On the relative importance of cross and homotermination in radical copolymerization

Computer simulations of the copolymerization of styrene and methyl methacrylate have been carried out in an attempt to assess the relative importance of the cross and the two homotermination processes. During the copolymerization, termination by methacrylyl-methacrylyl interaction is of relatively little significance. Termination occurs mainly through styryl-styryl and styryl-methacrylyl interaction. Features of models commonly used to describe polymerization kinetics are discussed

Soft-Hard Janus Nanoparticles for Polymer Encapsulation of Solid Particulate

We demonstrate a scalable continuous feed method for the synthesis of polymer Janus nanoparticles with different composition and with different aspect ratios between lobes, including with one hard cross-linked polystyrene lobe and one soft film-forming poly(methyl methacrylate-co-butyl acrylate) (P(MMA-co-BA)) lobe, through reversible addition-fragmentation chain transfer (RAFT)-mediated emulsion polymerization. Snowman shaped particles of size around 40 nm are synthesized through a continuous monomer feeding method, which enables kilogram-scale synthesis of diverse polymer Janus nanoparticles, with a solids content greater than 30%. The Janus nanoparticles with the soft P(MMA-co-BA) lobes spontaneously self-assemble around solid particles in an aqueous phase, forming a thin (5 -100 nm) polymer film that completely encapsulates the solid particles. The process is achieved at room temperature and under mild conditions. The film-forming Janus nanoparticles show excellent encapsulation ability for a variety of solid particles, such as organic and inorganic pigments, carbon nanotubes and calcite, without requiring polymerization to be conducted in the presence of the solid particles. When the Janus nanoparticles were used to encapsulate calcite particles in low sheen paints, the encapsulation provided superior stain resistance to the formed paint film

Molecular watchmaking: ab initio Emulsion polymerization by RAFT-controlled self-assembly

Controlled radical polymerization using RAFT has the potential to make polymers with virtually any desired molecular architecture. For this to be implemented on an industrial scale, it must be performed by polymerization in disperse media. However, simply adding a RAFT agent to a conventional emulsion polymerization recipe leads to a loss of molecular weight control and formation of coagulum, probably because of nucleation in droplets, which is normally an unlikely phenomenon in emulsion polymerizations. Recently, a method has been devised for implementing RAFT in ab initio emulsion polymerization that avoids droplets in the particle formation stage. The molecular weight distribution of the polymer thus formed shows that molecular weight control is maintained throughout the polymerization. A model is developed to predict the particle size formed in this new type of emulsion polymerization. The new methodology enables synthesis of novel dispersions where molecular architecture can be precisely controlled, such as structured core-shell particles

Aqueous Polymeric Hollow Particles as an Opacifier by Emulsion Polymerization Using Macro-RAFT Amphiphiles

A robust polymerization technique that enables the surfactant-free aqueous synthesis of a high solid content latex containing polymeric hollow particles is presented. Uniquely designed amphiphilic macro-reversible addition fragmentation chain transfer (RAFT) copolymers were used as sole stabilizers for monomer emulsification as well as for free-radical emulsion polymerization. The polymerization was found to be under RAFT control, generating various morphologies from spherical particles, wormlike structures to polymer vesicles. The final particles were dominantly polymeric vesicles which had a substantially uniform and continuous polymer layer around a single aqueous filled void. They produced hollow particles once dried and were successfully used as opacifiers to impart opacity into polymer paint films. This method is simple, can be performed in a controllable and reproducible manner, and may be performed using diverse procedures