Preparation And Polymerization Of Phosphorus-containing Monomer

Reactive phosphate esters have a widely aspects of applications in fire-resistantpolymers. Double bonds-containing phosphite is an important organic synthetic in-termediate that can be widely used in fields like biology and agriculture chemistry.But its synthesis is seldom studied, and thus in this work, we synthesized tow phos-phate ester monomers: diallylamine methyl diethylphosphite and [(2-oxiranemeth-oxy)methyl]-diethylphosphite. And explore the preparation methods of phosphonate-containing monomer as raw material for new high-performance phosphorus-containing materials.In this work, with diethylphosphite as the main raw material, heated the diethylphosphite and diallylamine to65℃and then adding paraformaldehyde to the sys-tem until it all dissolved obtained the first phosphorus-nitrogen compounddiallylamine methyl diethylphosphite. The second monomer is synthesis by three-stepwith diethyl phosphate as raw materials. Firstly, by the action of potassium carbonatesynthsis of (hydroxymethyl) phosphonate, and then reacted with allyl chloride toget2[(2-propenyloxy)methyl]-diethylphosphite, and then using of m-chloroper-oxybenzoic acid to oxidation of the double bond to an epoxy, this method can besynthesis of high purity novel phosphorus-nitrogen compound monomer[(2-oxiranemethoxy)methyl]-diethylphosphite, and characterized with FTIR, NMRand MS, the results showed the two approaches would yield target substances withrelatively high efficiency.In addition, we studied the preparation of a new high-performance materials usediallylamine methyl diethylphosphite as raw material, phosphorus, addingallyl-terminated PEG and thiol for thoil-ene addition reaction. We mainly studied theUV curing of allyl-terminated PEG, diallylamine methylphosphonate and thiol, and the effect of concentration of phosphonates, the molecule weight of PEG and curingtime on gel content, swelling ratio, hydrolysis properties, the effect of Ca(II) on gelmorphology, tensile property and TGA were studied. Researched showed with propercuring time the resulting gel content can be as high as95%. The swelling ratio im-proved with the increasement of PEG molecular weight and the concentration ofphosphonates, and swelling property in hydrochloric system is5-7times better com-pared to that of water system. Tensile property showed that in a certain range, the in-troduction of phosphonates improved tensile strength and breaking elongation tosome degree. TGA showed obtained polymer was thermal stable and no breakdownwas observed below350℃.Furthermore, we discussed the copolymerization of polystyrene withdiallylaminemethylphosphonate. We discussed the effect of concentration of phosphonates on the copolymerization behavior utilizing solution polymerization, and FTIRand NMR to determine if phosphonates took part in the reaction. TGA showed ob-tained polymer was thermal stable and no breakdown was observed below400℃.