Synthesis Of Novel Phosphorus-containing Trialkynes From Green THPS And Properties Of Crosslinked Polytriazole Polymers

China is one of the most abundant countries in phosphate rock resources in the world, however, its utilization was not reasonable and the market share of fine phosphorus chemicals in the phosphorus-realterd industry is relatively low; at the same time the application of green technology in phosphorus chemical industry, recycling of byproducts is also bottleneck which restricts the development of the industry. In order to utilization of phosphate resources easonably and efficiently, exploring environment-friendly process to preparation of fine phosphorus chemical products with high added value, a novel trialkynes, tris(prop-2-yn-1-yloxy methyl)phosphane oxide(TPOPO) was prepared in this research and an environmentally friendly tetrakis(hydroxymethyl) phosphonium sulfate(THPS) was used as raw material. And then TPOPO underwent metal-free 1,3-dipolar cycloaddition reaction with different azide compunds to prepare high performance phosphorus-containing crosslinked polytriazoles.First the novel hydrolysis-resistant TPOPO was preapared by phase transfer catalytic reaction and its chemical structure was inetnified NMR(1H, 13 C, 31P), MS, IR. The experimental results fitted vey well to theoretical prediction. The new trialkyns is a light brown liquidPhosphorus-containing crosslinked polytriazoles(P1o?P1m?P1p) were obtained via metal-free 1,3-dipolar cycloaddition of TPOPO with bis(azidomethyl)benzene(o, m, p). Curing kinetics were investigated under non-isothermal DSC method at different heating rates. The activation energies of polymerization reaction were calculated, the reaction type was verified as autocatalytic reaction and the best conditions for the curing process were received. TGA shows that the 5% weight loss temperature of the three polymers were about 310 ? ~320 ?, and the char yield of polymers at 800 ? were about 50%, demonstrating their good thermal stability. DMA analysis showed that the storage modulus of polymers were 2.96 GPa, 3.51 GPa and 2.50 GPa respectively in 25 ?, the glass transition temperature of the polymers were 107.2?, 102.0? and 115.5? respectively. The polymers were hydrophilic materials. The dielectric contant of the polymers were about 7~10.5 at 1000 Hz. Higher than general polytriazoles.TPOPO also acted as an effective crosslinker to azide soybean oil(AzSBO) though metal-free 1,3-dipolar cycloaddition. Composition and properties of three polymers were researched, their functional group ratio of alkyne(C?C) to azide(N3) were 1:1, 1:0.9 and 1:0.8. The gel content of the polymers higher than 95%, TGA shows that the 5% weight loss temperature of the three polymers were 278.4?, 276.1? and 289.1? respectively, and the char yield of polymers at 850? were 16.4%, 16.4% and 18.6%, limiting oxygen index of the polymers which were calculated by TGA were about 24.1%~24.9%, the flame retardant properties of the polymers can be improved when TPOPO added. DMA analysis shows that the system crosslink density were 1.02 GPa, 0.97 GPa and 0.70 GPa, the glass transition temperature were 57.0?, 53.0?, 45.9? respectively. The polymers were hydrophilic materials, The hydroxyl content of the systems increased when the amount of AzSBO increased, enhanced the hydrophilicity of the polymers. The dielectric constant of the polymers were about 8.9~10.0 at 1000 Hz.