Synthesis And Structure-activity Research Of Spirocyclic Phosphate Flame Retardants

Polypropylene polymer materials is closely related to people’s life, which have many advantages such as excellent transparency, chemical resistance, thermostability, folding endurance and high strength and so on, so that, they are used widely in many areas such as automobile industry, electrical equipment, spinning, national defense, medical device, complex coating and packing belt. Which, combustible materials, are easily giving off a lot of heat during they’re burning and in result posing a big threat to people’s lives. In order to reduce the frequency of fire accidents, researchers from all around the world have been devoting to develop flame retardant materials and successfully gain a series of excellent fire retardant. Spirocyclic phosphate synthesized by PER and POCl3/PCl3 have better fire resistance, heat stability and hydrolysis resistance than aliphatic phosphate, which used as efficient phosphorus-nitrogen containing flame retardant are added to polylefin and polyester materials to improve the flame resistance without serious destruction on the mechanical properties of polymer composite.SPDPC was synthesized in ion liquid [Bmim]BF4 as solvent and catalyst, and characterized by FTIR and 1HNMR; whose optimal synthesis conditions were obtained by orthogonal experiment:n(PER):n(POCl3)=1:2.2, m([BMIM]BF4):m(PER)=2.5:1, T=40℃, t=7h, yield=66%. We have done three circulation experiments with good yield. In addition, the catalytic mechanism of Ion Liquid was speculated.Spirocyclic hydroxybenzene phosphate was synthesized and characterized by FTIR, 1HNMR, single crystal X-ray diffraction analysis. Molecular formula is C17H18O8P2, the relative weight is 412.25, the crystal structure belongs to orthorhombic, Pan21 space group, with a=1.1529(2)nm,b=0.61851(12)nm, c=2.6164(5)nm, α=90°,β=90°,γ=90°, V=1.8658(6)nm3.TPSP was synthesized with a new method and characterized by FTIR,1HNMR, single crystal X-ray diffraction analysis; whose optimal synthesis conditions were obtained by orthogonal experiment:n(SPDPC):n(pyrrolidine)=1:2.2, v(acetone):v(pyrrolidine)=54.6:1, t=6h, rest over night with yield over 90%. Molecular formula is C13H24N2O6P2, the relative weight is 366.28, the crystal structure belongs to monoclinic, C2/c space group, with a=1.10798(15)nm,b=0.59861 (10)nm, c=2.5807(4)nm, α=90°,β=98.765(11)°, γ=90°.Using TPSP as the flame retardant to treat PP. When TPSP addition was 15%, the LOI of PP reached 20.4%, the tensile strength/flexural strength/impact strength were 28.540Mpa(risen by 15.40),42.245Mpa(risen by 13.7%) and 2.940 kJ·m-2(fall by 16.4%) respectively. The crystal data and structure-activity of TPSP was analyzed. At the end of the article, the difference on thermodynamic property between TPSP-PP, SPDC-PP and TSPB-PP, moreover, the structure and structure-activity of SPDP and TSPB were deduced.