(Meth)acrylic monomers with heteroatom-containing ester side chains: a systematic PLP-SEC and polymerization studyElectronic supplementary information (ESI) available: For the PLP-SEC experiments exemplary SEC chromatograms are shown for each monomer at 4 temperatures as well as tables with the exact PLP sample conditions. Furthermore, the temperature-dependent density curves for each monomer and the differential scanning calorimetry (DSC) curves are provided and the results are summarized in Ta

• Main Authors: Haehnel, Alexander P, Stach, Marek, Chovancová, Anna, Rueb, Jannick M, Delaittre, Guillaume, Misske, Andrea M, Lacík, Igor, Barner-Kowollik, Christopher
• Format: Journal Article
• Language: English
• Published: 24.12.2013
• ISSN: 1759-9954; 1759-9962
• DOI: 10.1039/c3py00948c

The Arrhenius parameters of the propagation rate coefficient for two hetero-atom containing (meth)-acrylates (studied as 1 M solution in N , N -dimethylacetamide (DMAc)) are determined via the pulsed laser polymerization - size-exclusion chromatography (PLP-SEC) method. Absolute molar mass determination is achieved via SEC coupled to on-line multi-angle laser light scattering (MALLS). The data obtained for hydroxypropylcarbamate acrylate (HPCA, A = 3.97 (−1.44 to 1.63) × 10 6 L mol −1 s −1 and E a = 14.3 (−1.38 to 5.13) kJ mol −1 ) are critically compared with the literature known data sets of two structural derivatives, i.e. , 2-(phenylcarbamoyloxy)isopropyl acrylate (PhCPA) and 2-(hexylcarbamoyloxy)isopropyl acrylate (HCPA), indicating an increase in the propagation rate coefficient with increasing ester side chain length. Ureidoethyl methacrylate (UMA, A = 2.08 (−0.45 to 0.91) × 10 6 L mol −1 s −1 and E a = 19.9 (−0.89 to 0.91) kJ mol −1 ) represents the first hetero-atom containing methacrylate to be studied via PLP-SEC, evidencing a significantly higher propagation rate coefficient compared to earlier investigated methacrylate-type monomers. Furthermore, the free-radical polymerization behavior of HPCA and UMA is studied via in situ 1 H-NMR experiments at elevated temperatures allowing for an estimation of average termination rate coefficients (at low conversion) in conjunction with the determined k p data. Furthermore, the polymerization of UMA was successfully controlled by reversible addition-fragmentation chain transfer (RAFT) polymerization as evidenced by the linear evolution of the number-average molar mass, M n , with conversion (3000 g mol −1 ≤ M n ≤ 23 000 g mol −1 , 1.15 ≤ ≤ 1.3) as well as by nitroxide-mediated polymerization (NMP), as demonstrated by the linear evolution of M n with conversion (4000 g mol −1 ≤ M n ≤ 40 000 g mol −1 , 1.3 ≤ ≤ 1.4). In addition, HPCA polymerization was successfully controlled by the RAFT process, as evidenced by the linear evolution of M n with conversion (2000 g mol −1 ≤ M n ≤ 21 000 g mol −1 , 1.2 ≤ ≤ 1.4) and successful chain extension experiments. Finally, the NMP of HPCA exhibited uniform shifts of the molar mass distributions in the range of 5000 g mol −1 ≤ M n ≤ 70 000 g mol −1 and successful chain extension experiments. The FRP and RDRP behavior of hydroxypropylcarbamate acrylate (HPCA) and ureidoethyl methacrylate (UMA) is studied via high frequency PLP-SEC-MALLS as well as on-line NMR experiments.