Automated Parallel Synthesis of MADIX (Co)Polymers

Abstract

An automated parallel synthetic approach has been developed for synthesizing polymer libraries by the Macromolecular Design via the Interchange of Xanthates (MADIX) process. The experimental set‐up, parallel polymerizations, characterization, and reproducibility tests are detailed. Examples of acrylic diblock copolymers synthesized in this way are given. Automated MADIX polymerizations of BA in the presence of a X1‐capped PEA.magnified imageAutomated MADIX polymerizations of BA in the presence of a X1‐capped PEA.

Combinatorial Methods, Automated Synthesis and High‐Throughput Screening in Polymer Research: The Evolution Continues

“…As described previously, [26] automated synthesis robots have been successfully applied to various controlled radical polymerization techniques like reversible addition fragmentation transfer (RAFT/MADIX) polymerization, [43,44] atom transfer radical polymerization (ATRP) [45,46] and nitroxide-mediated polymerizations. [47] Recently, Schubert and co-workers reported automated parallel investigations of new reaction conditions and catalysts for ATRP.…”

MADIX Polymerization of Captodative Ethyl α‐Acetoxyacrylate with Acrylate Monomers

“…Butyl acrylate was chosen as the comonomer to compare the obtained results with a previous study. [16] Reactions were sampled periodically to monitor monomer conversion, molecular weight and polydispersity by means of gravimetry, 1 H NMR and size exclusion chromatography (SEC). SEC traces of BuA/EAA copolymers obtained using THF eluent, revealed monomodal and relatively narrow molecular weight distributions.…”

“…This can be partly attributed to transfer to the solvent which occurs to a significant degree of conversion with these initial monomer concentrations and with these dilution as already described in the literature. [16,37] Figure 1 shows the plot of ln([M] 0 /[M]) versus time for the copolymerization of butyl acrylate and EAA for different targeted molecular weights. A blank experiment (without transfer agent) is also indicated for comparison.…”

“…[40] Indeed, when Ctr app is close to 1.7, the experimental M n is close to the final theoretical M n all along the polymerization reaction together with a high polydispersity index ( Figure 2) as it has been already described in the literature. [16,17] The difference observed between experimental and theoretical molecular weight can be attributed to the inadequacy of the polystyrene (PSt) standards used for the calibration of the SEC columns. Indeed, some of the copolymers have been further analyzed by SEC equipped with both multiangle laser light scattering and refractometric detectors (see footnote a in Table 2).…”

“…[11][12][13][14][15][16][17][18][19] Indeed, MADIX polymerization is a very efficient way to produce polymers from acrylates and vinyl acetate with predictable molecular weights. [11][12][13][14][16][17][18]20] Because one part of the chemical structure of EAA (Scheme 1) resembles vinyl acetate and the other part resembles ethyl acrylate, it seemed interesting to study the behavior of this monomer in MADIX polymerization.…”