A series of hyperbranched polyurethane-benzyltetrazoles （H-PBTZs） with different linkage structures were synthesized via the polycondensation of hexamethylenediisocyanate as an A2 type monomer with （4-（1H-tetrazol-5- yl）benzyl）-diethanolamine （TBDEA） as a BB＇2 type monomer in the absence of catalyst at different temperatures. The FTIR, and 13C and 1H-NMR spectroscopy were used to characterize the molecular structures of TBDEA and H-PBTZs as well as the counterpart linear polyurethane-benzyltetrazole （L-PBTZ）. The molecular composition was determined by the reaction selectivity that the isocyanate group reacted with the hydroxyl group in diethanolamine segment or the active hydrogen atom on tetrazole ring. Raising reaction temperature was propitious to the reaction of isocyanate group with the active hydrogen atom on tetrazole ring. The degrees of branching （DB） for H-PBTZs obtained from the 1H-NMR spectra increased with raising reaction temperature. The wider molecular weight distribution of 1.7-2.9 for H-PBTZs was obtained via GPC analysis. TGA results showed that H-PBTZs had high thermal stability compared with L-PBTZ.
A series of novel amphibious organic/inorganic hybrid proton exchange membranes with H3PO4 doped which could be used under both wet and dry conditions was prepared through a sol-gel process based on acrylated triethoxysilane（A-TES） and benzyltetrazole-modified triethoxysilane（BT-TES）.The dual-curing approach including UV-curing and thermal curing was used to obtain the crosslinked membranes.Polyethylene glycol（400） diacrylate（PEGDA） was used as an oligomer to form the polymeric matrix.The molecular structures of precursors were characterized by 1 H,13 C and 29 Si NMR spectra.The thermogravimetric analysis（TGA） results show that the membranes exhibit acceptable thermal stability for their application at above 200 oC.The differential scanning calorimeter（DSC） determination indicates that the crosslinked membranes with the mass ratios of below 1.6 of BT-TES to A-TES and the same mass of H3PO4 doped as that of A-TES possess the-T g s,and the lowest T g（-28.9 ℃） exists for the membrane with double mass of H3PO4 doped as well.The high proton conductivity in a range of 9.4―17.3 mS/cm with the corresponding water uptake of 19.1%―32.8% of the membranes was detected at 90 oC under wet conditions.Meanwhile,the proton conductivity in a dry environment for the membrane with a mass ratio of 2.4 of BT-TES to A-TES and double H3PO4 loading increases from 4.89×10-2 mS/cm at 30 ℃ to 25.7 mS/cm at 140 ℃.The excellent proton transport ability under both hydrous and anhydrous conditions demonstrates a potential application in the polymer electrolyte membrane fuel cells.
Dodecyl-benzophenone（DBP） and hexadecoxyl-benzophenone（HDBP） as type 11 photoinitiators used for radical photopolymerization systems were synthesized by Friedel-Crafts reaction, and characterized by 1H NMR and FTIR spectroscopy. The UV-Vis absorption spectra of DBP and HDBP, propitious to photopolymerization under a commercial mercury UV bulb are centered at 345 and 335 nm, respectively. HDBP has higher extinction coefficient than DBP, but lower photoinitiating efficiency. Their photoinitiating performances for EB605, a bisphenol A epoxy acrylate with 40%（mass fraction） tripropyleneglycol diacrylate （TPGDA）, resin consisting of bisphenol A epoxy acrylate and tripropyleneglycol diacrylate in the presence of triethanolamine as a coinitiator were investigated by photo-differential scanning calorimetry（photo-DSC）. DBP initiates the curing of acrylate more efficiently than HDBP, showing higher photopolymerization rate and unsaturation conversion, resulted from the poor compatibility of HDBP with the resin. The photoinitiating activity of DBP to epoxy acrylate resin is even higher than that of BP at lower loadings.
The UV-cured organic-inorganic hybrid nanocomposite （nano-Si-m-PI） was prepared through the photopolymeri- zation of acrylic resin initiated by ethoxysilane-modified multifunctional oligomeric photoinitiator （Si-m-PI）. The es- terification reaction of 2-hydroxy-4＇-（2-hydroxyethoxy）-2-methylpropiophenone （Irgacure 2959） with thioglycolic acid, and the following addition reactions with dipentaerythritol hexaacrylate and then 3-aminopropyltriethoxysilane were carried out for preparing the Si-m-PI. The Si-m-PI exhibits the similar UV absorption and molar extinction coefficient with Irgacure 2959. The photoinitiating activity study by photo-DSC analysis showed that the Si-m-PI possesses high photopolymerization rate at the peak maximum （Rpax） and final unsaturation conversion （Pf） in the cured hybrid films. From the scanning electron microscope （SEM） observation, the SiO2 nanoparticles dispersed uniformly in the formed nano-Si-m-PI, whereas the aggregation of nanoparticals occurred in nano-Irg, which was prepared through the photopolymerization of acrylic resin initiated by Irgacure 2959. Moreover, compared with the UV-cured pure polymer and nano-Irg, the nano-Si-m-PI showed remarkably enhanced thermal stability and mechanical properties.
