We combined several analytical techniques (NMR, matrix assisted laser desorption ionizationtime-of-flight mass spectroscopy MALDI-TOF MS, GPC, functional analysis on the first block, liquid chromatography at the point of exclusion adsorption transition LC-PEAT, and capillary electrophoresis CE) to analyze and quantify the characteristics of homopolymer precursors and amphiphilic diblocks synthesized by controlled radical polymerization process (CRP). We present here a detailed quantitative characterization of amphiphilic diblock copolymers (poly(butyl acrylate)-poly(acrylic acid) or PBA-b-PAA, and poly(di(ethylene glycol) ethyl ether acrylate)-poly(acrylic acid) or PDEGA-b-PAA). The samples were synthesized in ethanol by macromolecular design via inter-exchange of xanthate (MADIX), a reversible addition fragmentation transfer (RAFT) polymerization process using xanthates as control agents. The analytical results have permitted a determination of the transfer constant of xanthate C Xa (≈ 2.7 and 1.5 for respectively PBA and PDEGA) and the transfer constant to solvent C s (≈ 6 × 10 -4 ). In the final diblock products, homopolymer side products were characterized. The amount of hydrophobic homopolymer was quantified by a specially developed LCPEAT technique in critical conditions for PBA. The hydrophilic homopolymer h-PAA amount was determined by quantitative capillary electrophoresis CE experiments. These analytical approaches allowed the quantification of the side products in a CRP system as well as the improvement of the reaction conditions via a thorough knowledge of the reaction mechanism.

The on-line monitoring of a styrene/butadiene latex emulsion polymerization was completed. Our aim was to determine in real time the dry extract percentage or the amount of styrene monomer in the reactor. We constructed two partial least-squares (PLS) calibration models with mean-centered spectra over the 3500–2700 U 1800–500 cm−1 spectral range. Four factors were required to model the evolution of the dry extract, and a two-factors model calibrated the amount of free styrene. The results were very satisfactory: the dry extract was predicted with a root mean squared error of prediction (RMSEP) lower than 1% over the 2–50% dry extract range, and for the amount of styrene monomer, the RMSEP was lower than 5000 ppm over the 0–70 000 ppm range. The nonlinear effects of temperature and water reabsorption were considered, and they did not prevent PLS from giving good-quality results.