Living Anionic Surface Initiated Polymerization (SIP) of Styrene from Clay Surfaces

Abstract

Anionic surface initiated polymerization (SIP) was investigated to improve the stabilities and grafting densities of polymers on clay. This is a challenge because of the difficulties with the anionic polymerization mechanism and the presence of adventitious H2O molecules in silicates and clay. Our results showed the living anionic polymerization was only possible with the 1,1-diphenylethylene (DPE) initiator and a reaction protocol involving heating to 120 °C. The reaction serves to distinguish between surface and intergallery initiation.

Polymer brushes and self-assembled monolayers: Versatile platforms to control cell adhesion to biomaterials (Review)

“…This approach is extremely flexible, with the development of synthetic approaches which make use of cationic, 137,138 anionic, 139 controlled radical, and ringopening polymerizations ͑ROPs͒ ͑e.g., ring opening of lactide monomers and ring-opening metathesis polymerization of cyclic alkenes͒. [140][141][142][143][144][145][146][147] Of these methods, controlled radical polymerization of vinyl monomers affords a diverse array of methods to prepare new functional surfaces. These include atom transfer radical polymerizations ͑ATRPs͒ from alkyl halides, [148][149][150][151] nitroxide-mediated polymerizations ͑NMPs͒, 151 and reversible addition-fragmentation chain transfer polymerizations from benzyl N , N-diethyldithiocarbamates.…”

Nano-Scale Reinforcing and Toughening Thermoplastics: Processing, Structure and Mechanical Properties

“…In situ polymerization is a challenging one, as it allows us to adjust the chemistry to optimize the affinity between filler and the resulting polymer. Different types of polymerization methods have been used to prepare polymer nanocomposites, such as solution, suspension or emulsion, and free radical polymerizations (Akelah & Moet, 1996;Wang et al, 2002;Chen et al, 2000;Zhou et al, 2001). This variety to prepare polymer nanocomposites by in situ polymerization was mostly explored with clays.…”

Mechanical and Thermal Properties of Clay-poly(norbornene) Nanocomposites from Ruthenium Alkylidene-mediated Surface-initiated Polymerization

“…The synthetic route and characterization of the nanocomposites prepared from this metholodogy was previously published (Penaloza et al, 2015). In our previous work, not only a stable attachment between the polymer and the clay could be achieved but having relatively longer polymer chains (as compared to alkyl chains from ammonium modifiers commonly used in clay additives for nanocomposite preparation) increases the possibility of clay structure delamination (exfoliation) Zhou et al, 2001). Here, a surface-attached ruthenium alkylidine catalyst was used to mediate the norbornene polymerization directly from an organoclay surface resulting in nanocomposites where the polymer chains are grafted to the clay by covalent attachment as shown in Figure 1.…”