Surface Modification of Nanoporous 1,2-Polybutadiene by Atom Transfer Radical Polymerization or Click Chemistry

Abstract

Surface-initiated atom transfer radical polymerization (ATRP) and click chemistry were used to obtain functional nanoporous polymers based on nanoporous 1,2-polybutadiene (PB) with gyroid morphology. The ATRP monolith initiator was prepared by immobilizing bromoester initiators onto the pore walls through two different methodologies: (1) three-step chemical conversion of double bonds of PB into bromoisobutyrate, and (2) photochemical functionalization of PB with bromoisobutyrate groups. Azide functional groups were attached onto the pore walls before click reaction with alkynated MPEG. Following ATRP-grafting of hydrophilic polyacrylates and click of MPEG, the originally hydrophobic samples transformed into hydrophilic nanoporous materials. The successful modification was confirmed by infrared spectroscopy, contact angle measurements and measurements of spontaneous water uptake, while the morphology was investigated by small-angle X-ray scattering and transmission electron microscopy.

Engineering Gyroid‐Structured Functional Materials via Templates Discovered in Nature and in the Lab

“…A Knudsen diffusion mechanism was proposed for gas permeation, while for liquids it can be described by a generalized Hagen–Poiseuille equation ( Figure a,b). What's more, the surface chemistry and permeability were reported to be versatile, controlled by importing functional groups through chemical methods, or by simply altering the interface energy in the process of membrane fabrication, resulting in flexibly tuned diffusion (Figure c,d) . The opened and closed conditions of the nanopores can also be selectively tuned by controlling their physical and chemical environments, such as pH and solvent .…”

“…c,d) FTIR and water‐contacting experiments verifying the chemically modified DG membranes. Reproduced with permission . Copyright 2009, ACS.…”

Sodium Dodecyl Sulfate (SDS)-Loaded Nanoporous Polymer as Anti-Biofilm Surface Coating Material

“…A gyroid nanostructure was designed from the polymer synthesis stage [19] in order to ensure isotropic percolation with no need for structure alignment. The composition of the nanoporous matrix is essentially hydrocarbonic and is therefore hydrophobic, showing a static contact angle of 119° with water [20]. Therefore water cannot spontaneously wet and fill the nanoporous volume, while methanol can [19,20].…”

“…The composition of the nanoporous matrix is essentially hydrocarbonic and is therefore hydrophobic, showing a static contact angle of 119° with water [20]. Therefore water cannot spontaneously wet and fill the nanoporous volume, while methanol can [19,20]. For this reason SDS loading was realized by first conditioning the nanoporous 1,2-PB film in methanol before dipping it into SDS aqueous solution (Figure 1c).…”

Efficient Gene Carriers Composed of 2‐Hydroxypropyl‐β‐Cyclodextrin, Ethanolamine‐Functionalized Poly(glycidyl methacrylate), and Poly((2‐dimethyl amino)ethyl methacrylate) by Combination of ATRP and Click Chemistry

“…Copper(I)‐catalyzed azide‐alkyne cycloaddition or “click chemistry” has been widely used for polymer functionalization . Click reactions can be applied under mild reaction conditions with high efficiency and quantitative yields, suitable to a variety of groups .…”