diverse applications.

Rights and Permissions

Citation: J Polym Sci A Polym Chem. 2016 May 1;54(9):1268-1277. Epub 2015 Nov 12. Link to article on publisher's site

Related Resources

Link to Article in PubMed

Keywords

SI-ATRP, alloy, atom transfer radical polymerization (ATRP), azido-bearing methacrylate, click chemistry, kinetics (polym.)

PubMed ID

27616816