Hyperbranched poly(ether amine)(hPEA)as novel backbone for amphiphilic one-component type-Ⅱ polymeric photoinitiators

To make photoinitiators （PI） to be polymeric and water-soluble is an effective approach to develop the high efficient photoinitiator systems with low-migration, low-toxic and environment-friend. We developed a series of novel amphiphilic hyperhranched polymeric photoinitiators （hPEA-TXs, and hPEA- BPs） by introducing thioxanthone （TX） or benzophenone （BP） moieties into the periphery of the hyperbranched poly（ether amine） （hPEA） comprised of the hydrophilic poly（ethylene oxide） （PEO） short chain and coinitiator amine moieties in the backbone. Compared with their water-soluble low-molecular weight analogues, the resulting hyperbranched polymeric photoinitiators hPEA101-TX, hPEA211-TX, hPEA101-BP and hPEA211-BP could be dissolved very well not only in many organic systems including acrylate monomers, but also in water with high solubility of 10 wt~. The photopolymerization kinetics of water-soluble monomer acrylamide （AM） and three hydrophobic multifunctional acrylate monomers initiated by these hyperbranched photoinitiators were investigated in detail by photo-differential scanning calorimetric （photo-DSC）. Both hPEA-TXs and hPEA-BPs can initiate photopolymerization of AM as efficiently as their low-molecular weight analogues MGA-TX and MGA-BP, respectively. The final double bond conversion （DBC） of oil-soluble monomer hexanediol diacrylate （HDDA） photoinitiated by these hyperbranched photoinitiators can reach as high as 99%. Especially for photopolymerization of multifunctional monomers initiated by these hyperbranched polymeric photoinitiators, the final DBC of trimethylolpropane triacrylate （TMPTA） and pentaerythritol tetraacrylate （PETTA） can reach 80% and 60%, respectively, which is much higher than that of low-molecular weight photoinitiators.

Synthesis and Properties of Novel Poly（amine ether）s

Using aromatic bis（4-bromophenyl） ether and various aromatic diamines as the monomers, a series of novel poly（amine ether）s （PAEs） have been synthesized via palladium-catalyzed aryl amination, which is the Hartwig-Buchwald polycondensation reaction. Their structures were characterized by means of elemental analysis, FT-IR, 1^H NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structures. Their general properties were studied by DSC and TG and it＇s obvious that they show high glass transition temperatures （Tg〉200 ℃）, good thermal stability with high decomposition temperatures （TD〉500℃） and excellent solubility. The mechanical behavior of these polymers suggested that they could be considered a new class of high-performance polymers.