Synthesis of butyl acrylate-styrene block copolymers in emulsion by reversible addition-fragmentation chain transfer: Effect of surfactant migration upon film formation

The synthesis of block copolymers in an environmentally friendly medium was carried out in emulsion polymerizations through the reversible addition‐fragmentation chain transfer process, using a transfer active xanthate (MADIX) agent, under batch and starved‐feed conditions. First, ab initio experiments were carried out to prepare a seed of PBA dormant chains (i.e., poly(butyl acrylate) (PBA) polymer attached with a transfer active xanthate). The M̄n and polydispersity were predicted accurately with numerical simulations and equations derived by Müller from the method of moments. Those seeds were then used in a second‐stage polymerization under starved‐feed and batch conditions to prepare composite polymer colloids of block PBA‐co‐poly(styrene). Under starved feed conditions, approximately 90% of total polymer consisted of blocks, whereas under batch conditions only 70% consisted of blocks, which is proposed to be due a higher entry efficiency and thus greater termination rate. The films of these latexes were examined by atomic force microscopy. Surfactant migration to the surface increased with an increase in the amount of MADIX, resulting from a combination of a smaller particle size and a lower average molecular weight. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4206–4217, 2000 The synthesis of block copolymers in an environmentally friendly medium was prepared in emulsion polymerizations using the reversible addition‐fragmentation chain transfer (RAFT) process under batch and starved‐feed conditions. First, ab initio experiments were carried out in the presence of an RAFT agent, which has Ctr close to 1, to prepare a seed of polybutyl acrylate dormant chains (i.e., PBA polymer attached with a transfer active xanthate) with a polydispersity (PD) close to 2. The M̄n and PD were predicted accurately with numerical simulations and also equations derived by Müller from the method of moments. Those seeds were then used in a second‐stage polymerization under starved feed and batch conditions to prepare composite polymer colloids of block PBA‐co‐PSTY. Under starved‐feed conditions the total polymer consisted of approximately 90% blocks, whereas under batch conditions only 70% of the polymer consisted of blocks, which is proposed to be due a higher entry efficiency and thus greater termination rate. The films of these latexes were examined by atomic force microscopy. It was found that surfactant migration to the surface increased with an increa