Synthesis and end-group control of soluble, high-molecular-weight hyperbranched poly(phenylene thienylene)s by non-stoichiometric A2 + B3 Suzuki-Miyaura polycondensation without gelation

Non-stoichiometric Suzuki-Miyaura polycondensation of tribromo monomer 1, containing a thienylene group, with diboronic acid (ester) monomer 7 in the presence of tBuPPd catalyst, which has a propensity for intramolecular catalyst transfer on a π-electron face, was investigated. We anticipated that the presence of thienylene groups in the obtained hyperbranched polymer would increase the detection sensitivity in matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry and enable the analysis of the polymer end groups up to the high-molecular-weight region. We first conducted Suzuki-Miyaura reaction of several kinds of 1 with phenylboronic acid 2 in the presence of tBuPPd precatalyst 3. The reaction of tris(5-bromo-4-hexylthien-2-yl)benzene 1c with 2 afforded exclusively tri-substituted product 4c, indicating that the tBuPPd catalyst undergoes intramolecular catalyst transfer on 1c after the first and second substitutions of 1c with 2. The polycondensation of equimolar 1c and pinacol phenylenediboronate 7a (reaction site ratio of Br:BPin = 1.5:1.0 (BPin = pinacol boronate)) was then carried out in the presence of 3 for 3 h, affording hyperbranched polymer with Mn = 37500 without gelation. The product was purified by precipitation. The degree of polymerization (DP) was calculated from the absolute molecular weight, determined by multi-angle light scattering (MALLS) analysis, to be 200, which is a far higher than would be predicted from the Flory-Stockmayer theory at the critical gel point (DP = 6.6). Furthermore, the MALDI-TOF mass spectra showed two series of peaks due to polymer with boronate ends and boronate ends along with one cyclic unit up to m/z of about 7500, as we had expected. The absence of peaks due to polymer with Br ends indicates that the degree of branching (DB) of this hyperbranched polymer is 100 %.