Yang Hu,Boyuan Shen,Botian Li,Min Xu,Guoqiang Jiang,Chengyou Kan
A novel polymerizable amphiphilic purple dye, 4-((4-(p-toluidino)anthraquinone-1-yl)oxy)-N-(2-(methacryloyloxy)ethyl)-N,N-dimethylbutan-1-aminium bromide (TAQMAB), was first designed and synthesized, and then used to prepare cationic covalently purple copolymer latexes through semi-continuous emulsion polymerization using water-soluble 2,2′-azobis(2-methylpropionamide) dihydrochloride (AIBA) as initiator. The chemical structure and properties of the dye were confirmed and characterized. Results showed that the critical micelle concentration and the hydrophilic lipophilic balance of TAQMAB were 975 mg L−1 and 32.8, respectively. The amphiphilic structure of TAQMAB gave the dye considerable water solubility and an ability to migrate from the monomer droplets into the latex particles during emulsion polymerization, which overcame the limitation of solubility, dye conversion, color depth of the latexes, and made the polymerization proceed smoothly. The total monomer conversion decreased gradually with dye amount increasing, while the dye still kept a relatively high conversion when an adequate amount of AIBA was used. Both the total monomer conversion and the dye conversion decreased with AIBA amount decreasing. The light fastness of the covalently colored film was significantly enhanced compared with the noncovalently colored one, which was ascribed to electrons flowing through the polymer chains.
Yiye Wang,Xueyan Luo,Ye Han,Baijun Liu,Yiwei Hu,Xiangchi Liu
Styrene emulsion polymerizations using sodium dodecyl sulfate as an anionic surfactant and in the presence of cationic initiators 2, 2′- Azobis (2-methylpropionamidine) dihydrochloride (AIBA) and 2,2′-azobis(N,N′-dimethyleneisobutyramidine) dihydrochloride (ADIBA) were studied. In this work, an explanation for in situ charge neutralization is proposed, and the effect of in situ charge neutralization on the particle size distribution of the ultimate polymer particles is discussed. Charges of cationic radicals from initiator decomposition shield the anionic charges of surfactant molecules adsorbed on the particle surface and induce particle coagulation during the early particle formation period. As the occurrence of in situ charge neutralization, the particle number decreases and the rate of micelle capture for the initiator radical is enhanced. Thus, the particle nucleation period is shortened, and monodisperse polymer particles with a diameter of ～200−300 nm are prepared using this simple emulsion polymerization process. In addition, hydrolysis of the initiator AIBA at different pH conditions is used to control particle size and stability. Compared to conventional emulsion polymerization theories, the emulsion polymerization in the presence of in situ charge neutralization presents unique kinetics.
Sustainable alkaline metal ion batteries using organic electrodes are promising for large-scale renewable energy storage. Traditional anode compounds are always anchored with harmful aromatic rings , which results in high toxicity. In this work, a series of aromatics-free organic electrode material based on an azo group is applied in alkaline metal ion batteries . Lithium-, sodium- and potassium-ion batteries based on acyclic compound 2, 2′-azobis(2-methylpropionitrile) (AIBN) as an anode material exhibit low toxicity. In situ Raman and ex situ Fourier-transform infrared spectroscopy results reveal that the azo group serves as the electrochemical active site for the reversible insertion and extraction of alkaline metal ions. Another compound with low toxic, 2,2′-azobis(2-methylpropionamidine) dihydrochloride (AIBA), which containing two active sites of azo and imine groups confirmed with in situ Raman and ex situ FT-IR, are applied in lithium-ion batteries. Furthermore, harmless sodium ion battery has been assembled with azodicarbonamide (CONH). Therefore, this acyclic compound offers possibilities in novel organic electrode materials for developing toxin-free and environmental-friendly alkaline metal ion batteries.
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