The accurate characterization of molar-mass distributions of poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) by size-exclusion chromatography (SEC) is addressed. Two methods are employed: direct aqueous-phase SEC on P(M)AA and THF-based SEC after esterifi cation of P(M)AA to the associated methyl esters, P(M)MA. P(M)AA calibration standards, P(M)AA samples prepared by pulsed-laser polymerization (PLP), and PAA samples prepared by reversible addition-fragmentation chain transfer (RAFT) are characterized in a joint initiative of seven laboratories, with satisfactory agreement achieved between the institutions. Both SEC methods provide reliable results for PMAA. In the case of PAA, close agreement between the two SEC methods is only observed for samples prepared by RAFT polymerization with weightaverage molar mass between 80 000 and 145 000 g mol −1 and for standards with peak molar masses below 20 000 g mol −1 . For standards with higher molar masses and for PLP-prepared PAA, the values from THF-based SEC are as much as 40% below the molar masses determined by aqueous-phase SEC. This discrepancy may be due to branching or degradation of branched PAA during methylation. While both SEC methods can be recommended for PMAA, aqueous-phase SEC should be used for molar-mass analysis of PAA unless the sample is not branched.

A robust and reproducible method for the molar mass analysis of neutral and anionic copolymers based on methacrylic acid and different (meth)acrylates has been developed. Size exclusion chromatography (SEC) using a novel polyester- based packing as the stationary phase and dimethylacetamide (DMAC) as the mobile phase yields highly accurate results for copolymers with a methacrylic acid content up to 50 wt.-%. To suppress the different polar and ionic interactions between the sample molecules, the stationary phase and the eluent, DMAC was modified with LiBr and acetic acid. Calibrating the SEC system with poly(methyl methacrylate) of narrow polydispersity, molar masses were obtained that are in good agreement with data obtained by SEC-MALLS (multi-angle laser light scattering) and SEC measurements of methylated samples. The reproducibility and the robustness of the novel method were proven by running similar samples in three different laboratories and for an extended period of two weeks.

A robust and reproducible method for the molar mass analysis of cationic copolymers based on dimethylaminoethyl methacrylate or trimethylammonioethyl methacrylate and different (meth)acrylates has been developed. Size exclusion chromatography (SEC) using a novel polyester-based packing as the stationary phase and dimethylacetamide (DMAC) as the mobile phase yields highly accurate results for copolymers with an amino comonomer content up to 50 wt.-%. To suppress the different polar and ionic interactions between sample molecules, stationary phase and eluent, DMAC was modified with LiBr and tris(hydroxymethylamino)methane (TRIS). Calibrating the SEC system with poly(methyl methacrylate) of narrow polydispersity, molar masses were obtained that are in good agreement with viscosity data. Reproducibility and robustness of the novel method were proven by running samples for an extended period of two weeks.

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The influence of basic reaction parameters -the ratio of catalyst components, the composition of the monomer mixture and the temperatureon the progress of the copolymerization, the molecular weight and the molecular weight distribution as well as on the composition of the copolymers obtained is reported. Conversion data for the variation of the mole ratio of comonomers show a maximum for an [AI]/[V] mole ratio of approximately 7, whereas the molecular weight of copolymers is not significantly influenced. An increase in the molecular weight of the copolymers can be obtained by an increase of butadiene content in the monomer mixture. However, there is also an increasing incorporation of butadiene into the copolymer. Raising the temperature from -60 "C to 0 "C results in a significant decrease in molecular weight, whereas the composition of the copolymers is not significantly changed.